1

AgCl - SILVER CHLORIDE................................ ..................................................6 AgCl conversion using Karo syrup and NaOH.......................................................... 6 Dangers of torch melting silver chloride..................................................................... 7 Methods of converting silver chloride to silver .......................................................... 8 Dont dry silver chloride .............................................................................................. 8 Silver chloride uses and manufacture ......................................................................... 9 Conversion methods and avoiding the production of silver chloride....................... 9 Possible tips when converting silver chloride........................................................... 10 AQUA REGIA ..................................................................................................... 11 Using nitric first on low karat gold ........................................................................... 11 My method of using nitric and hydrochloric when dissolving gold ....................... 11 Refining karat gold ..................................................................................................... 13 Removing silver plus other ways of dropping gold.................................................. 14 Inquarting tips............................................................................................................. 17 Dissolving silver........................................................................................................... 18 Gold refining tips ........................................................................................................ 19 Getting high gold purity ............................................................................................. 20 Getting high gold purity - 2........................................................................................ 21 Gold refining outline................................................................................................... 23 What is aqua regia ...................................................................................................... 24 More refining tips ....................................................................................................... 25 Inquarting Obtaining nitric Miscellaneous tips ................................................. 28 Preparing gold for dissolving..................................................................................... 30 Dissolving base metals with aqua regia..................................................................... 31 Nitric acid .................................................................................................................... 32 Using acids in aqua regia............................................................................................ 33 Using nitric acid .......................................................................................................... 33 ASSAYING .........................................................................................................33 Scale errors .................................................................................................................. 33 Should you pay for a fire assay?................................................................................ 34 Lead reduction from litharge Other assay tips ..................................................... 35 Collecting PGMs in nickel sulfide ............................................................................. 36 BUYING AND SELLING................................ ..................................................... 37 Buying tips ................................................................................................................... 37 Selling gold................................................................................................................... 38 Dealing with gold filled............................................................................................... 38 Using professional reps Big number deals Buying in mining areas ................. 40 Stamping on sterling and karat golds ....................................................................... 41 Buying tips ................................................................................................................... 42 Coins............................................................................................................................. 42 Selling gold bearing electronics scrap ....................................................................... 42 Precious metals prophets............................................................................................ 44 CHEMICALS................................................................ ....................................... 44 Buying nitric Safely handling nitric ....................................................................... 44

2 Testing for nickel......................................................................................................... 46 Using dimethyl gloxime (DMG)................................................................................. 46 More on DMG ............................................................................................................. 46 Still more on DMG...................................................................................................... 47 Hydrazine sulfate ........................................................................................................ 47 Dont use alcohol in aqua regia.................................................................................. 47 Hydrazine chemicals................................................................................................... 47 Nitric acid purity......................................................................................................... 48 CIRCUIT BOARDS................................ ............................................................. 48 Circuit boards from a professional refiners viewpoint .......................................... 48 COLLOIDAL SILVER ................................................................ ......................... 50 General information Making CS ............................................................................ 50 CONTACT POINTS ................................................................ ............................ 52 Processing large silver contact points ....................................................................... 52 More on contact points ............................................................................................... 54 Even more on contact points...................................................................................... 54 CYANIDE................................ ................................................................ ............55 Refining Technistrip AU ............................................................................................ 55 Cyanide dangers.......................................................................................................... 55 More on commercial cyanide strippers..................................................................... 56 Refining cyanide solutions.......................................................................................... 56 Using zinc dust............................................................................................................. 57 A stupid question about using acids to drop PMs from cyanide solutions ............ 57 Testing for gold in cyanide solutions......................................................................... 58 DENTAL GOLD ................................................................ .................................. 58 Dental gold info ........................................................................................................... 58 Refining dental golds .................................................................................................. 59 A person had this solution and solids from trying to refine dental gold................ 65 DISSOLVING METALS................................................................ ...................... 67 Avoid foamovers.......................................................................................................... 67 How much nitric does it take to dissolve copper or silver?..................................... 68 Using nitric on gold plated base metals..................................................................... 71 A patent for eliminating the brown fumes................................................................ 71 EQUIPMENT ................................ ................................................................ ......72 Pyrex containers.......................................................................................................... 72 Siphoning ..................................................................................................................... 72 More on Pyrex ............................................................................................................. 73 A Mortar and Pestle for Ceramic Parts - With No Guarantee............................... 73 EXPLODING COMPOUNDS ................................................................ .............. 75 Beware of making PM explosives!............................................................................. 75 FILM ................................ ................................ ................................................... 76 Film info....................................................................................................................... 76 Film on reels Processing film using nitric (not really recommended)................. 77 Info on film-part 2....................................................................................................... 78 Info on film-part 3....................................................................................................... 80 How film is processed ................................................................................................. 81

3 The problem with chloride methods of processing film .......................................... 82 More info on film processing ..................................................................................... 83 FILTERING................................ ................................................................ .........84 A simple filtering setup............................................................................................... 84 Buckets vs. glass Miscellaneous info....................................................................... 86 FUME HOODS................................................................ .................................... 87 Fume hood info............................................................................................................ 87 GOLD LEAF ................................................................ ....................................... 89 Thickness of gold leaf.................................................................................................. 89 Beware of EBay much fake gold leaf being sold as the real stuff ........................ 89 GOLD PLATING................................................................ ................................ .89 Gold plating purity ..................................................................................................... 89 GOLD PURITY ................................ ................................................................ ...90 Determining gold purity ............................................................................................. 90 GOLD TESTING................................................................ ................................ .91 Gold and silver testing solution formulas ................................................................. 91 Using a touchstone ...................................................................................................... 92 Acids used in testing solutions ................................................................................... 92 Eraser thickness test ................................................................................................... 92 My way of testing for PMs in acid solutions with stannous chloride ..................... 93 ICs ................................ ................................................................ ...................... 93 Aluminum bonding wire............................................................................................. 93 Traces ........................................................................................................................... 93 Gold values on an IC................................................................................................... 94 IODINE ................................................................ ............................................... 95 Homick patent - 3957505............................................................................................ 95 MANUFACTURING SCRAP................................ ............................................... 95 The best gold bearing electronics scrap .................................................................... 96 MELTING................................ ................................................................ ............97 Gas furnace info .......................................................................................................... 97 Kerr Electromelt ......................................................................................................... 99 Advantages of a gas furnace....................................................................................... 99 Gas furnace info part 2.......................................................................................... 100 Gas furnace info part 3.......................................................................................... 100 Propane fired furnaces ............................................................................................. 101 Furnace temperature colors..................................................................................... 101 MEMBRANES ................................................................ .................................. 101 Membrane cells for nitric......................................................................................... 101 Types of membranes ................................................................................................. 103 MISCELLANEOUS................................ ........................................................... 103 Selectively stripping gold plating............................................................................. 103 More on stripping ..................................................................................................... 104 Electrowinning and electrorefining......................................................................... 105 List of scrap items that contain precious metals .................................................... 106 SO2 water .................................................................................................................. 109 Nickel silver ............................................................................................................... 110

4 The Electromotive Series.......................................................................................... 110 Refining suggestions.................................................................................................. 111 An offer ...................................................................................................................... 112 Fluxing with soda ash? ............................................................................................. 112 Tantalum and Ta/silver electrolytic capacitors...................................................... 113 Gold plating ............................................................................................................... 114 Migration of gold plating ......................................................................................... 115 Recycling IC packages a business......................................................................... 115 Electrolytic copper .................................................................................................... 117 Silver plating on boards............................................................................................ 117 Oscilloscopes.............................................................................................................. 118 Anaconda copper ...................................................................................................... 118 Freezing circuit boards............................................................................................. 118 Silverplate thickness on flatware and hollowware................................................. 119 Reed switches............................................................................................................. 119 Gold prophets ............................................................................................................ 119 Relay contact points.................................................................................................. 120 Connectors on backplanes........................................................................................ 120 Gold precipitants....................................................................................................... 120 Transistors and ICs................................................................................................... 120 Miscellaneous tips ..................................................................................................... 121 Copper from motors ................................................................................................. 122 Gold and silver bearing jet engine scrap ................................................................ 123 MOBILE REFINERY................................ ......................................................... 124 Refiners Paradise..................................................................................................... 124 MOLDS................................................................ ............................................. 125 Types of molds........................................................................................................... 125 PLATING THICKNESS ................................................................ .................... 125 Gold plating thickness and how to estimate values ............................................... 125 PLATINUM GROUP METALS................................................................ ..........133 Rhodium plating solutions ....................................................................................... 133 Palladium contact points on telephone scrap ......................................................... 134 Testing platinum thermocouple wire ...................................................................... 135 REFINERS................................................................ ........................................ 136 Pin samples ................................................................................................................ 136 SAFETY................................ ................................................................ ............139 Gloves ......................................................................................................................... 139 A few comments about diluting acids with water .................................................. 140 Cyanide safety ........................................................................................................... 140 Sulfuric drain cleaner............................................................................................... 140 Osmium...................................................................................................................... 141 Silicon wafers............................................................................................................. 141 Hydrofluoric acid ...................................................................................................... 142 Chemical safety ......................................................................................................... 142 More chemical safety ................................................................................................ 143 Graphite ..................................................................................................................... 144

5 SAMPLING................................ ................................................................ .......144 Sampling bars and molten metal ............................................................................. 144 SCAMS................................................................ ............................................. 145 A common con game................................................................................................. 145 SCRUBBERS ................................................................ ...................................146 Fume scrubber info................................................................................................... 147 SHOR ................................ ................................................................ ...............148 Shor patents, chemicals, and equipment................................................................ 148 Shor patents part 2................................................................................................. 148 Shor patents part 3................................................................................................. 149 Shor and Wohlwill cells............................................................................................ 149 Shor cell...................................................................................................................... 150 SILVER CELL................................................................ ...................................150 Silver cells part 1 .................................................................................................... 150 Silver cells part 2 .................................................................................................... 151 Silver cells part 3 .................................................................................................... 154 Silver cells part 4 .................................................................................................... 156 Silver cells part 5 .................................................................................................... 157 SILVER REFINING................................ ........................................................... 157 AgCl and cement silver............................................................................................. 157 Cementing.................................................................................................................. 158 Tin............................................................................................................................... 159 Silver plated items..................................................................................................... 160 Dental amalgam ........................................................................................................ 161 More on silver plate .................................................................................................. 162 Dissolving silver in sulfuric acid .............................................................................. 162 Silver coins................................................................................................................. 162 Steel wool canisters for photo fixer ......................................................................... 163 SULFURIC STRIPPER................................................................ .....................165 Sulfuric stripper part 1.......................................................................................... 165 Sulfuric stripper part 2.......................................................................................... 167 Sulfuric stripper Get a free plating book............................................................. 168 Sulfuric stripper part 3.......................................................................................... 169 Sulfuric stripper part 4.......................................................................................... 170 Silver in the sulfuric stripper ................................................................................... 170 Sulfuric stripper part 5.......................................................................................... 171 Sulfuric stripper part 6.......................................................................................... 172 Using sulfuric drain cleaner..................................................................................... 173 Sulfuric stripper part 7.......................................................................................... 173 Sulfuric stripper part 8.......................................................................................... 174 Sulfuric stripper part 9.......................................................................................... 174 Sulfuric stripper part 10........................................................................................ 175 Sulfuric stripper part 11........................................................................................ 175 Sulfuric stripper part 12........................................................................................ 176 Sulfuric stripper part 13........................................................................................ 176 Sulfuric stripper part 14........................................................................................ 178

6 Sulfuric stripper part 15........................................................................................ 180 Sulfuric stripper part 16........................................................................................ 180 Sulfuric stripper part 17........................................................................................ 180 Sulfuric stripper part 18........................................................................................ 181 Sulfuric stripper part 19........................................................................................ 181 TELEPHONE SCRAP ................................ ...................................................... 182 Palladium points........................................................................................................ 182 TORCH MELTING................................ ............................................................ 183 Cleaning gold in the melt.......................................................................................... 183 Removing slag from the bar..................................................................................... 184 Melting dishes ............................................................................................................ 184 WASTE DISPOSAL................................................................ .......................... 185 Waste disposal part 1............................................................................................. 185 Waste disposal part 2............................................................................................. 186 Waste disposal part 3............................................................................................. 186 Waste disposal - part 4 ............................................................................................. 186 Waste disposal - part 5 ............................................................................................. 187 Waste disposal part 6............................................................................................. 188

AgCl - SILVER CHLORIDE

AgCl conversion using Karo syrup and NaOH
I watched your AgCl to Ag conversion video, with interest, and would like to make a few comments. Please don't take offence, but I feel that your technique will not usually convert all of the chloride to metal. It might work sometimes but other times it won't. I think that most of the problem lies in the understanding of what is really happening. Have you tried melting any of this metal? Have you noticed a tenacious, milky, iridescent layer on top of the cooled metal? If so, this is unconverted silver chloride. Probably the best way to prove your process would be to dissolve a weighed amount of silver in nitric, salt it out, convert it, melt it, remove any coating, reweigh it, and compare the weights. You will probably lose a little silver in a torch melt but it shouldn't exceed 1 or 2%. About 30 years, I spent some time in a lab determining exactly how much Karo syrup and sodium hydroxide (caustic soda, lye) it would take to convert a known quantity of silver chloride to silver. Since then, I have processed at least 10,000 ozs of silver using this method. This is what I found: 1) If you don't crush all of the dried silver chloride to a very fine powder, you won't get complete conversion. I noticed a few chunks in the video. When you try to convert these chunks, a layer of silver oxide or silver metal forms on the surface and blocks the chemicals from penetrating to the center of the chunk. I

7 would suggest grinding in a mortar and pestle. Actually, the best way is to never dry the silver chloride. Keep it submerged in water, cover it when in storage to keep the light out, and stir it good before adding and while adding the chemicals. You're going to need water, anyway, in the process. 2) The purpose of the sodium hydroxide is to convert the silver chloride to silver oxide. The silver oxide is then converted to silver metal by the Karo syrup (corn sugar). The purpose of the Karo syrup is not to act as a flocculating agent. It is actually what produces the silver metal. Theoretically, you don't really need the syrup. You could easily flux melt the silver oxide directly to convert it to metal. However, it is a bear to filter silver oxide and it is, therefore, best to use the syrup. 3) When I did the lab experiments, I used 31.1 grams of silver chloride, which contains 23.4 grams of silver metal. This took 15 grams of sodium hydroxide, 10 mL (cc's) of light Karo syrup, and 100mL of water for complete conversion. In practice, I use about 10% extra chemicals. 4) If the process is being used to semi-purify items of known silver content, such as sterling silver, keep track of how much silver you have so you'll know the amount of needed chemicals. If the silver amount is unknown, such as in aqua regia residues, you'll have to make a guess. Just make sure you add enough. A little extra won't hurt. 5) To test for complete conversion: Put a small sample, about a half gram, of the converted solids into a beaker and cover with distilled water. Stir and then allow the solids to settle. Carefully pour out the rinse water without disturbing the solids. Repeat several times until the rinse water runs perfectly clear. Add a small amount of good nitric acid and an equal amount of distilled water. This will dissolve the silver metal. When the silver has dissolved, add distilled water to about an inch depth. If a white cloud (silver chloride) forms, the conversion is not complete and, either you need more chemicals or, the chunks weren't completely broken up.

Dangers of torch melting silver chloride

The thing that really worried me was when you were converting the silver chloride to metal with a torch. I would never use a torch for silver because it's very easy to get things too hot. Silver chloride melts at a low 850 deg F (the flow you saw) and starts evaporating at less than 1560 deg F., along with the NaCl that is produced in the conversion. This was the white smoke you saw. The silver losses you experienced probably went into the air. I hope you were wearing your SCBA gear. The extremely rough button produced, in the photo, is not only an indication of high purity but, also, of way too much heat. I had a friend that died

8 from breathing these fumes. He always had his head over the furnace because he liked watching the AgCl convert. Some years back, a man named Kunda came up with a much lower temp. furnace method for conversion. This method is used widely today.

Methods of converting silver chloride to silver

I actually base my method on the type material I'm running. I use the copper method when I have little or no free nitric acid present, as in when I dissolve contact points in nitric. One time, I setup to dissolve the silver braze off of about 50,000# of jet engine stators, the big fan blade like parts that you see in the engine in photos. The silver only ran 1% to 2% of the total weight. We had about 500 gallons of 50/50 nitric to do this and we wanted to use the same solution over and over. We harvested the silver every few days. When we harvested, the nitric still had about 90% of its original strength. If I had used copper 2 things would happen. First, I couldn't reuse the solution. Second, there was so much free acid left that we would eaten about 500# of copper before the silver even started dropping. So, I used HCl to drop the silver. Cement silver is hard to rinse. About the only source of contamination is the copper solution. If you could get it all out, you would have silver that is close to pure. Sometimes, slivers of copper fall off into the silver but, this doesn't usually add up to much. If you were to dry and melt with copper solution still in the silver, the result would not be very pure. Each rinse gets rid of more copper. Hot tap water is best. Zinc, iron, aluminum - all of these things work on silver chloride. Harold had a good write up on using aluminum. Converting silver chloride to metal is not as easy as you might think. Look for the posts that Lazersteve and I made on the subject.

Dont dry silver chloride

Remember the IMPI article on silver chloride we discussed the other day? I attended the seminar and found a note that I had made on the paper, while listening to the lecture. The author said that, when silver chloride dries, it combines together to form crystals and that is why it becomes so impossible to work with. Even if ground fine, the fine particles are still crystals and the AgCl would only convert on their surface.

Silver chloride uses and manufacture

Silver Chloride Uses: -As a laboratory reagent. -Waterproof infrared lenses. It can be compressed into durable translucent shapes. -Preparation of Ultra Pure Silver Metal. (Smelted with Soda Ash: 1:1 Molar ratio, 1112F, 1 hour). MY NOTE: The parameters given here are quite interesting! -A precursor to the preparation of Silver (II) Oxide, Ag2O. (It is heated in dilute NaOH solution). -In Photography, as a sensitizer, but to a much lesser extent than Silver Bromide. -Electroplating - both electroless and as an anode in an electric cell. -Inquartation in electric arc furnaces - smelting Gold and Platinum Group Metals. -As a thin coating on the surface of Medical Electrodes for EKG machines. (Placed against the skin). -Antibacterial agent for concrete (1 Lb Silver Chloride per cubic yard of Concrete (4,050 lbs) . -Used as an anti microbial agent in some infection resistant surgical fabric materials. -Used to help prevent bacteria from growing on Latex (mixed into the Latex before it is formed). -Used to help prevent bacteria from growing on Glass (when melted into the glass). -Decorative etching of high quality steel. (Apply damp Silver Chloride to steel, let stand for several hours). Making acceptable pure AgCl is much more difficult than it appears. I was slightly involved in this several years ago. It has to be made in the dark or under a rubyred light, to prevent reduction to silver (purple). It is made by starting with pure silver, dissolving in nitric, dropping with hydrochloric, and boiling. It is then dissolved with ammonia and re-dropped with hydrochloric. This may have to be repeated several times. About the only time I've seen it in scrap (besides on film), it was used as one of the electrodes in large silver military batteries. It had been melted and cast into a sheet form. I also seem to remember seeing it used, in cast form, on some sort of electronic or aircraft part.

Conversion methods and avoiding the production of silver chloride

I would use a chemical method, such as Karo/lye or aluminum, as Harold suggested. You can also use powered zinc or mix it with slugs of iron and dilute sulfuric. Before melting, I would test for complete conversion using the simple

10 method covered here in my post - item #5. When the conversion is complete you can melt it quickly with a cool torch or in a furnace. Silver metal will also evaporate, if you get it too hot for too long. Several times I have forgotten and left a pure silver bead in a cupel in about a 1700 deg F. furnace. When I found it, after 5 or 6 hours, it had evaporated to almost nothing. A friend of mine blends the silver chloride with enough soda ash for conversion, puts it in a crucible and covers it with borax. He then puts it in a hot pot furnace and allows it to get up to temperature. When it's hot, he turns the furnace off allows it to cool overnight. He claims good conversion. In the last 150 years, or so, refiners have practiced what is called "chloride aversion or avoidance". In other words, they don't produce silver chloride unless they have to. I do the same. About the only AgCl I HAVE to produce are the residues from aqua regia. I really don't have to do that but, I do. It takes less work in the long run. I could inquart and get the silver out with nitric. It's really easy and tempting to make AgCl - you just add some HCl or salt water. Getting the silver out of the chloride is another story. Even with silver nitrate solutions, I don't form AgCl. Instead, I cement out the silver on copper buss bar.

Possible tips when converting silver chloride

I've been thinking of how the Karo syrup method could be used to get 100% conversion. When I did this on a large scale, in an open top 55 gallon plastic drum, I had the best luck when using a Lightnin' mixer to stir the mix. This type mixer tends to chop up the AgCl, which allows the chemicals to penetrate and completely convert it to Ag metal. On a smaller scale, I think a dedicated blender (garage sale) would work great. It would really chop up the silver chloride. It would probably work even if the AgCl was dried out. Of course, the AgCl would have to be very well rinsed before doing this, to remove any nitric and dissolved metals. The seal in the blender might be attacked by the sodium hydroxide but, if no excess is used, this may not happen. With the blender action, the conversion wouldn't take long. After removing everything from the blender, one might rinse the blender with a little vinegar to remove any traces of sodium hydroxide. Then, rinse it well with hot water. For 1 tr.oz. of silver metal, about 41.5 grams of silver chloride, it takes about 20 grams of sodium hydroxide, 13.3 mL of light Karo syrup, and 133 mL of water. Just an idea. I think it would work great. The only problem might be the seal.

11 On a medium large scale - bucket size - one of those stainless paint mixers chucked in a drill might work well. They also have a good chopping action.

AQUA REGIA
Using nitric first on low karat gold
Here's a trick. If you only have 10KT gold, or below (a lot of Mexican gold is 6KT or 8KT, or worse), you can dissolve everything but the gold with hot 60/40 to 70/30 (nitric/distilled water) nitric acid, without inquarting. It may take 3 or 4 hours and the solution should be just below boiling. It won't work on anything higher than 10KT. This is especially interesting on 10KT class rings. When everything is gone but the gold, the class ring will maintain it's shape and you'll still be able to read the writing on it. The difference is that it will be totally composed of brown gold powder. When you touch it with a stir rod, it will collapse. You can tell when all is finished by mashing everything with a stir rod. If all the pieces collapse, they are finished. If all is not finished, add a little straight nitric and keep driving it hard. If it still won't finish, you have some things that are higher than 10KT. I can't ever remember this method failing. After leaching the 10KT and removing the nitric solution, with a few rinses, you dissolve the remaining gold powder with a very small amount of AR. You could, probably, use HCl/Cl2 or HCl/H2O2 to dissolve the gold powder instead of using AR.

My method of using nitric and hydrochloric when dissolving gold

I guess I had misunderstood you earlier. I thought you were alternating acids to prevent excess nitric, as I was. But, both ways work.

12 I probably haven't evaporated an AR solution in 28 years. I have never used urea in aqua regia solutions. This is because I never have any excess nitric, ever. The first few drops of my precipitating agent dropped gold. This is the proof of no excess nitric. If you have excess nitric, the precipitant reacts with the nitric before it drops gold. I started out following Hoke to the letter and, in 1979; I worked for a guy that was the greatest refiner I have ever known. He showed me the trick. I've covered this several times but, no one seemed to pay attention. I've never heard of anyone else doing this. The last time I owned a refinery, I shipped gold weekly as 99.99% and got top dollar. This was spectroed several times and always was up to par. I never had a lot rejected. (1) As you did, I calculated, approximately, how much of each I needed and measured them out. For uninquarted Karat gold, this was about 125-150 mL of HCl and 25 mL of HNO3. My mentor didn't measure anything out. He just poured the acids back and forth from gallon jugs and never overadded (2) Put the gold in a beaker or Pyrex coffee pot and put this in a 5 quart white Corning Ware dish, in case of breaks and dribbles. Cover the gold with the HCl and heat it until steaming. I usually also add about 5% - 10% water. To make things easier, try to make sure you've added a little more HCl than necessary. This extra won't cause any problems. (3) Add a small amount of nitric and let it work until the reaction slows down. Give it a slow stir and then another addition. Repeat this until there is no reaction with a fresh addition. Note: At the first addition, the reaction is vigorous and then, it slows down quickly - this addition is consumed quickly. The next addition will be less active at first and will take longer to complete - and, so on. When you first learn this, you might overshoot the nitric. After doing it a few times, you'll hit it right on the button. You have to get used to how it feels. At first, if you add too much nitric, you can always use urea but, it'll never be as pure. (4) Add a bit of HCl, let it heat up, and watch for a reaction. If there is no reaction, you are finished. If you started with an excess, this will be the case. If there is a reaction, add some more HCl and let it heat up. (5) If the HCl reacted, add a bit more HNO3 and watch. If there's a reaction, wait until it stops and add a bit more. Repeat until no reaction and try the HCl again. (6) The idea is to go back and forth until you've hit the exact amount of nitric and, at least enough HCl. If you added a slight excess of HCl to start with, however, you won't have to go back and forth much. I rarely used all of the nitric that I had initially measured out. Towards the end, go very easy on the nitric additions and give them a long time to completely be consumed. Towards the end, the pieces will be well caked with silver chloride and the acid penetrates slowly. Towards the end, keep it real hot -

13 just below boiling. Towards the end, stir often. Also, during the process, stir before each addition. Always keep the beaker or Pyrex coffee pot covered with a watch glass or a kitchen saucer when you're not stirring or adding. Never boil the solution. If you do, you can't tell the difference between fizzing and boiling. When it's finished, transfer to a clean bucket. Add 3 times its volume of tap water. This dilution will precipitate about 99% of the silver as silver chloride. To about 4 gallons of dilute aqua regia, add about 60 mL of battery acid and stir. This precipitates the lead. Allow to settle. I'll go over the precipitation later. NOTES: (1) For Karat Gold, this direct dissolving could take as much as 8 hours. You will probably dissolve only about 98% of the gold, on the average. The remaing undissolved gold should be inquarted. (2) To speed things up and dissolve 100% of the gold, you can first inquart the karat gold (reduce to 25% gold) with copper or silver, dissolve in nitric, pour off the nitric and rinse a few times, and treat the remaining gold powder in a much smaller amount of aqua regia. This process will take about 4 hours, after the gold has been shotted. (3) If you only have 10Kt gold, or less, you can leach all of the silver, copper, zinc, etc., with nitric, without inquarting. Keep it quite hot. (4) This method will do about 5 tr.oz. of karat gold in a coffee pot and about 10 oz. in a 4 liter beaker. I keep the amount of gold low to keep the solution levels low. Once the solution level is more than about 3" deep, the reaction is slower. I usually had 8 or 10 setups working at the same time.

Refining karat gold

I'm glad that this all important thread finally occurred. This stuff is hard to explain but, is very straightforward in practice. Hopefully, the readers can understand what we're saying. If not, they should ask specific questions until they understand the mechanisms used in both our processes. Also, those others who are producing good gold should participate and detail their processes. Every good refiner uses the same basics but, all vary in the details. The more variations we know, the better we can settle on our own excellent process. We both understood early that, besides getting all of the gold, high purity had to be the main goal. This is what separates the men from the boys, in this business. It's just as easy to produce good gold as it is to produce bad gold. The basic

14 steps are the same. It's all in the details - the tricks. You're right. It's always possible to add too much nitric. At the start, I did it more than a few times. More nitric makes things go faster and there's a tendency to over add. However, when I discovered that I had to pay the piper, down the line, I developed more patience. Urea produced less pure gold and I avoided boiling down like the plague. With a little experience, I learned to avoid over adding and it got to the point that it didn't happen. There's one thing I don't understand. How did you get rid of the silver? You obviously did, but I can't see how. When I first started, I ran experiments to find out how much silver would dissolve in aqua regia. I found that silver was quite soluble in concentrated aqua regia but most of it dropped out at a dilution of 3 to 1. After that, the curve flattened out and further dilution didn't drop much more. I found that, if I didn't dilute at the start, the silver would come out later, when the aqua regia was diluted by the rinses. This would combine with the dropped gold and contaminate it. Sometimes, when my one furnace was tied up, I ran the karat gold scrap as is. Usually, though, I inquarted. Inquarting gives several advantages. It is faster in the long run, although there are additional steps. The aqua regia dissolving is very fast, the solution gives much less volume to work with, and the solution is mainly gold, since most of the other metals are eliminated by the nitric. This higher purity aqua regia makes it easier to end up with pure bars. And, maybe the most important, you don't have to deal with that nasty silver chloride that sets up like concrete on the stuff you're trying to dissolve. I don't remember the nitric leaching of 10KT gold taking that long. I would guess 3 or 4 hours. I usually did it on large batches of class rings. I had a couple of class ring manufacturers that gave me their scrap. In recent years, I rarely had to redissolve and go through the aqua regia process twice. The times I remember involved the first drop being contaminated with platinum group metals. I eventually learned to get rid of the Pt. Gp. early on.

Removing silver plus other ways of dropping gold

One of the first things I learned was that silver chloride is soluble is strong aqua regia. Not a lot but, certainly enough to severely affect the final purity of the gold. It reacts similarly to lead but, to a lesser extent. Before dilution, the filtered solution is perfectly clear. Upon dilution, the dissolved silver chloride precipitates. Therefore, the standard way of precipitating it is to dilute the aqua regia. Some say 2 volumes. Some say 4. My experiments said 3. I was quite surprised that you didn't agree with it. Nearly every refining book I've ever read states this fact.

15 And, it is a fact. I don't have a copy of Hoke any more but, I seem to remember that she mentioned it. You might check your copy. My experiments were simple. I cooked some AgCl in standard 3/1 aqua regia, filtered it, most probably through glass fiber filter media, and then analyzed the silver dissolved in the aqua regia by atomic absorption. Then a I diluted it a bit, filtered it, and again ran it on the AA. I repeated this several times and then plotted it on a graph. Three dilutions removed most of it. I only have 4 refining books left. Two didn't mention it. The first edition of Ammen (pp117) said to dilute it 3 or 4 times but, didn't say why. I did find more than a mention of it in the last book. This was in a an IPMI (International Precious Metals Institute) book of the papers that were given at the 1980 IPMI Symposium on Recovery, Reclamation, and Refining of Precious Metals, held in San Diego. I was an IPMI member at the time and attended. The IPMI is probably the most prestigious PM organization in the world. In the papers, is a long article entitled "Silver Chloride". Here's a quote from that paper, page 3. The author documents these statements but, I won't supply the references unless you want them. "It (silver chloride) is somewhat soluble in concentrated HCl and heavy metal chlorides. Solubility in these increases with temperature and concentration. Solubility in chlorides appears to be by the formation of complex chloroargentate ions.... Solubility in HCl and heavy metal chlorides is of interest because of how it relates to aqua regia systems. In aqua regia dissolution the liquid consists of a very concentrated mixture of heavy metal chlorides, usually at elevated temperatures. These are ideal conditions for the dissolution of AgCl. Even small amounts of silver chloride, if left in solution, can have a marked effect on the purity of the gold produced. This is especially true for the third and forth decimal places of fineness. Fortunately most of the AgCl can be removed with water. One to two volumes are usually recommended for this dilution during the clarification stage." So, what I said is true. I've thought about your process to try and determine why you had no silver problems. (1) If you always inquarted, your aqua regia would have much less heavy metal chlorides so, less AgCl would be retained. The experiments I ran, however, showed some retention with no heavy metal chlorides but only aqua regia alone. (2) After boiling down, I assume you added water (diluted) and filtered. This is probably where you got rid of it. Quote: Before you prime newbies with the idea that they can run karat gold that way, with success, please try to remember that silver is not soluble in

16 AR. It converts to a hard, impenetrable crust that stops AR dead in its tracks. I've done my share of experimenting in that regard, and know all too well that you can literally boil 14K gold in AR for days and not have it dissolve.

Although neither of us likes the direct aqua regia process, without inquaration, it is the standard aqua regia process that most refiners use. You and I are in the minority. As I understand, one reason you used it was because you wanted to get every milligram of gold dissolved so you could be honest in accounting with your customers. Most refiners could give a damn about 100% honest accounting. They know that, sooner or later, it'll all come out in the wash. Of course, by that point, it would belong to the refiner. In my case, when using direct aqua regia, it was on already purchased material. I rarely worked on a recovery basis. I preferred inquarting because, as one of your reasons, I hated fighting with the silver chloride. If you reread my post, you will see that I never promoted direct aqua regia. I just showed how it was done. Quote: You're not going to try to convince me your achieved 9999 that way, are you? Nothing I've ever read indicates that's a reasonable expectation, and my personal experience, and I'm damned thorough and careful, lead me to believe that it's nearly impossible.

Quote: What do you mean by 'early on' ? Please explain how you would remove the PGM's.

Early on in life. In 1969, I was head chemist for a large refinery in L.A. Our Wohlwill Cell (gold purification cell) solution was often too contaminated with base metals and required frequent solution changes, in order to maintain high purity gold. I started experimenting with ways to extend the life of the solution. We had a well stocked lab and had quite an assortment of chelating agents. Most were variations of EDTA. Chelate comes from the Greek word Chelos, which means "claw". It grips metals in several places, like a claw, and holds them in solution. I figured that, if I added EDTA to the solution, it would chelate the base metals and prevent them from plating out with the gold. When I added the specific type of EDTA to a sample of cell solution, all of the gold dropped out. Surprise, surprise. For about an hour, I was very disappointed. I really thought it would work. Then, it dawned on me that I might have a new

17 precipitating agent for gold. I started doing lots of experiments and maximized the process. We melted several batches of gold dropped from heavily contaminated aqua regia, under pristine conditions, and sent off samples to be analyzed for all impurities. To my amazement, none were under 99.99% pure. Some approached 99.999%, believe it or not. Some of these aqua regia solutions were intentionally contaminated with the entire platinum group. Still, the gold was above 99.99% pure, with only one drop. I'm not saying that the company always shipped 99.99% gold, because they could introduce impurities during the melt. I am saying that the powder was most always 99.99%. None of the company experts could figure out why it worked. Later, I concluded that formaldehyde, a common gold precipitant, was released when the EDTA product neutralized the aqua regia. You could smell it. The base metals were tightly held into the solution and didn't come out with the gold. I never could figure out what happened with the silver and platinum group but, somehow, they were held into the solution. The company pretty much shut down the Wohlwill operation and went with my invention for everything. We called it EZ-Drop. I was a hero based on a failed experiment. The company was running about 10,000 ozs/month and ran the process for several years, until they were bought out by a big conglomerate. When I left, I continued using it until about 1980, although I always kept some around for gold containing platinum group. From the late '80's though the mid '90's, when I owned my last refinery, I had no need for EZ-drop. I specialized in recovering 80/20, gold/nickel braze from military and commercial jet engine parts. Another reason I stopped using this product was that chelating agent wastes, with their tightly bound heavy metals, are very difficult to waste treat. The EPA hates them. Also, the EDTA product was expensive. In 1969, it cost about $650 per drum, of which, under optimum conditions, you could drop about 3000 ozs of gold.

Inquarting tips
The gold powder forms a crust on the pieces you're dissolving just as silver chloride forms a crust in the aqua regia. This greatly slows down penetration of the nitric. Heat would help enormously. With strong heat, you could most probably get 100% dissolution quickly. I have used nitric, many times, on 10KT (40% gold) and have been left with nothing but gold powder. Another possibility. I assume you torch melted when you inquarted. If so, you may have gotten incomplete mixing of the alloy. This could have created some pieces that were richer in gold when you poured the shot. It's easier to mix the melt in a crucible furnace. You simply stir with a carbon rod. You can buy these rods or scrounge them. They are used in arc lights. You could probably use

18 these to stir the torch melt. If you preheat them to red, before stirring, no gold will stick to them. You can also use the rods to remove slag, although it won't stick to a red hot rod. To remove slag and not the gold, just heat the rod slightly. This is touchy. If it's too cold, it will pick up gold and slag. If it's too hot, it won't pick up anything. If it does pick up gold, just melt it back into the dish. I've never tried it on a torch melt but it should work. Probably, just holding the rod above the melt for a few seconds would heat it enough. Just wipe the rod quickly around the edge of the melt and remove it. In the tutorial, you may have had less than 25% gold. I wouldn't recommend going much lower than 25%, though. When you do so, the gold can come out as a very fine slime. It seems to never settle and it is very hard to filter.

Dissolving silver
Quote: Reagent grade nitric is slow to attack silver, but does so with a vengeance with the slightest addition of water.

Very true. I think you hit the nail on the head. I've always read that a 50/50 blend of concentrated nitric and water works the best. In practice, I've found this is true and always end up cutting my nitric 50/50. Of course, I always use a lot of heat. When cold it will probably be different. Try about 10% - 20% distilled water. You might need a little more power, than normal, to cut through the gold barrier. Another problem is that, in most cases, strong acids hold less metal, per volume, than weaker acids. Remember your working with solubility constants in chemistry. One exception is the solubility of silver in sulfuric, which works opposite - don't ask me why. When using concentrated nitric, the solution quickly becomes saturated with silver. Sometimes, you'll see silver nitrate crystals form on the chunks of metal. This can grind the reaction to a halt. Dilution increases the solubility of the silver. I always dissolve big silver contact points in nitric. I cover the points with cold distilled water and start feeding in the nitric, a little at a time, to keep it from foaming over. A vigorous reaction starts almost immediately, even though the solution, to start, only contains about 10% nitric and the solution is cold. Soon, I have all the nitric in that I've calculated it needs, plus enough water to make 50%, by volume. The bucket is so hot you can hardly touch it. In the morning, everything is dissolved. The only thing left is the crud.

19

Gold refining tips

I agree with you in most every aspect. You know my feelings in the plastic vs glass controversy, so I won't get into that. I would like to discuss the subject of cleaning up impure gold in the melt. It's much more difficult to clean off purity gold in a melting dish than in a crucible furnace. However, it can be done in both. I'm talking about gold that still has base metals in it. I'm not talking about gold contaminated with Pt group metals. With Pt group contamination, you have to start over and redissolve it in aqua regia. I try, as you do, to do everything possible to get the gold very pure before melting it. Sometimes, though, it is slightly off purity and needs a little flux work. At this point, I will play with it until it is pure. It takes, at the most, 10 extra minutes. Probably, 98% of the time, I am successful. If I understand your past posts, you see the need for fluxing as a bad thing and will put it right back through aqua regia. I don't understand your reasoning and maybe I have misunderstood you. I look at flux cleaning as only another gun in my arsenal. The end product is all that counts. It doesn't matter how I get there. The blond gold is great when you get it, but it's not necessary for pure gold. At least, not that I've ever noticed. Most times, the darker gold is just as pure. The darker gold is more finely divided and, therefore, is harder to rinse. I never really paid much attention to color, since I had developed good rinsing techniques and I knew I could clean most anything off purity in the melt. We both knew what high purity gold looked like. The gold we both produced met these stringent visual requirements. You ran your gold through twice. I ran mine once and cleaned up problems in the melt. Both ways worked. Same end product. Same deep pipe, gorgeous color, and super well-defined crystal. I worked for a guy that was the best refiner I've ever known. Along with silver cells, his main expertise was karat golds and he could do them faster than either of us could imagine. He didn't inquart but he cast a bar and ran it through a huge set of power rolls. He rolled it paper thin, then coiled it up and put it into aqua regia. If it was brittle, the rolls crumbled it into a jillion pieces. In both cases, it had much more surface area than any shot you've ever seen. After aqua regia, he melted in a dedicated pure gold furnace and was a master at flux cleaning. I would guess that he could clean gold as low as 99.5%, or less. For gold he couldn't clean - a rarity - or gold with Pt group, he ran it back through aqua regia and used a different precipitating agent. I noticed that, in the link for the Italian refining machine that aflac gave, they use a metal atomizing gun to shot the gold. This would be the absolute best way to optimize the dissolving speed of the aqua regia.

20

Getting high gold purity

We could argue about these things till the cows come home. I just hope our bantering is instructive to the readers. I think we both have to search our memories to come up with this stuff. I know I do. No matter how we did it, we both came out with very similar final products. I admire you for perfecting a system to put out pure gold. You should realize, however, that probably no one else in the world uses your exact system yet, there are many other aqua regia refiners that put out gold as pure as yours, with one drop, myself included. From day one and many 10's of thousands of ounces later, besides the economic aspects, super pure gold has always been a pride thing with me. You're the only person I've ever met that routinely uses double aqua regia. I see your logic behind this. I just took a different approach. About half of the gold I sold went into the manufacture of gold plating salts. Since I started out in the gold plating salts industry, this is where my contacts were. This industry has some of the most stringent gold purity requirements of any other industry. These salts were mainly sold to electronics mfgrs. and were all made with 9999 gold. Anything less would show up in faulty plating and the salts mfgrs. would be out of business. My gold was suitable to enter this system. Since pure gold ingots have a specific visual appearance, I chose to do nothing that would eliminate these visual effects. I wanted any educated buyer to have no doubts that my gold was pure. I didn't fire polish or buff the surface, for example. I didn't stamp my bars. I NEVER tried to sell gold that had oxide discoloration and never used acid to remove it. In my system, this discoloration was rare. When it happened, I remelted and cleaned it up. When I couldn't clean it up, I put it back into aqua regia, the last resort, as far as I was concerned. In your post, you used words like, "the thinking is flawed" and "stupid", when referring to my methods. Although these words get my blood pressure up a bit, I try to calm down and look at this thing logically. I think that sometimes you feel that anyone with different experiences than you is flat out wrong. When we were refining, we operated in different worlds of industry. Your business was mainly with jewelers. Mine was in the more broad high tech world in L.A., mainly in the electronics manufacturing sector. We both satisfied our customers with pure gold. Most likely, your gold would be satisfactory in my sector and mine in yours. As Steve's signature says, "The proof is in the pudding." I don't know where you got the idea that I cover the gold with flux. I never allowed that to happen. That would have really been stupid. I only used very small pinches of flux, mainly alternating between borax and niter. I usually used one pinch of soda ash, at the start, to adjust the flow of the flux. If it did reduce

21 oxides, it made no difference, since all were eventually removed with niter. The molten gold forms a convex meniscus and the flux slides to the edge of the button. When I had too much flux, I usually let the gold barely solidify and then poured off the still molten flux. I'm talking about when using a melting dish. When using a crucible, it's diameter was much larger than a melting dish and the buildup of flux around the edge of the meniscus isn't as much of a problem. When you add niter, you can see the oxides rise to the top from the interior. The melt is always kept moving with the torch. When base metals are still present, there is a whitish film on the surface. This is a surface effect caused by the oxidizing flame and/or the oxygen in the air. When the base metals are gone, the gold has a brilliant metallic mirror surface with no evidence of white. Further additions of niter don't affect this surface. All of this is much easier to perform in a crucible furnace. In order of decreasing particle size, gold goes - shiny metallic - blond - tan - light brown - medium brown - dark brown - almost black - black - black slime - purple, all with intermediate shades in between. With all of these, on a microscopic level. the individual particles are bright and shiny and probably crystalline. Only the eye sees them in bulk, in these colors. I would wager that I could, with some experimentation, start with 9999 gold and produce each of these colors, by varying the parameters. When refining, I have seen every one of these. In my experience, the finer gold is, the more difficult it is to filter, leach, and rinse out the contaminates. When really fine, these things become impossible. Therefore, the finer the gold, the more likely the gold will be impure. I always shot for lumpy, fluffy, light or medium brown gold. More like a sponge than a powder. This stuff rinses and leaches beautifully, maybe even easier than the heavier blond powder. Sometimes, the last, maybe 1%, of the gold dropped darker than the rest. I don't know why this happened, but it seemed to cause no problems, since the bulk was of good color. When filtering, our leaching/rinsing system was a bit different. I went hot water rinses - approx. 50% nitric leach - hot water rinses - ammonia leach - hot distilled water rinses. We both used ammonia. I used it for silver chloride and, I think, you used it to detect any blue solution of nickel or copper. Only traces of these metals produce a strong blue color in the ammoniacal solution. I rarely got any blue because of the large amount of rinsing done, on my spongy gold, before the ammonia. You used HCl and I used nitric. I feel that nitric will remove everything that HCl removes, plus more. I never did understand why you used HCl.

Getting high gold purity - 2

I'm going to bow out of this, with a few closing statements. These long argumentative posts are wearing me out and we both are saying the same things over and over. It's a fact that we both produced excellent gold using different

22 methods. This doesn't surprise me as much as it does you. I've probably known 50 professional refiners in my life and, with few exceptions; they all had similar goals and developed their own ways of producing good gold. I once worked for a guy who could care less about making pure gold. He shipped 99% and took a beating. This philosophy drove me nuts and I quit after a month. Maybe, your dropping gold from concentrated solutions caused the first drop to be crappy. I seem to remember having trouble along those lines, At an early point in life, I started diluting the aqua regia 3 times before filtering and that seemed to take care of a lot of former problems. I will concede that doing double aqua regia is a more guaranteed method of getting pure gold, especially for the novice. Maybe you're right in wanting these guys to do it. For me and every other professional refiner I've ever known, however, it's a big waste of time, energy, and money. Also, few or none of these guys inquarted. The Hoke book is the best book for the beginner that I know of. However, it was written 67 years ago and, since then, there have been a lot of innovations in aqua regia refining. Although an old method, the Miller chlorine/Wohlwill cell method is still the state of the art for refining gold. Once the initial outlay is covered, it's the cheapest, most reliable way of refining large quantities of gold. It's not used because the refiner can't get 9999 with aqua regia, no matter what you've read. It's like a refining machine, with set parameters and few variables. It avoids the very subjective method of using aqua regia. It avoids the workers screwing up the more sensitive aqua regia process. But, since it's very expensive to set up, only the big boys can afford it. The definition of an ingot is metal in a bar form. The standard method for processing circuit boards is to burn - grind - screen - melt the metallics - ship the dust (pulps) and ingots to a copper smelter. The ingots produced run about 65% copper and, along with the pulps, they contain all of the other 20, or so, odd metals and PM's on the boards. These big 50# ingots have slag all over them, which must be removed. The needle gun worked the best for this purpose. These are the only ingots I have ever used the needle gun on. I haven't read Ms.Hoke for awhile but, if I remember right, she used HCl to get rid of the iron from the ferrous sulfate she used to drop the gold. You and I don't normally use ferrous sulfate so, why use HCl? I can't think of anything else that would be present for it to dissolve. I haven't done aqua regia for awhile and I told you I have to search my memory to recall how I did certain things. I'm 67 and the CRS, Can't Remember S_ _t, gets a little worse each year. Of course, I thought of the presence of chlorides in tap water and from the aqua regia. My mamma didn't raise no stooped kids. Since you reminded me, I remember rinsing with

23 distilled water in between the tap water rinses and the nitric acid. I also remember testing the last rinse before nitric for chlorides, with silver nitrate. On to different things. Refining isn't a one trick pony. Enough has been written on aqua regia refining for the novice to do it. The info is scattered but, it's just about all there. In 1989, I made a list of 250 refining topics to write articles on. Refining karat gold was only one item on that list. I still have that list. I was going to do a refining newsletter. I could probably double the list today. Only about 10-20 of these have been covered on this forum. On to bigger and better things!

Gold refining outline

I think the reason you haven't gotten a response from your question yet, is that it's very broad. To answer you right, in every needed detail, it would literally take 2 days to write. Karat golds are probably the most difficult form of gold to process. You have to know so many different things, to do it right. I do have about 6 pages written, on the whole process, on a Word Doc. that I will eventually finish and post. I'll probably end up with 15-20 pages. At this point, I will at least give you an outline of what to do. There are several ways to refine karat gold, but this is the way I do it. Try to search out the details on the forum. They're all here, somewhere. Actually, Harold has more experience on karat gold than I do. He'll probably add to this. If you do this, and still have specific questions, I will be happy to try and answer them. (1) Inquartation. Calculate how much silver it will take to lower the gold percentage to 25%. For example, if the total gold in your whole batch runs 50%, you will need the same weight of silver as you have karat gold. Combine the silver with the gold, melt it, and pour it into water in a tall stainless steel container to form shot. (2) Nitric Dissolving. Under a fume hood, dissolve all of the non-gold metals in 50/50 nitric acid, leaving the gold undissolved. The gold is now a brown powder. Save the solution for silver recovery, so that you can use the silver to inquart more gold, (3) Aqua Regia. Separate the nitric solution from the brown gold powder. Dissolve the powder in aqua regia. (4) Silver and Lead Removal. Dilute the aqua regia 3 times to drop the silver. Add sulfuric acid to drop the lead. (5) Filter. Filter the aqua regia to remove all solids.

24 (6) Precipitate the Gold. There are several different chemicals that will drop the gold out of the solution as a brown powder. I use sodium sulfite. Unlike the last brown powder, this time the brown powder is pure gold. (7) Filter. Filter the brown gold powder, rinse it well, acid treat it, rinse it some more, ammonia treat it, rinse it more. Dry the powder. ( 8 ) Melt the Gold. Melt it with a torch in a melting dish or, better still, melt it in a crucible furnace. If it's not perfectly pure, treat it with fluxes. (9) Cast the Gold. Pour the gold into a prepared ingot mold. Congratulate yourself on a job well done. I hope I didn't leave anything out. Except for steps 4 and 9, I could write a page or two or three on each step. Please don't get discouraged. Other people have learned to do it on this forum. It's all worth it when you pour the molten gold into the mold and see the beautiful pure gold bar you've made. There's nothing else in the world that looks like it.

What is aqua regia

I don't use the name "aqua regia" when talking about HCl and sodium nitrate. To me, aqua regia is HCl plus nitric acid. The two systems are very different in power and speed. With HCl plus sodium nitrate, you have contaminated the solution with a lot of sodium ion and have diluted it with all the water that is needed to first dissolve the sodium nitrate. These things zap it of a lot of its strength. On the other hand, real aqua regia is full strength and will go after the metals with much more vigor. Using HCl plus sodium nitrate is probably fine on plated materials or gold powder but, for bulky gold alloys, such as karat golds, you need the power of real aqua regia. Sounds like a detergent commercial. If you put 18KT in boiling nitric acid for 5 years, it would never touch it. The ring would still be a ring that you could wear and it would still be as bright and shiny as the day you put it in. The nitric doesn't attack the gold but only base metals. In 10KT gold, the gold is only 40% and this lower amount will allow the very hot nitric to penetrate and attack the base metals and silver. This leaves only the gold, as a porous gold powder. With 18KT, however, the gold content is 75%. The gold is so high that it forms an impervious barrier and prevents the nitric acid from penetrating at all. Aqua regia is a totally different animal than nitric. It actually will dissolve every type of metal involved, including gold and silver, in the alloy. It makes no different what karat the gold is. However, the dissolved silver immediately combines with the chloride from the HCl to form silver chloride. The silver chloride forms a crust

25 on the surface of the karat gold and slows down the penetration of the aqua regia. If the silver content is high enough, the penetration of the acid completely stops. This problem is solved by inquarting with enough silver (preferably) or copper to reduce the gold content to 25%. Then, everything but the gold can be easily be dissolved in hot nitric acid. The remaining gold powder is then easily dissolved in aqua regia. #13 I've never used sodium bisulfite. I have used sodium metabisulfite. My preference is sodium sulfite. They all smell badly of sulfur dioxide in use, but the sodium sulfite seems to smell the least. This may be a subjective judgment, though. I started out with sodium sulfite and learned how to use it. I get consistently pure gold from it. It's commonly used to process photographs and I buy the photo grade, which is fairly inexpensive but quite pure. The Kodak brand is available in some camera stores in 1# packages. The last time I bought it, it ran about $5. It's much, much cheaper in 50# bags. The photo grade bag brand I used to buy was Stauffer (may not be spelled right). You can buy it from most chemical suppliers.

More refining tips

Quote: What are the best containers to use? I prefer 4 liter beakers for dissolving and use a watch glass to cover it. In case of breakage or spillage, I place the beaker in a 5 quart, white, flat bottomed, Corning Ware dish and put the dish on the hotplate. For 5 ozs, or less, you can use a Pyrex, 10 or 12 cup, replacement drip coffee pot. The best is the one with a stainless steel ring holding the short plastic handle, only at the top. Don't get the type where the bottom of the handle is attached. It will burn. After dissolving, I transfer the solution to a clean, white, 5 gallon plastic bucket. I add 3 times the volume of tap water that I have acid plus about 60 mL of battery acid per each gallon of acid. These two additions will drop out any silver or lead that is dissolved in the acid and these will be removed by filtering. Stir the solution. The long straight part from a plastic clothes hanger works great. I sit the bucket on a table or a bench. I place a piece of 2" X 4" underneath the back edge of the bucket. This tilts the bucket towards you and allows the solids

26 to settle in one spot on the front bottom of the bucket. I put the lid of the bucket and allow the solids to settle overnight, Quote: What is the best way to decant my solution w/o disturbing the gold sediment after precipitating? There are three ways to do this. I do all three, depending on what I'm dealing with. More often than not, I siphon. No matter which one I use, I always end up filtering the entire solution. Super clean solutions, before precipitating, is necessary for good gold purity. This goes fast, however, if you first use one of these methods to get a gross separation of the liquid and the solids. Decant, dip, or siphon off the liquid. Filter the liquid first and then filter the solids plus the remaining liquid last. If you were to try and filter the entire thing, without first separating the liquid and solids, it would take forever. (1) Decanting. You can carefully pour off the solution into another bucket. This is the fastest way. When you tilted the bucket, the solids settled together in one pile. Before pouring, put the receiving bucket inside a plastic tray with about a 7 gallon capacity (WalMart), to catch drips and spills. Put the tray on the floor. When you pour, keep the pile nearest the bucket you are pouring into. In other words, try not to disturb the pile. Go slow and steady. Keep an eye on the solids. Just before the solids start to go over, stop. After pouring, there will be a slight film of solution, where you poured from, at the rim of the bucket. Either have a friend rinse this gold bearing film into the receiving bucket or, rinse it back into the bucket containing the solids. If there are drips remaining anywhere on the outside of the bucket, wipe them off with a piece of paper towel. Save this and any other paper towels you've used to wipe up spills that contain PM's. Eventually, you can burn the towels and recover the values. It's actually better to have 3 separate buckets to save PM laden towels - gold, silver, and Pt group. (2) Dipping. I don't use this method much when working with buckets. I use it a lot when working with open plastic drums. Often, it is difficult to raise a heavy drum high enough to completely siphon it. So, I keep it on the floor and siphon it into an empty plastic drum sitting next to it. When half of the solution is siphoned, the solution level in the 2 drums will be equal, and, therefore, the siphon will stop working. I dip the other half of the solution out with a neat scoop that I cut from 1 gallon plastic jugs. With the bucket still tilted, carefully dip the solution out, and into the filter, with a 1 cup Pyrex measuring cup - the type with a handle. To keep from disturbing the solids, use this technique. Turn the cup sideways and slowly immerse it part way. As it fills, slowly turn it upright and, at the same time, bring it out of the solution. If you do it right, the solution surface will hardly make a ripple. As you get near the bottom, you have to be more careful and fill the cup less and less each time. To keep from dripping solution all over, hold a bucket lid under the cup, with the

27 other hand, when moving the solution to the filter. When safely over the filter, remove the bucket lid. When finished, rinse off the lid and the cup into the filter. When the liquid is completely finished filtering, start filtering the solids. (3) Siphoning. Proper siphoning can remove the most liquid without disturbing the solids. This makes the filtering go faster because there are fewer solids to filter. And, the solids are what clogs the paper and slows down the filtering. I don't use gloves when siphoning because the tubing is harder to manipulate. Of, course, I always have purple hands. I do recommend that you use gloves. The thinner the gloves, the better, for this operation. Practice the siphoning a few times to get the hang of it. Put a little sand in a bucket of water. Tilt the bucket, let the sand settle, and siphon off the water. This is a little harder to explain without pictures. Put a clean bucket inside a plastic tray and put the tray on the floor beneath the tilted bucket on the bench. Get about a 4' length of 3/8" ID clear, flexible, plastic tubing from the hardware store. With this size tubing, a full bucket will take about 5 minutes to siphon. These instructions are for a right handed person. Reverse them if you are left handed. Fold the tubing double so that the ends meet and are together. Fill the tubing with water to the brims of both ends of the tubing. Stand on the right side of the buckets. Hold the ends of the tubing together in your left hand. Keeping the ends at the same level, hold the right end in your right hand and put your left index finger over the left end, to seal it. Keeping the left end sealed, lower it to the bucket on the floor, until your hand is partway inside the bucket. And, here's the tricky part. At almost the same time, put the right end about an inch into the solution and release your left index finger. Actually, the left finger release should occur about a half second after you stick the right end into the solution. If the solution flows, release the left hand completely and allow the tubing to hang in the lower bucket. If it doesn't flow, start over. As you're siphoning keep an eye glued to the end of the tubing that's in the liquid. Try to keep the tubing only about an inch deep in the liquid. This is hard to see if the liquid is dark colored. I usually color about 1-1/2" (measure it) of the end of the tubing with a red Magic Marker. Black is OK but you can see the red better. This enables you to determine how deep the tubing is in the liquid. The marker will wear off after a few times and you will have to redo it. It's hard to hold the tubing steady and keep from disturbing the solids. To remedy this, I put the very edge of the tip of the tubing against the front side of the bucket, while keeping it about an inch deep. As the liquid level goes down, slide the tip down with it, against the side of the bucket. As you approach the solids, reduce the depth of the tip in the liquid and, with your left hand, slowly tilt the bucket a little more towards you. . I repeat, keep your eyes on the tubing. If the tubing comes out of the liquid, for

28 only an instant, the siphon will break and you'll have to start over. After siphoning, rinse the tubing, inside and out, into the top bucket along with the solids. The best thing to use for rinsing and, for filling the siphon tubing with water, is a lab type, plastic, squeeze type, squirt bottle with a long spout. The spout points sideways from the lid. I have also seen these in sporting goods stores. Joggers use them. Quote: Can excess urea affect the way gold precipitates?

With no urea, the Storm (sodium metabisulfite) reacts with the excess nitric before it starts dropping out the gold. With too little urea, the same thing happens. If you don't have any excess nitric to start with, you don't need urea. That is my approach and I've covered how to do it on several other threads. With a lot of extra nitric and no urea, you may have to add several pounds of Storm before anything happens. With way too much urea, the excess will sit on the bottom and won't dissolve. Quote: How do I filter my aqua regia acid.....Can coffee filters be utilized There is a good discussion of filtering on several threads and this thread, especially. With coffee filters, Lazersteves setup would be best. With lab type filter papers, mine would probably be better.

Quote: do I use urea before Filtering? Interesting question. I don't use urea any more and haven't really thought about this question. Either way would work, although most people do it after filtering. However, if you are heavy handed, add an excess, and have undissolved urea sitting on the bottom, it would be better to filter after adding. Of course, how do you know in advance that you will add too much urea? Were I to start using it, I would probably add it before filtering.

Inquarting Obtaining nitric Miscellaneous tips

Here's one way to calculate the amount of silver you need. You could use copper instead of silver but silver works better. You have 10 grams of 14KT gold. 14KT is about 58% gold. Most karat gold is made up of gold, silver, copper, and a little

29 zinc. Therefore, in 10 grams, you would have 5.8 grams of gold and 4.2 grams of mainly copper and silver. To find out how much total silver and/or copper you need, multiply 5.8 times 3. This is 17.4 grams. You already have 4.2 grams in the alloy. Therefore, you need to add 17.4 - 4.2 = 13.4 grams of silver to your 10 grams of 14KT gold to end up with 25% gold. For 10KT, the gold is 40%. For 18KT, it is 75%. Although it will certainly work, I hate to see you use your superpure 99.99% silver for this purpose. Scrap sterling silver will work as well. Getting nitric is always a problem. If you're in a city, try to find a company that repackages technical grade chemicals in smaller quantities. Don't buy high purity reagent grade, as it will cost you about 10 times more. Look under chemicals or lab supplies in the yellow pages and call around. You shouldn't have to pay much more than $12 per gallon, in one gallon jugs. You should try to find a place close enough where you could pick it up. It's Hazmat and the shipping could run twice, or more, what you're paying for the acid. If you can't buy nitric, you'll have to make it. (However, it's a hassle and, if you can find technical grade nitric, in gallon quantities, for sale, I would suggest buying it. A gallon of tech grade nitric will dissolve about 100 ozs. of silver or 30 ozs. of copper). You basically start with battery acid and sodium nitrate. Battery acid, although weak, is about the purest form of sulfuric available from common sources. You first have to increase the strength of the battery acid. Catfish wrote an excellent tutorial on this. This can be dangerous because it can get very hot, so study the safety parts carefully. When dissolving silver, always use distilled water to dilute the nitric. I usually cover the metal with water, heat it up, and start feeding in the straight nitric, in increments. If you add too much nitric at one time, it could foam over. When diluting the aqua regia 3 volumes, tap water is fine. Quote: One last question. When working with nitric, do I need a fume hood. I have 5 acres out in the sticks I can work from without anybody being bothered and is that safe. I want to know what molar strength is needed and can it be handled outside and other than glasses and gloves is there any other precautions to take.

A fume hood is best but I've done my share of refining out in the sticks. Sometimes, you'll have days of an inverse temperature gradient. This is when the ground is colder than the air. On these days, it's a little harder to get out of the fumes because they tend to cling close to the ground. But still, working outside is fine as far as safety is concerned. The fumes produced from nitric or aqua regia

30 are reddish brown and are quite visible. With small quantities, this is no problem. With very large quantities, someone may see it and turn you in. A little wind is good because it disperses the fumes quickly. The only problem with wind is that it sometimes changes direction and this makes it harder to stay upwind. I'm big on proverbs and, "Look before you leap", is one of the biggest when doing refining. I would use a welder's type full face shield instead of glasses. The clear plastic type with an adjustable head band - about $7. They're easier to see out of and are more comfortable and safer. When you don't need it, you just flip it up. No matter how careful you are, you're going to get a drop of acid flying in the air. This usually happens when you're pouring the fresh acid. These drops always seemed to land on my nose and I usually had a scab or two there. A face shield is much more protective. A liter of 70% nitric, the standard strength of industrial grade nitric, contains 15.4 Moles of HNO3. The other 30% is water. Rarely is this information needed for refining. In practice, I consider the 70% product as being 100% and go from there. If I want 50/50, I just double the volume with water. One of the most important things I've learned is to always put the container you're working with inside of a larger container. Everyone has spills, dribbles, glass breakage, and foamovers. This tip will save you a lot of grief. If the solution needs to be heated in a beaker, the outer container needs to be heatproof. The best is a 5 quart, white, flat-bottomed, Corning Ware dish. New, they cost about $25 but, you can usually find them in resale shops or flea markets. These things are incredibly strong. If you're working in a bucket, without heat, use a plastic tray as the outer container. A 7 gallon tray from WalMart runs about $7.

Preparing gold for dissolving

Rolling. I definitely recommend rolls for karat gold. Motorized rolls are, of course, much better. The trick for fast dissolving is high surface area. If you were to roll a 1 ounce cube of gold to even 20 mils thick, you would have about 20 square inches of surface area. On the other hand, if you were to shot this same ounce of gold to 1/8" spheres, pretty small, you would only have 5 square inches. This means that the 20 mil rolled gold will dissolve 4 times faster than 1/8" shot. When rolling, you'll end up with a long strip. The 20 mil strip above would be 20" long by .45" wide. Coil the strip in a spiral shape, without anything touching, and place it in the bottom of your dissolving container. Rolling the gold is much, much faster than shotting. Sometimes, when rolling gold with lead in it, the gold is brittle and it crumbles to pieces with good surface

31 area. Shotting. If you shot and, if you have nitric, you may as well inquart and end up with purer gold. Getting high surface shot is not as easy it sounds. The container must be stainless and it should be tall enough so that the gold is solid by the time it hits the bottom. Otherwise, it will glob up and, it could stick to the bottom. The object is to get the highest possible surface area. There are several ways of achieving this. The first is "Popcorn". See the photo. Harold can best describe this. I usually use one of these three. They tend to produce a small flat, high surface area shot: 1) The old standard is to place a board nearly flat in the water, a few inches deep, and pour the gold onto the board. 2) My favorite. One time we were shotting karat gold in a stainless restaurant container, about 6-8"square X 24" deep and, we were getting big shot and clumps. I carved a propeller, about 4" long, out of hardwood. I drilled a hole it it and mounted it to a length of all-thread with two nuts and two lock nuts, tightened pretty good. I chucked it in a drill and had someone hold it about 6", or less, under the water. I then poured the gold directly into the prop. I got the smallest shot I have ever seen. 3) Handy & Harman used this method. They had two water inlets near the bottom of the vessel, set to make the water swirl. The water continually overflowed.

Dissolving base metals with aqua regia

AR is not the way to go on pins. However, if you do happen to use "real" aqua regia for pins, there is an easy way to prevent it from foaming over. First of all, never premix the aqua regia. Use the acids separately. Cover the pins with HCl and heat. When you get a little steam coming off, add a little nitric. You should get an immediate reaction and some foaming. When the action dies down and the foam subsides, give it a slight stir and add a little more nitric. Repeat until the pins are dissolved. The size and frequency of the nitric additions is determined by the amount of foam produced. It may take more HCl. It takes 1/2 gallon of either nitric or aqua regia to dissolve 1 pound of copper or brass.

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You can do this at room temperature but, I prefer heating it, for this reason. At room temp., the reaction is somewhat slow in starting. This makes you think that not much is happening and you, therefore, add more nitric. The reaction generates heat. At some critical temperature and concentration, the reaction starts going at full speed and the solution foams over. By pre-heating the solution, the first addition of nitric goes full speed immediately and this will prevent you from adding too much nitric at one time. If you don't pre-heat, put the pins in a 5 gallon plastic bucket and put the bucket in a plastic tray (a safety net for foam-overs). The bucket gives you plenty of room for the foam. I wouldn't run over 2# of pins per batch. Cover with HCl and add a little nitric. Be patient and wait for this first reaction. Stir well when the reaction slows down. Repeat as above. You can also pre-heat the HCl to about 130 deg F before you put it into the bucket. I learned this stuff the hard way. I've had my share of foam overs and have lost gold in the process. However, the vast majority of these foam overs occurred by starting with cold solutions. Were I to use nitric acid only to dissolve the copper or copper alloys and leave the gold undissolved, I would put the pins in a bucket and cover them with very hot water. I would then start making nitric additions as above. Live and learn. Patience is a virtue. Look before you leap.

Nitric acid
Yes. All in all, when using nitric alone or in any acid combination, about half is lost in brown fumes. This varies a bit as to temp., concentration, etc. You are better off to either first dissolve the gold or the base metals but not both at the same time. In this case, nitric is precious - why waste it. Use Steve's method of dissolving the base metals first, without nitric. On the original question: It's all equal. With small additions of nitric, you're just releasing the fumes at a slower rate. The total is the same. It's based on the total metal dissolved. In 40 years, I have never ever seen gold "locked" in acid solutions, under any conditions. If it's dissolved, it will always drop out, using the common precipitants. Just make sure the solution is filtered clean before doing it.

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Using acids in aqua regia

When I started refining, in 1966, I used a standard AR mix of 3/1 or 4/1, HCl/HNO3, and always evaporated to eliminate the HNO3. In about 1980, I worked for a guy that ran mostly karat gold - about 50 to 100 oz/day. He never evaporated or used urea. His trick was to only use enough nitric to dissolve the gold - with no excess. Then, after dissolving, diluting, and filtering, he could directly use sodium sulfite to precipitate the gold. To dissolve, he would first cover the gold with a calculated excess of HCl and heat. Then, he would add small increments of nitric. When a small addition of nitric produced no reaction, he was finished. There's a little more to it, but that was the general idea. When I later owned a refinery, I totally adopted his method. It dissolved a bit slower, but was faster overall, since evaporation wasn't necessary. Occasionally I would have to evaporate, but it was rare. I have covered this method in greater detail in previous posts. I know it goes against present thinking, but it really works well.

Using nitric acid

If you don't use an excess of nitric, you don't need any urea. Even if you have a very slight excess of nitric, the first addition of SMB or sodium sulfite will take care of it.

ASSAYING
Scale errors

34 Your scale is not accurate enough to use for fire assay. It is only accurate to +/- 0.1 grams. That's the same as 100mg. The sample size is 250mg (.25 grams). Therefore, your possible error is 100/250 or, +/- 40%. If you started with super pure 100% gold, you could get an answer of somewhere between 60% and 140%. With a 2 digit scale (+/- .01 grams), the potential error is +/- 4%. With a 3 digit scale, the error could be +/- .4%. A 4 digit scale (+/.0001 grams) would be a error of +/- .04%. Fire assaying doesn't allow for very large samples. You could probably run as much as a .5 gram sample but, that wouldn't help much. Assume that your gold sample is actually 3 nines - 99.90% pure. Using these 4 different scales, here's the possible ranges of answers you could get. +/- .1 gms - from 59.9% to 139.9% pure +/- .01 gms - from 95.9% to 103.9% pure +/- .001 gms - from 99.5% to 100.3% pure +/- .0001 gms - from 99.86% to 99.94% pure As you can see, the only scale that is even somewhat reliable is a +/- .0001 gram balance. It will weigh a hair. Also notice that even a scale of this accuracy is worthless when trying to distinguish between a purity of, say, 99.95% and 99.99%. And, fire assay is the most accurate method on the planet. To analyze very high purity gold, the only way is to analyze all of the impurities, add all their percentages together, and subtract from 100%. Another typical example. If you're fire assaying 2 grams of pins, worth $50 per pound, the final bead weight would be about .0105 grams. This can't be weighed with a 1 or 2 digit scale. A 3 digit scale can be 10% in error. A 4 digit scale is only 1% in error. These 4 digit, +/- .0001 gram scales are called "analytical balances." The new digital ones start at about $1200. There are lots of old used mechanical ones out there for several hundred dollars but, you don't know if they are reliable. It doesn't take much to screw one up.

Should you pay for a fire assay?

I just hate to see you guys wasting money to have your pure gold assayed. The thing I have trouble getting across is that, with high purity gold, the accuracy of fire assay just isn't good enough, even though it's the most accurate direct method on the planet. There are quite a few things that affect this accuracy: the balance accuracy; the skill of the assayer; the purity of the silver used to inquart the gold; the purity of the lead foil; traces of microscopic dirt or slag in the

35 sample; etc. None of these things are 100% without error. They are all present in every assay and they all add up to give a net error. For example, let's look at only the balance (scale) error. Most assayers use a balance that reads to +/-, .0001 grams. The standard gold sample size is .2500 grams. Lets say you ran the assay and got a final gold weight of .2498 grams. This gives a purity of .2498/.2500 = .9992 gold or. 99.92%. However, due to the built in scale inaccuracy, the weight might range from .2497 to .2499. This gives a gold percentage range from .2497/.2500 = 99.88% to .2499/.2500 = 99.96%. This is quite a difference and doesn't even take into consideration the other sources of error. If you run duplicate or quadruple samples, you average the answers, and get more accuracy. However, to do this costs more money. Also, $25 for an assay is very low. They can't be spending much time, cost, or effort doing your assay. That same assay will cost $250 at the best assay labs. It's best to not let the people you're selling to do your assays. It's possible that they actually didn't even run an assay. They could have just looked at the gold, held it to their forehead, made up a number, and charged you $25. I can't tell you how many times I've seen this happen. The amount of gold you're selling them is minuscule compared with their total business. If you want a high number, they'll give you a high number. No skin off their butt. They're going to buy it, no matter what. The best, and cheapest, way for you to determine purity is to simply look at the bar. Make it a go/no-go thing. If it has large, well defined crystal, a deep pipe, brilliant deep color, non frosty surface, no discoloration, it's a go. If not, re-refine it.

Lead reduction from litharge Other assay tips

I haven't looked at the chemistry of fire assaying for quite awhile but, concerning the reduction of litharge to lead metal, and the subsequent release of oxygen, here's what I remember. The heat is not what causes the litharge to give up it's oxygen. This is shown in the scorifying process. One purpose of scorifying is to reduce the weight of a lead button to a convenient size so it can be cupelled. This is done by melting the lead in a shallow wide dish, called a scorifying dish. The oxygen in the air oxidizes the surface of the lead to form litharge, lead oxide. The longer this is done, the more lead oxide will be produced and the less the weight of the lead metal that remains at the bottom of the dish. The point is that the heat does not re-convert any of the lead oxide back to lead metal. Also, all of the precious metals that were originally in the lead metal, before scorification, are now

36 retained in the lead metal (most probably, very uniformly) that exists, after scorification. None goes into the lead oxide phase. Reduction of the litharge, and the subsequent release of oxygen, requires some ingredient in the fusion melt which will act as a reducing agent. Commonly, this would be carbon, sulfides, or iron. Ideally, when assaying electronic parts, the fusion should result in a 30 gram chunk of lead. If no reducing agents are inherent in the sample, an exact amount of lead can be reduced by adding an exact amount of some ingredient that contains carbon. Sugar, flour, or charcoal are commonly used. I learned to use sugar when I started. If I remember right, 1.4 grams of sugar (depending on the brand) will produce 30 grams of lead. I think that the ancients used lees, a substance that settles out in wine. A couple of times, I forgot to add the sugar. I ended up with no lead button - zero. All of the litharge had gone into the slag. CERAMICS AND LEAD In my days, I have assayed many 100's of PM containing, ceramic electronic component samples. With no exceptions, the ceramic pieces, large or small, floated above the lead. If I remember right, the ceramic even floated on top of the slag which was on top of the lead. If any ceramics had sunk into the lead, this would have made cupellation of the lead impossible.

Collecting PGMs in nickel sulfide

F. E. Beamish wrote an excellent series of books on the analysis (all methods are covered) of the noble metals in the '60's and '70's. They include an outline for a fire assay method for the collection of all 6 PGM's using nickel sulfide. The collection is at least as good as when using lead, although neither are as complete as when using the best direct acid extraction methods. Perhaps, the NiS collection can be adapted to a larger scale. Here's Beamish's procedure: (1) Basic Flux mix for up to 50 g of ore: 60 g of fused borax; 30 g soda ash; 32 g nickel carbonate; 12.5 g powdered sulfur (2) At a temp. of 1832 deg F., fuse for 75 minutes (3) Pour into an iron mold. Separate the button from the slag. (4) Shatter the brittle button in a hydraulic press. Grind until fine. (5) Overnight, dissolve away the NiS using 400 mL of conc. HCl, at low heat. The PGM's remain as sulfides, which are easily treated with acids.

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BUYING AND SELLING

Buying tips
The pricing depends on who you're buying from and how much you're able to sell it for. If you buy from the public, the profit margin is much greater than if you buy from pawn shops, coin stores, jewelers, or other buyers. However, both are lucrative if you get your numbers straight. Buying from the buyers is lower margin but higher volume. Although some would disagree, I think more money can be made on karat gold by simply buying and selling, without refining it. In my experience, the secret is to turn your money as often and as many times as possible per unit time. The refining process slows this down considerably. Also, by turning the metal fast, you are not as affected by daily changes in the market price. If you get to the point where you're doing big volume, that's when you MIGHT consider doing your own refining. When I bought and sold karat gold, I sometimes quoted how much I was paying, per gram or pennyweight, for 10Kt, 14Kt, 18Kt, and 22Kt, based on a certain percentage of the market price. I never mentioned the market price - only what I was paying. These numbers change daily and sometimes hourly, depending on what the market is doing. You really have to keep on top of it. Another way is to keep silent about what you paying until you have evaluated and weighed the material. Then you say something like, "I will give you X dollars for this bunch of material." When buying from the public, they will usually take what you offer, unless they've been shopping around. If you quote on the low side, you can always negotiate and increase your offering price. A friend of mine, who owns a scrap metal yard, often says, "It's not my job to educate the public." When buying from buyers, they are more savvy and will often ask what you are paying for 10Kt, 14Kt, etc. You can usually buy from the pubic at somewhere between 50% to about 80% of spot. If you buy from buyers, you will pay from about 80% to 90% of spot. Whatever the traffic will bear. When selling your karat gold, the price you can get depends on volume, the honesty of the buyer (or, refiner), how you have prepared the scrap, and how well you've covered your butt. When selling small amounts, you'll usually get somewhere between 93% and 98% of spot. For very large amounts, you might get over 99%. Always shop around when looking for a buyer. Also, don't forget that, when you buy, you're paying cash and, when you sell, you usually get a check. Catfish may disagree with these numbers. I haven't done this in awhile and different strategies are needed in different markets. As in all things, buy low and sell high but, don't price too low or, you'll price yourself out of the market. There is plenty of competition out there.

38 You will have to go through a learning curve on how to determine the karat of gold objects. Some gold is not marked and, even that that is marked can be marked wrong. Catfish tests everything, even if it's marked. This is a very good idea. When I was manager of a refinery in Hong Kong, I once asked the owner of the largest Hong Kong gold exchange what he thought the gold market was going to do. He said that there were only 2 great experts in this field. One thought the market was going to go up and the other thought the market was going to go down. I have never forgotten this. In other words, when buying and selling, never worry about the market. Just make sure the proper buying/selling spread is present, on every deal, and turn your money as fast as possible. This is only the tip of the iceberg and these things are only my ideas.

Selling gold
My son lives near Dallas and I've been helping him get set up to buy karat gold. I suggested that he try out the above-mentioned company that Tom Smith and Lou have been selling to. http://aragold.com/ I called them the other day and this is what I was told: They pay 98% over the counter (OTC) for karat gold. However, all OTC calculations are based on 1/2 karat less. For example, 14K is figured as 13.5K. The 3-5 day period, mentioned on the website, is based on a melt and assay, in which case they would pay 98% of the assay. They don't pay for the Ag in karat gold or the Pd in older white gold. OTC, they pay 88% of the calculated silver content of 92.5% for sterling. OTC, they pay 80% of the Pt content of Pt jewelry. For Pt/Ir, the Pt runs 90%. For Pt/Ru jewelry, the Pt runs 95%. They don't pay for the Ir or Ru. These prices seem pretty good to me. Since my son lives close, I told him to buy for 1/2K under and sell everything OTC. The old "bird in hand" thing.

Dealing with gold filled

Refine It When new, the worst gold filled (10K, 1/40 - 1%gold) I've seen, runs about $100 per pound. The best I've ever seen ran 5.8%(14K, 1/10) - $580/pound. If you can

39 get a lot of it, it might be worth thinking about refining. It might sound heretical but, I would shot it and dissolve everthing but gold nitric, even the gold is only 1% to 5.8%. The gold will be extremely fine, black/brown, hard to handle and hard to settle. You'll even have a little purple colloidal gold. It all will eventually settle, however. A little heat can help agglomerate (bring them together) the particles. Then, shut the heat off and let it settle. If you have glass fiber papers and a vacuum filter, you can filter it. After it settles, filter the top solution and then filter the gold, in the same filter. You can't use regular paper. It will go right through it. If you don't have a vacuum filter, you can settle the gold and then siphon the solution off. Add some rinse water, stir, settle, pour off, repeat a couple of times. Transfer the black powder to a beaker and dissolve it in aqua regia and go from there. Sell It Here's the way I would do it (1) Remove all non-gold filled materials, including grease or oil. (2) Go through the material and sort it by markings. Keep unmarked stuff in a pile. You'll probably (3) Weigh each pile and estimate the value per pound, based on the markings. You are now armed. (4) Type in Google, "gold filled" scrap paying . There are literally 100's of refiners, taking in gold filled with toll-free numbers. Start calling them and getting quotes. Don't bullshit the buyer but, try to sell it. I would tell them that you're shopping around. See what they'll buy it for, outright, rather than refine it. See if they'll send you a quote, for exactly what you have, by fax (good luck). If they start changing things after they receive it, tell them to send it back. If they won't buy it, outright, see what their refining charges are. Shop around Make a decision. Do you want to sell it, have it refined, or refine it yourself. It's all economics. If the lot is small, the buyer could care less. If it is pretty large, the buyer will want it. Another wild way to sell this is to call around and find buyers that will buy it, for a good price, in ingot form. This would only work for large volume. They would buy it based on assay. A buyer may be hard to find. You would need a crucible furnace and molds. It would be better to have a furnace big enough so you only have one ingot. Otherwise you pay for assays for each ingot. You melt it - Cast it - Drill it - Have the drillings assayed - Put your stamp on the ingot - Make photos of drilled, stamped ingot(s) - Send the ingot to the buyer - Have the buyer drill it and assay it. Don't let the buyer re-melt it to do this. Have him drill the original

40 ingot. Otherwise, don't let him alter it - When the refiner finishes the assay, have him give you a quote - Take the offer or have him return it.

Using professional reps Big number deals Buying in mining areas

1.) You guys suggested we hire an expert to navigate thru the money laundering or illicit risks. Do you have anyone you would suggest?

The most qualified are the old established assayers-representatives-umpires (google these keywords). They are very expensive but very reliable. Whether they would do the type work you need, or not, I don't know. It would be worth a call. If you could find someone to talk to you about your problem, they could at least steer you in the right direction. Probably the best known is: http://www.ledoux.com/ Many years ago, the companies I worked for always used Ledoux. Here's a quote from their website. Sounds like what you need. If you pay them enough, they will probably travel anywhere. After 128 years, they surely know all the tricks and scams. Your particular type deal is quite common and I'm sure they've dealt with it 100's of times. "Ledoux and Company is an independent commercial metallurgical chemical laboratory which has been family owned and operated continuously since 1880. The company acts as representative for importers and exporters, providing analytical services for many ores and concentrates. We provide facilities for the composition analysis of a wide range of materials. Samples are submitted by major refiners and traders for exchange quality results; and for more rigorous umpire type.Virtually all elements can be measured but particular expertise is available in the determination of precious metals, base metals and trace impurities." I would suggest not going with bargain basement assayers-reps. Were it me, I would go with the tried and true. It will probably cost several thousand dollars, but that's a trifle when you're talking about the possibility of losing millions. Actually, you probably won't do the deal at all. After talking with Ledoux, you'll likely be convinced that it's a scam. You should realize, however, that Ledoux is in the business of actually doing the rep and assay work. They will probably do what you want, whether this is a scam or the real deal. When you first talk to them, do a little probing and find out what their thoughts are about whether or not it is real.

41 Quote: 2.) In your experience or knowledge has any deal like this ever taken place successfully? Ie. one where gold bullion or sponge is bought for less than 65% of market value?

I have personally been involved in two of these deals, when I was young, foolish and greedy, but they both just fizzled out. I have never heard of any of these type deals actually happening. I could never figure out the scam. It surely has something to do with paperwork, money up front, sleight of hand, or ??? I do feel that, once they see that you're doing things right, in a way to totally cover your butt, they will just disappear. That's been my experience. Quote: 3.) If one were to go physically to impoverished mining regions of the world would it be possible to negotiate purchases along these prices directly from the mines or miners? Hvae you heard of anyone other than Theodore Rhodes doing this?

In most of these third world gold producing countries, there are individuals that work the slag piles and dig a bit on their own. In some countries, maybe 10% of the total gold is in the hands of these individuals. You could probably buy cheap (probably more than 65%, though) from them but, getting the gold out of the country might be a big problem. Also, you'll have to pay cash and carrying cash could be very dangerous in gold country. About 30 years ago, a big mining company in Alaska wanted to hire me and helicopter me into mining camps, along with armed guards, to buy gold for cash. I said Thanks but No Thanks. In my experience, buying large quantities of good gold anywhere, for anywhere near 65% of spot, is a dream. I know that I come across as pessimistic but, after 40 years in the business, I have learned to always first think of all the negatives and then work backwards. Gold attracts crooks, maybe more than in any other industry that I can think of. A problem with these deals is, when you get slightly hooked (as you are), it always wastes a lot of time, effort, brainwork, and usually money, just to try and figure out what's going on and, if you decide to go ahead, to try and plan for all of the possible bad things that can happen.

Stamping on sterling and karat golds

42 The stamping on modern silverware in the U.S is very reliable. I don't ever remember seeing any that was stamped sterling that wasn't sterling (my buyer was fooled once by a stamp that said, "Sterling Manufacturing Co."). And, I can't remember seeing any that wasn't stamped sterling (or, 925) that was sterling. I'm not saying these things don't exist. I just haven't seen them. Older antique sterling and foreign sterling (or other alloys) can be a lot trickier. Karat gold markings are another story. Mis-markings are rare but, due to the gold price, when you get hurt, it can be quite expensive. With gold, you have to always be skeptical.

Buying tips
Always be skeptical about any precious metals items that come out of Mexico. A common inexpensive gold alloy down there is 6K. It is often stamped 10K or 14K. Also be aware that all sterling knife handles are made with with a fairly thick sterling foil, with resin (usually) inside the foil. The same with candlesticks and many other items - these are called hollowware.

Coins
Most jewelers also sell gold coins and bars to their customers. They may be interested in buying yours but I would guess that they would only pay slightly under spot. The pouches and bars would have to be in perfect condition to get the best price.

Selling gold bearing electronics scrap

Quote: I have about 4+ 55 gallon barrels of gold fingers and other misc industrial gold (connectors, pins, etc) that I'd like to refine. Would anyone be able to help me or recommend someone in the area to help? I own 3 business's and am just to busy to do all the research I think should be done to start this project. I can supply the site, labor, funding, and material to be refined I just need the brains. (maybe all my teachers were right,LOL)

43 What is the net weight of the 4 drums? Before weighing, make sure there is no rain or snow water in the drums. If there is, use a pick and punch a couple of holes very near the bottom of the drums and let them drain. Can you put several fairly large representative samples of the material (maybe 10# each) on the floor and take good separate photos with some close ups? Depending on the bulk density of the material, I would guess the total weight to be between 600# and 2500#. Depending on the types of material involved, I would guess the gold content to be between $3,000 and $50,000. Don't assume the higher value!!! You have several options: (1) You can take the material to a refiner. There should be some refiners in St. Louis that could handle your material. This can be dangerous because of the way that you have mixed the material. It sounds like the mix is very nonhomogeneous. This produces a very large gray area in the value of your material and, if the refiner wants to cheat you, he very easily could, since you have no idea of the value. A way around this is to hire a rep to accompany the material at the refinery and live with it until representative samples can be taken. I have performed this rep function many times in the past. (2) Sort the material into like types and small lots and sell it outright. You have an Ebay business and this might be the best place to sell it. (3) Set up to refine it in your facilities. The processes that have been covered in this forum are inadequate, I feel, to handle such a large amount of material. In fact, I would advise against any acid system. There would be lots of waste and it would take many days or weeks. Fume control would be a very big problem. A large refinery would simply burn it, melt it, sample and assay the bars, and ship them to a large primary smelter. The whole thing would take about 2 days. For you to set up to do this legally, it would be very costly. Also, the quantity you have is way too small to economically set up to do this. Were I to refine this material, I would definitely use cyanide/peroxide to strip the gold selectively from the base metals. I am assuming the gold is visible and not encapsulated. This might sound scary, but it is more safe than acids in the right hands. There are essentially no fumes and it would only be a 3 or 4 day deal, for the 4 drums. I used cyanide for this purpose, for at least 20 years, with no mishaps. It basically would require a cement mixer surrounded by a berm, a few plastic drums and buckets, and maybe $500-$1000 in chemicals. There would be some acid work at the end that would require some fume control. There are some problems in obtaining cyanide and having the waste hauled off, but I think they could be easily solved, legally.

44 Maybe, (2) above is your best bet. Of course, you still don't know if you're getting true value.

Precious metals prophets

I never listened to gold prophets. Half are right and half are wrong. The best way is to turn your money, ASAP. A large number of intelligent buying/selling cycles will always make more money than holding it and hoping the market will smile on you. Pay not much attention to the market. Buy and sell. Buy and sell. Turn your money

CHEMICALS
Buying nitric Safely handling nitric
Getting nitric acid seems to be a problem for most of you. The last time I bought it was about 2 years ago. I bought a 55 gal drum in Houston. It was used in a large industrial plant so, there were never any problems getting it. I think the name of the company we bought it from was Industrial something. Maybe, Industrial Chemicals and Supplies. Industrial was a company that repackaged industrial grade chemicals into smaller lots. For example, they sold nitric in 1, 5, 15 and 55 gal. containers. If you go to a large chemical supplier, such as Univar, you can only buy 55 gal drums. The big suppliers don't usually repackage. There's usually at least one company in each city that repackages. You have to call around. In the L.A. area, there used to be Tri-ess Sciences. When I bought the nitric, two years ago, I asked the salesman what the laws were concerning buying nitric in Texas. He said that anyone could buy it if they picked it up themselves. They would only deliver or ship to companies. Due to the hazards, shipping costs could be several times more than the cost of the nitric. Local delivery was free if you bought a certain amount. He said that, in Texas, any quantity above 5 gallons had to be in stainless containers. One and five gallons could be in plastic. Prices at that time were as follows: A 1 gallon jug was $12. A 55 gal drum was $2.50/gallon. The other sizes were somewhere in between. The 5 gallon container ran about $7/gallon. The 15 gallon carboy about $4/gallon. The 15 and 55 gallon containers were stainless and both required large refundable deposits. The deposit on the 55 gallon drum was $750. The 15 gallon was around $200 or

45 $300. Call around to chemical companies and get info for your state. When I got the acid in, I always pumped about 8 gallons into good one gallon plastic jugs, for ease and safety of handling. Don't use milk jugs. They're too thin. I always bought new jugs from Industrial. They were only a dollar, or so, each. Make sure they give you lids. Transferring acids can be dangerous. Here's the way I did it. This method works for any liquid chemicals. Most chemical companies sell inexpensive plastic, siphon type drum pumps. You can also get them at Grangers. They can be used on any size container, up to 55 gal. There are basically two types, the more expensive heavier red ones at about $10-$20 and the green ones at at about $7-$12. I prefer the green ones. They are less bulky. Also, the green ones have a fast flip type seal cap (vent) whereas, the seal cap on the red ones is a more cumbersome screw on type. Here's the red type. This company's prices are much cheaper than normal. Maybe, the first one listed is the green one. You can see the red screw on seal cap (vent) at the very top of the handle. http://www.bascousa.com/store/.....TEM_ID=165 Before pumping, I get everything ready. You'll need rubber gloves and a welder's type face shield. Have a couple of milk jugs full of water to rinse off any nitric drips that get onto the jugs you are filling. If you're outside, use a hose. Put a jug into an empty 5 gal. plastic bucket. With the seal cap open, put the stem of the pump into the nitric. Put the hose part of the pump into the empty jug. Close the seal cap and pump a few times to get the siphon going. When the jug is filled to about 3" from the top, immediately open the seal cap to break the seal and stop the siphoning. You'll have to move fast. When you open the seal cap, the jug will keep filling until the hose is empty. If your timing is right, the jug will finally be filled to about 1" from the top. Be careful. It's very easy to overflow the jug. The seal caps on the green pumps can be manipulated, with practice, much faster than the red pumps. Fill a bucket with water, raise it about a foot, and practice a few times siphoning the water into jugs. Hold the tip of the pump hose above the jug opening until it stops dripping. Put the hose into a second empty bucket. Put the jug lid on and rinse the jug with water. Repeat When you're through, pull the pump stem out of the nitric and allow it to drip dry. Put the stem into the second bucket with the pump hose. Hold onto both the bucket and pump and carry them outside. Open the seal cap and, grabbing both hose and stem together, turn the pump upside down. Pour water into the stem and hose until the pump is thoroughly rinsed. It will drain from the open seal cap. Turn the pump upright and hang it up to dry. If you don't rinse the pump well, any trapped acid will eventually degrade the pump and it will stop working properly. It

46 will mess up the internal valves. The next time you use the pump, check to see if it's perfectly dry. If it isn't, rinse the pump with a little distilled water. You don't want to get any tap water in the nitric. Tap water contains chlorine. This will cause problems if you dissolve silver. The chlorine in the tap water combines with the dissolved silver to form the insoluble silver chloride. I also give any jugs that have contained tap water a couple of small distilled water rinses. Reagent grade lab chemicals cost as much as 50 to 100 times more than technical grade chemicals, I know of no refining process that requires the use of any reagent grade chemicals. They are a waste of money.

Testing for nickel

Clean the area. Drop of 50/50 nitric - let it work; several drops (2, or 3 - you must neutralize the acid) of ammonia; drop of dimethyl gloxime (1% in alcohol or dist. water - it dissolves very, very slowly in water). Nickel will turn bright red. I hope I remember that right - I didn't look it up. If the nitric goes slow (cold outside), first heat the area a little bit with a lighter. It the part is thin, heat from underneath. Or, put it in a warm place and let it warm up first.

Using dimethyl gloxime (DMG)

DMG will turn bright yellow (precipitate) in the presence of palladium, on the acid side. On the ammonia(cal) side, nickel turns bright red.

More on DMG
A gram of DMG is about a lifetime supply. One gram makes a 100 mL. of solution. One mL is about 20-25 eyedropper drops. It only takes one drop. That's 2000-2500 tests per gram. Fisher Scientific, on the net, has 100 grams for $116. You could probably find it cheaper. You could spread the costs among, say, 15, or more, people and have someone get it, divide it up, and mail it out. Or, someone could buy it and sell it by the gram for a few bucks. Let him make a few bucks for the effort. It is harmless to ship, I think. Just use a small ziplock baggie inside of a pill bottle.

47

Still more on DMG

I think I remember that 1% DMG will dissolve, in distilled water, in about 2 days. Make in up in a dropper bottle and shake it occasionally. DMG dissolves immediately in alcohol. I usually used grain alcohol (ethyl) Everclear in a liquor store. Or, I might use denatured alcohol (pharmacy), which I think is ethyl with a little bit of methyl, just to make you blind if you drink it. I don't use rubbing alcohol, which is 30% water and 70% isopropyl alcohol. When it said alcohol, I used alcohol. DMG in water or alcohol seem to do the same thing. Make both up at 1% - 1 gram per 100 mL of solution. I read somewhere that the 1% DMG distilled water solution works faster and more efficiently than the alcohol solution. I know, from experience, that the DMG will finally dissolve in water. Takes a little heat, time, and shaking or stirring.

Hydrazine sulfate
I have often used mono hydrazine sulfate to drop gold, although I think it is considered a carcinogen. I used it when I had large amounts of nitric acid in the solution. When using it, the nitric doesn't have to be removed or tied up.

Dont use alcohol in aqua regia

Every once in awhile, in the literature, you'll read a procedure that uses alcohol to eliminate nitrogen oxides from aqua regia. Besides the possible explosiveness of doing this, I never liked using it. I hated the smell and the sputtering reaction. The only thing I used alcohol for was to quick-dry gold powder.

Hydrazine chemicals
I once worked for a refiner that used full strength liquid hydrazine to drop gold from aqua regia. It only took a small amount and it reacted violently and generated a lot of heat. It seemed like someone was always getting acid burns. I vowed to never use it.

48 Hydrazine sulfate is another story - no violent reaction. Although it's somewhat carcinogenic (especially the dust), I used it often for dropping gold out of aqua regia that contained large amounts of nitric acid. Nitric acid doesn't affect the precipitation. You don't have to boil the AR, add urea, or treat it in any other way. When you buy it, a slight amount of water has been added to prevent dusting. I used to break up the clumps by grinding it with the bottom of a small beaker. I then sprinkled the powder into the aqua regia, in small increments, and gave the solution a stir. It doesn't take much. Use gloves, a mask, and a fume hood. Hydrazine sulfate is also used, by some of the large refiners, to selectively drop PGMs. The precipitations are pH dependent. Check the patents.

Nitric acid purity

For 40 years, I have used tech. grade nitric to refine gold and silver, with zero problems. I even used it for parting in fire assaying. I don't ever remember finding chlorides in tech. grade nitric. If you do find chlorides, you need to change suppliers. For our purposes, reagent grade is a huge waste of money, at about $50 for a 5 pint jug.

CIRCUIT BOARDS
Circuit boards from a professional refiners viewpoint
NO refiner, worth his salt, uses chemical methods to go after the PM's on circuit boards. They know that there's no money in it, due mainly to chemical costs, fume control, and waste disposal costs. They may hi-grade the boards for fingers and hi-grade IC's but, few other components, if any. The fingers are cyanide stripped and the IC's are put through aqua regia. Here's how they all run the boards. They burn the material and then grind it up, usually in a ball mill. Then, they separate the dust (pulp, they call it) from most of the metallics with an 8 or 10 mesh screen. The metallics are melted, cast into bars, numbered, weighed, and drilled scientifically. The drillings are blended and assayed for all PM contents and copper. The pulps are blended, thief sampled (a tube is run down into the pulp), and assayed. The bars and pulps are then shipped to a huge refiner or a copper smelter. In the past, most of these places were in Europe, mainly in Belgium. In the U.S., ASARCO would take material in some of their plants but, it was an on again, off again proposition. These

49 companies have great rates and slow payout, about 3 months, awhile back. They even pay for a major portion of the copper. Nickel over 5% draws a penalty. After sampling and assaying, the smelters advance money against recovery but, they charge interest. I haven't been involved with smelters for quite awhile. Some details might have changed since then. The present trend for the amateurs to chemically process boards is, as far as I'm concerned, a sucker deal. I imagine this is the main thing that Scott Andrews has in mind in his aversion to refining by amateurs. I know that this stuff is fun to play with. However, when you gear up and try to make money, you will lose. The numbers just aren't there. Chemical costs and waste disposal are the biggest money eaters. It's easy to deal with small amounts of waste. When you get bigger, the amounts of heavy metal, acidic toxic waste will grow much faster than you realize. To dissolve a pound of base metals, it will take at least a gallon of 50% acid plus rinses. If you dump large amounts down the drain, you'll be caught in no time. In some states, you need a license to generate this waste. There's a whole cottage industry bilking the public, selling info and chemicals to process boards. This all seemed to start with Shor International. I must admit, however, that Peter Shor's stuff keeps you as safe as possible and, it works. I can't say the same for a lot of the other stuff out there. I hate the sodium nitrate system since it gives people false hopes. If you seriously want to refine, it's a lot easier to get real nitric acid than you're led to believe. The best way to make money with boards is to buy low, sell high, and don't refine them yourself. I'm not saying you shouldn't hi-grade them. It usually pays to sort the stuff into homogeneous lots rather then having a large mixed lot. Buyers and refiners lick their chops when they see a mixed lot. They know that you don't know. When taking a lot of boards to a refiner (I would suggest a ton, or more), accompany (most refiners allow this - it's called repping - representing your material) the lot and don't leave until the material is homogeneous and you have good samples in your hand - the more different samples - the merrier. You will have to schedule this with the refiner. Don't be lazy or let the refiner distract you or take you away from the material. Stay with it, when required, until you have samples. Even when the stuff is being burned, if you're not around to watch it, the refiner could throw in some barren burnables to reduce your values. Think of ways that the refiner can screw you and avoid these traps. Repping is a boring job and it may take 2 or 3 days. At the end of the day, try to make the refiner put the stuff into sealed drums, sealed with lead or plastic numbered tags. If you rep your own stuff correctly, it's less important to sort it. In any case, pull off the good gold ceramic IC's and deal with them separately. They won't burn or chop and are hard to grind. Even though they're the best stuff on the boards, they may not turn up in the samples. I'm not saying that all refiners are dishonest. However, enough of them are to make preparation always necessary. Get your ducks in a row before taking the material to a refiner. It doesn't pay on

50 real low grade stuff. Check on his charges. He may have a whole slough of them. There are processing charges, refining charges, assay charges, etc. Most refiners charge at least $2.50 a pound just for processing charges and, they deserve it. If your stuff is too low grade, you may end up owing him money. What do you do with the samples? If you are big enough to generate a ton of good boards, you are big enough to set up fire assaying equipment and learn how to use it. You can send samples to a professional assayer but a good one will charge from $50 to $300 per sample. The higher rates include the platinum group. I would avoid most mining type assayers, although their rates are much less, unless they have a background in scrap. They are good in their field but scrap is a different deal.

COLLOIDAL SILVER
General information Making CS
Argyria is a rare bluish grey tint to the skin caused by ingesting fairly large amounts of silver. I think I read somewhere that there are, presently, only 70 known cases. The color comes from silver sulfide, which is produced by sulfur bearing materials in the body Colloidal silver has powerful antiseptic qualities. I think that Silvadene is a CS salve. I heard it was developed for skin grafts. It kept the area moist and prevented infection. I used it once on a 2nd degree nitric burn that covered my lower leg. It was healed in just a few days. Probably, millions of people drink small quantities of CS daily. They buy it pre-made or they make their own (very easy to make). Google "colloidal silver" and you get a million hits. You can either buy CS making equipment or simply make your own. CS can simply be made with the following: Distilled water, the purist you can find. Walgreens is the best I found. If you have no Walgreens, buy a brand that says steam distilled. About one foot of pure (I prefer 9999) silver wire, about 1/16" diameter, cut into 2, 6" pieces. A water glass, about 8 oz capacity 1, 2, or 3, 9V batteries (see discussion below).

51 Two snap connectors for attaching the batteries in series (Radio Shack). Two connectors with a snap plus a wire lead (Radio Shack). Several wire leads with clips on both ends. A milliamp meter (optional). Not necessary, but I like to watch the current. Also, it can be used to compare water purities. In general, the lower the initial current flow, the purer the water. How to make CS. (1) Fill a glass, to about 1" short of the top, with distilled water. (2) One at a time, put the silver wires into the water, about 1/2" shy of the bottom. Fold the top of the wires over the edge of the glass. Pinch it so the wire is held flat against the inside of the glass. This works best if the top of the glass is flared out, like a beaker. The 2 wires should be on opposite sides of the glass. (3) Batteries. The more batteries you use, the higher the current flow and the faster it will go. However, I prefer only using 1 or, maybe, 2 batteries. The solution goes through color changes and the lower current makes it easier to stop at the color I prefer (light yellow). Anyway, with more than 1 battery, snap them together with the connector(s), in series. (4) Snap on the single snap connectors to the batteries and clip the 2 leads from the batteries to the 2 silver wires. If you use a meter, connect it in series with one of the leads from the batteries, using two wire leads. Battery to meter. Meter to silver wire. (5) You are now making Colloidal Silver. In from 1 to 4 hours, it will turn a light yellow. That's where I stop, although many like it darker (it can get black). I'm more cautious, when I eat chemicals. The time depends on water volume and current flow. (6) I drank about 2 teaspoons a day, diluted in water. Nasty, metallic taste. I had the feeling it was kinda like buying a device to keep the tigers away from your door. It must work, since you haven't had any tigers at your door. On the internet, you will find all sorts of wonderful medical claims for CS. Notes: When you use very pure water and silver, the silver in the solution is a pure, metallic, silver colloid. If the water is impure or, if you dissolve certain salts in it (as in many of the commercially bottled solutions), the silver can form compounds. I have read that Argyria victims had used silver compounds, such as silver nitrate. On the internet, you can buy 999 or 9999 silver, both in 12" lengths. I buy the 9999. I think the safest CS is that that's made correctly at home. Read

52 what you can find on the internet and try to weed out the BS. CS is also supposed to be good for animals and plants. It probably even works on dandruff, like Listerine claimed to do. Some say that the smaller the particle size, the better. The lower the current/water volume, the smaller the particle size. Completely off the subject: A Helloweez Hint: Corn Huskers Lotion is great for chapped refiner's hands.

CONTACT POINTS
Processing large silver contact points
This is in response to someone who has 10# of industrial contact points and wants to know how to process them. I assume that you mean the type points that are pictured in the large photo on this thread. It's hard to spot the points in the photo, although I see one or two. Mainly, the copper bussing that the points are silver soldered to is the most visible This post does not concern the small points commonly found on relays. They are a totally different deal. The large points are found on large electrical panels, switches, starter motors, etc. There are two basic types: (1) those made of solid coin (90%) silver. (2) Those made of tungsten powder held together with silver. I've seen coin silver points as big as 2", or more, in diameter and 1/8" thick. The tungsten points are thinner and much harder than the coin silver ones. They are also worth much less although I don't remember their value. The figures 25% and 40% silver stick out in my mind. Harold probably knows the exact values. You can tell the difference by trying to cut a thin slice off one edge with a knife. The coin silver ones cut fairly easy whereas, the tungsten points hardly cut at all. The silver points are whiter. The tungsten points often have a cross hatch pattern on one side. Both types are attached to the copper bussing by the use of silver solder. Sometimes, the copper bussing is silver plated. Don't be fooled. Underneath the plating (scrape or cut some off), you will always find pink copper or a white copper alloy containing no silver. Also, silver plated copper is basically contaminated copper. When you sweat the points off of the copper, you must always assume that cadmium is present, usually in the silver solder. Cadmium is very toxic. When molten and very hot, it produces toxic red cobwebs that float in the air and can

53 enter your lungs. Zinc does the same thing except the cobwebs are white. Always sweat outside and use a particle mask. Heat the copper with a cool torch, behind the point and, when the solder melts, slide the point off with something like a stainless dinner knife. The problem is, this operation takes three hands. You can put the copper in a vise. Probably, the easiest way is to first secure a coffee can so it can't move. Then, slide the point off on the edge of the can. The point will then go into the can. I assume you want to make as much money off the points as you can. I assume your 10# are points plus solder alone and not points plus copper. To make any money, the points first must be removed from the copper. You have two options. You can refine the points to at least 99.95% pure, cast into bars, and sell the pure for a little under spot price. Or, you can shop around for prices and sell the points, as is, without refining, for about 60 to 70% of spot. I would sell the points as is, with no refining. Although 10# seems like a lot, it is no where near the quantity needed to economically set up the equipment required to refine to the necessary purity, at least 99.95% and better still, 99.99%. To refine, you need a fume hood, a melting furnace, a Thum silver cell, and lots of associated equipment and tools. Even for 10#, all this stuff is necessary. If you put effort and money into any other refining process, you will be disappointed. You won't get the required purity and will receive a lot less money. This is because that, to reuse the silver for most industrial purposes, it has to be at least 99.95% pure. Someone else will have to refine it to that level and, refining costs money. If you decide to sell, sort the points into 2 piles, the coin silver points and the tungsten silver points. Sell each pile separately. If the pile is mixed, you create doubt as to it's value and the buyer will take advantage and give you less money for the total. If you can find a buyer that is knowledgeable about points, you can probably get more money. Ignorant buyers are often afraid to give you the right price because they don't know the true values. The coin silver points are 90% silver. The silver solder runs much less. When you sweat off the points, you end up with a value of about 81% silver. This isn't always the case but, it was the average of all the points that I have processed. To figure out a fair price for selling your points, say 60% to 70%, first determine what a pound of pure silver is worth. Today's market is $14.01/tr.oz. and there are 14.58 tr.ozs. in a pound. Therefore, a pound of pure silver is worth 14.01 X 14.58 = $204.27/pound. To figure a 60% selling price, go 204.27 X .60 X .81 = $99.28/pound. For 70%, go 204.27 X .70 X .81 = $115.82/pound. If you don't often work in U.S. weights, there are 454 grams in a pound. When I looked up the silver price, I noticed that the gold price was $684.80. This is nearing a very interesting price because, at $685.73, gold is worth exactly

54 $10,000 per pound. A pound of pure gold is a cube about 1 7/16" or 3.64 cm., on a side. A 5 gallon bucket will hold about 800# of gold. A cubic foot, a little over 1200#.

More on contact points

I have run many 100's of pounds of the large contacts and have never run across palladium. That doesn't mean it's not possible. I have an old classic book, by Butts and Coxe (their real names), called "Silver: Economics, Metallurgy and Use", that mentions the use of PGM in some contacts. Mainly, they are said to be found in the smaller points found in relays, etc. Pure palladium points were commonly found on the wire relays used in telephone switching stations. These have mostly all been scrapped out by now. I have also seen pure Pd points on other relays. They are usually easy to recognize. Instead of being round, they are usually long (1/8"?) and narrow with 3 flat areas, like half of a hexagon shaped wire sliced lengthwise. They are grey in color. I usually sorted out the tungsten/silver contacts, saved them, and tried to sell them separately. When I tried to dissolve them, I ended up with a fluffy yellow mess. Harold actually processed them. Somewhere on this forum or the other forum, he tells how he did it. I didn't find many of them so, I didn't mess with them. I didn't ever try stannous chloride or KI to detect the W (tungsten). When I put the points in nitric and got the fluffy yellow gunk, I knew I had W. I seem to remember having some success dissolving W in straight 35% hydrogen peroxide or fairly strong sodium hydroxide. I might mention that stannous chloride is very specific for gold and PGM's., each of which produces different colors. The only base metal I know of that produces a color is cobalt - blue. C.M. Hoke wrote another book, "Testing Precious Metals", in which she thoroughly discusses the use of stannous chloride.

Even more on contact points

When I wrote that, I was thinking about the larger contacts that can be sweated off. These are usually coin silver (90%). The silver solder used to attach the points is much less pure and usually contains cadmium. After sweating, you end up with a product that is about 82% silver. This is something that buyers can deal with. They know the factors and, to determine the value, they simply weigh the points. In addition, this is a product that the refiner can process and make money with. On the other hand, let's look at your relay points. I assume that they have been clipped off. If so, your final product runs about 10-50% (who knows?) silver,

55 depending on how much of the copper alloy blade is left attached to the silver. Cadmium is probably present. This and the lower, unknown percentage creates big problems for the average refiner and makes it difficult for him to make a profit. He really doesn't want this kind of stuff, especially in 5# quantities. Even if you had a ton of the material, the refiner still might refuse it. For these reasons, it may be impossible to find someone to buy the material. Since the refiner doesn't want it, the buyer has no place to get rid of it. Also, due to the irregular pieces of copper backing, no one has any idea of the overall silver percentage. If you do happen to find a buyer, you will only get a small fraction of the silver value. Big, sweated, silver contact points are a great item. Small, clipped, points might be virtually worthless. Nothing has value if you can't sell it. If you could figure a way to mechanically separate the points from the copper, it would be a different story.

CYANIDE
Refining Technistrip AU
Techni-strip Au is a very poor choice of stripper for the refiner. It's very expensive and it's extremely difficult to remove all of the gold from the solution. Most of the gold is probably still in the solution. I imagine that your low yields are due to this difficulty. Usually, most users ship the loaded stripper back to Technic for gold extraction. Technic also sells proprietary additives to help get the gold out but, I haven't had much luck with them. The standard zinc dust method for removing gold from cyanides doesn't work on this product. There is a particularly nasty precipitation method using sodium hydrosulfite but, I certainly don't recommend it. The best way is to not use this product, to start with. Techni-Strip Au is a cyanide based stripper designed for platers to remove faulty gold plating so that the parts can be re-plated. The older commercial strippers didn't work too well. They attacked the underlying base metals and, also, the dissolved gold would tend to plate back onto the copper. Technic came up with additives to prevent these things from happening. These additives also prevent the user from being able to drop all of the gold out. It strips great but, it doesn't want to give up the gold.

Cyanide dangers

56 I knew the son of a guy that died from cyanide inhalation or ingestion. He was dissolving the silver solder that held the carbide tips on scrap coal mining bits. He was running several drum quantities and working inside with no fume control. A few rules for cyanide are: Don't get it in your mouth. Don't mix it with acids, even something as weak as coffee. Don't work in a confined area. Don't smoke or drink around it. Don't work over hot cyanide - your skin will break out with "cyanide itch". Wear gloves and a face shield. Get an excellent fume hood Your friend didn't know or obey the rules. You must obey the rules with cyanide.

More on commercial cyanide strippers

I have quite a bit of experience with cyanide gold strippers. I assume you are talking about proprietary strippers that are sold by such companies as Technic. If so, I must warn you that, with most of these, the gold is so tightly bound that it is very, very difficult to recover. Besides cyanide and an oxidizer, such as m-NBSS (meta-nitrobenzoate - sodium salt), there are other additives which prevent attack on the copper. These additives make it very difficult to recover the gold. For example, with the most common commercial stripper, Technistrip Au, it is virtually impossible to drop the gold with zinc. About the only way to recover the gold is to send the solution to Technic. This can be quite expensive, with shipping hazardous waste, paying refining fees, and perhaps taking a beating from the refiner's magic pencil. If you can find a product that is guaranteed to only contain cyanide and m-NBSS, you will be able to zinc out the gold. I don't know if these simpler solutions are still available as a commercial product. However, if you have no experience with handling cyanide or dealing with the wastes, I would definitely avoid it. Economically, cleverly selling the fingers on Ebay would most likely give you the best return

Refining cyanide solutions

Before using zinc dust, adjust the pH to 12 min. with sodium hydroxide. 12 is the safe pH - not 9. Also, in order for the gold to drop, some zinc must dissolve. This will occur more efficiently if the pH is 12, or a little higher. After adding enough zinc dust to drop all the gold, allow the gold plus excess zinc to settle, preferably overnight. During settling, hang a zinc bar in the solution. This will prevent the gold from redissolving in the cyanide.

57 The above assumes a cyanide matrix, of course. A true cyanide gold electroforming solution can contain about 4 tr.oz. of gold per gallon. Fume Hood! Fume Hood! Fume Hood!

Using zinc dust

The best thing to use in CN gold solutions is sold by the name, "zinc dust." It is normally 325 mesh. There are many manufacturers. It is usually packaged in 50# metal pails. It is also sold in smaller quantities by companies that repackage chemicals. Sorry, but I have no present sources. It is often lumpy, especially if it's not kept dry. I usually put it into a small squeeze type flour sifter, to break up the lumps, and sprinkle it into the solution, with stirring. When the precipitate turns slightly gray (from excess zinc), all of the gold should be out of solution. Go slow with the zinc. If the conditions are right, the Au/Zn weight ratio is about 1 to 1. After adjusting the pH to 12 (and, before adding the zinc), it often helps to add about 1 oz of sodium cyanide per gallon of solution. FUME HOOD!

A stupid question about using acids to drop PMs from cyanide solutions
I don't think the procedure will work on Au or Ag cyanide baths. When you acidify the sample, the free CN is eliminated but the Au remains as an acid insoluble AuCN. The same with silver - insoluble AgCN forms. The only acid treatment that I know that works, for either, is the hot H2SO4/HNO3 fuming method that I explained in an earlier post - it decomposes the AuCN or AgCN. This is the standard wet method for analyzing Au or Ag cyanide baths. The gold is converted to gold powder and then is separated and weighed. If silver, it is fumed, cooled, carefully diluted w/H2O and then titrated with .1N KSCN, using a ferric ammonium sulfate indicator. Both methods are available in any plating solution analysis text. The simpliest qualitative field test would be a battery or two and a couple of stainless electrodes. After plating for awhile, you can test a yellow or brown deposit for gold by applying a drop of nitric. If it doesn't dissolve, it is gold. If it does dissolve, it is brass, which is also deposited out of a CN matrix. If a white or

58 gray deposit, test for silver by applying first a drop of nitric and then a drop of HCl or table salt solution. If silver is present, a white silver chloride ppt. will form.

Testing for gold in cyanide solutions

I don't think a decent color spot test exists. The gold is too tightly bound in the cyanide complex. An AA is the best, of course. Takes about 1 minute. I also used to use 20mL of conc. H2SO4 and a 5mL sample, in a 250mL erlenmeyer flask, UNDER THE FUME HOOD - hydrogen cyanide gas (same as prison gas chamber gas) comes off. Fume 'til the solution is clear and the gold drops out as a brown powder. Very small amounts of gold will be visible. The solution will turn black (carbon) at the first. This is cleared up by the addition (only 1 or 2 drops every minute, or so, until the solution clears up) of nitric acid to the hot sulfuric - USING GREAT CAUTION - gloves and face shield. When you add the nitric drops, there will be much fizzing. Don't add an excess of nitric after each addition, let it cook for awhile. It takes about 10-20 minutes to do the test. You could also use stainless electrodes and electrolyze at 1.5 to 3 volts. Any indication of brown or gold color on the cathode (negative) indicates gold. This can also be done quantitatively with platinum electrodes, but it takes several hours. Also, it can be plated onto about 10-30 grams of lead sheet and then cupelled. Another is to - UNDER THE HOOD - acidify 1mL of sample solution. A canary yellow precipitate is most probably AuCN.

DENTAL GOLD
Dental gold info
I know you're in between a rock and a hard place with this. I've run quite a bit of dental gold but, it's all been yellow. In fact, there was always a general rule to never buy white dental gold unless you really knew what you were doing. Scott Andrews, the very knowledgeable owner of recyclebiz.com, wrote this dental gold guide on eBay. http://reviews.ebay.com/Advice.....0002336051

59 I spent an hour yesterday trying to research white metals used in dental materials without much luck. I did find that the white metal could be either be white gold, nickel/chromium alloys, or cobalt/chromium alloys. The reason the white dental gold is white is due to large amounts of palladium. The nickel and cobalt alloys contain no gold and could be magnetic. I found no mention of silver ever being used. In Hoke's, "Testing Precious Metals", she mentions that the lower grade yellow dental golds will tarnish and darken in the mouth. I noticed that, in the eBay photos, some of the yellow gold looks tarnished. Out of the 31 crowns in the photos, 6 are yellow gold - about 20% of the crowns, by count. Weight wise, since the gold is heavier, I would guess that about 35% of the lot to be yellow gold alloys - assuming that the white materials are non-gold. The only two metals on earth with color, other than white, are gold and copper and their alloys. Copper is poisonous and I can't imagine copper alloys being used alone. However, in all the yellow dental gold alloys, there is some copper in the formulas. Nickel solutions are usually green. The copper in the yellow gold would produce a blue color. Together, the color would be turquoise. All in all, you must have some gold in the solution, if everything has dissolved. There also is some platinum and palladium in all the yellow gold formulas that I could find. Have you tested the solution for gold, platinum, and palladium, using stannous chloride? Six of the crowns were yellow so, it seems to me, that there has to be some gold someplace. I know I haven't answered your question as to what to do as to the seller. Maybe someone else can answer this question. Never buy white dental materials unless you really, really, really know what you are doing. Never buy any dental materials on eBay.

Refining dental golds

I started writing this before Harold's excellent post. In refining, for each type of material, there are probably at least 6 different methods of doing things. These are good, bad, or stupid. Please note that both Harold's way and my way have been proven to work. It is best to learn every way of doing something and, then, you can think about what

60 is the best way for you, based on the equipment you have, turnaround time, cost, profits, efficiency, safety, etc. I hate to admit this but, if I ever refine karat gold or platinum group from jewelry or dental, again, I will adopt some of Harold's techniques and incorporate them with mine. I only hope that he has learned some tricks from me, on things like the sulfuric cell. Did you use real nitric or sodium nitrate? There is always platinum (from .5% to 8%) and palladium (from .5% to 2%) in dental gold. The amateur looks at the high numbers. The pro looks at the low numbers. The Main Problem -Silver Quote: I thought all nitric was gone as there were still undissolved appliances at the bottom. The silver in dental alloys can be quite high (3% to 24% - the average is about 12%). If the silver percentage is over 10%, it becomes very difficult to dissolve all the gold in AR. Silver chloride forms and it coats the gold. This is probably the gray color you now see on some of the metal. The silver chloride stops the action and that's why you thought there was no nitric left. From here, everything snowballed. It takes both hydrochloric and nitric to dissolve gold. If EITHER acid has been used up, the action will stop. So, excess metal on the bottom does not necessarily mean that all the nitric is gone. It could mean that the hydrochloric is all gone and there's still excess nitric. You should of inquarted, mainly because you must deal with the very possible high silver content. Quote: Thinking there might be some PL, I added some Sodium Chlorate. It boiled over into my heating element, so I unplugged it and dumped the solution back into my big solution. I added a ton of SMB (I guess the nitric) was not all gone. I sprinkled ammonium chloride into the solution moving very slowly through the filters and it turned red.

It was a mistake to add any of these chemicals before taking care of the nitric. However, it is less of a problem than you might think. How I would have done yellow Dental Gold. I am using real nitric acid.

61

All of the techniques not covered in detail are covered in detail elsewhere on this forum. INQUART (1) Weigh the metal (2) Inquart with silver or copper. First, though, calculate the copper or silver you need to end up with 25% gold. Make sure the molten alloy is well mixed before shotting. Stir with a carbon or quartz stirring rod (jewelry supplies). DISSOLVE THE COPPER, SILVER, ETC. IN NITRIC (3) Estimate the amount of nitric nedded to dissolve the Ag. One gram of copper needs about 4.2 mLs of concentrated nitric. A gram of silver will need 1.2 mLs. (4) Put the metal into the Pyrex dissolving container. You could use plastic and no heat but, it's slower. For small amounts, I prefer glass beakers so, I can heat them. (5) Cover the metal with distilled water, plus about 1/4". (6) Heat the solution until you first see wisps of steam coming off. I like the hot plate about medium. Medium low for very small amounts (7) Measure out the calculated total amount nitric you'll need. (8 ) Dissolve the Ag, Cu, etc., with nitric. Add about 5 mL of straight nitric. You will immediately get action. It will shortly (few minutes) slow down. Give it a gentle but complete stir. It will flare up a little bit. Let it relax. Add some more nitric. When it's finished, add some more. Repeat until all the the Ag, etc., is dissolved and you only have gold powder. Test this by dragging the powder to the side of the beaker and looking at it. You can, also, mash around with a stir rod, to check for lumps. You may need about 10%, or so, extra nitric. Try not to use too much. This whole thing should take 15 to 30 minutes. The reason to start with only 5 mL, is to prevent it from foaming over. The solution will get quite hot from the dissolving and, you have to be careful of instant foamovers. Towards the end, you can progressively add more nitric at one time. But, never add more until the last addition has died down. A good reason for working with heat is to eliminate foamovers. When you add a little nitric to a cold solution, it, at first, won't do much. You add a little more and, maybe, a little more. As you've been doing this, the dissolving action is heating the solution up, slowly. When it reaches a critical temp., it suddenly all works at

62 the same time and, boils the solution over. Don't ask me how I know this. Most boilovers are caused by working with cold solutions or, by dumping all the acid in at the same time. You will probably need more water, as you go, to keep the metal salts from crystallizing. At the end, you want to end up with 50% water. Stir. (9) Allow to cool and settle over overnight. I like to prop a piece of wood under it, so the solids settle to one corner. Note: Summary of what we have to this point. It's good to figure out what is where, no matter what you're working on.. ----(a) In the solution, we have all of the silver, palladium, and all the base metals. If we used silver to inquart, instead of copper, we will also have some platinum in the solution. ----(b) In the solids, sitting in the solution, there is most or all of the platinum and all of the gold and, some dirt. (10) Separate the solids from the liquid. You can filter and rinse it or you can pour off the solution with several rinses - pour off - rinse - settle - pour off repeat. For the best chance at good final purity, filter and rinse well. DISSOLVE THE GOLD AND PLATINUM IN AQUA REGIA (11) Put clean solids in beaker. [/b](12) Cover solids with the muriatic or hydrochloric.[/b] You should calculate how much HCl you need and add about 20%. For one ounce of gold, figure about 120 mL of HCl. It's very important to have extra HCl. But, it's wasteful and more cumbersome to add way too much. (13) Heat on medium until you see whisps of steam (14) Calculate and measure out how much nitric you'll need Figure about 2025 mL, per ounce of gold. Measure on the low side. The goal is to never add any more nitric than is necessary to dissolve the gold and platinum powder. (15) Add not over 5 mL of nitric Action will start immediately. When it dies down, stir it and add some more nitric. (16) Repeat adding nitric until the gold/platinum powder has dissolved. Add - wait until reaction slows - stir - repeat. This may or may not take all the nitric. Especially towards the end, allow the action to completely stop before adding more nitric. Note: The magic of adding a little too much HCl and just enough HNO3 is that,

63 when you finish, there will be none, or very little, extra nitric in the solution. Thus, boiling down or, adding urea, isn't necessary. The first addition of SMB or FeSO4 will start dropping gold!!! If, you used too much nitric, use urea, that you've dissolved in water, until you get a pH of one. IMPORTANT: Gold in powder dissolves rapidly. If you add too much nitric, the solution can foam over, quicker than you can say Jack Spratt. The depth of the solution will make a difference in the speed of the dissolving. The deeper it is, the slower things go. The acid is way up here and the solids are way down there. For maximum speed, use a container that will keep the acid under about 3" deep. To kill or slow down foamovers, buy a small container of Anti-Foam located on the same rack as carpet cleaner rentals in the supermarket. Add 1" of the concentrate to a spray bottle and fill it up with water. Spray a little on the climbing foam. Often, it stops the foam. Sometimes, especially when real hot, it only slows it down. Believe it or not, just water in a misty spray bottle does a pretty good job on foam. Another weird way to to put a little oil on you fingertip and wipe it around the top edge on the dissolving container. I don't like oil in the solution. It tracks over to the next processes. I only use it rarely with large amounts of acid when no values are in the solution. (17) Heat more strongly at the end but, don't boil. Platinum dissolves a little slow and needs some heat. (18 ) Check to see if everything's dissolved. Tilt the beaker, stir the solution, let it settle a bit, and, using good light, look at the settled solids, if there are any. If the container is small, pick it up and look at the bottom. (19) If needed, add more nitric. Heat it up and add only 2 or 3 mLs at a time. Let it settle totally down and stir before adding. Keep checking for solids. Don't add too much. FILTER AND RINSE (20) Add 3 times water and let it cool and let the dirt settle. (21) Filter Carefully pour the solution into the filter. Keep the solids in the beaker. When all the solution has drained through, rinse the solids (dirt) into the same filter. If things slow down, get a fresh filter. (22) Rinse the filter well. DROP THE GOLD

64 (23) Choose a precipitant. There's a long list of things you could use: Ferrous Sulfate; SO2 gas; Sodium Sulfite; Sodium Metabisulfite; Sodium Bisulfite; Oxalic acid; Sodium Nitrite; Hydroquinone; Metol; Etc. The last 4 are only used in special situations. For this job, I should (but, probably wouldn't) first use green Ferrous Sulfate (FeSO4 - Copperas). It will drop the gold, without dropping the platinum group, better than any other precipitant. I could use a sulfite first and then melt, shot, re-dissolve, and final drop with ferrous sulfate. (24)Drop the gold To drop with one of the 3 sulfites, put a couple of spoonfuls in a one cup Pyrex measuring cup. Fill with hot water and stir until most is dissolved. Pour some of the liquid into the solution, let it react, and stir. If all of the nitric is gone, you should see brown powder forming in the solution. If there is still nitric, the sulfite will react with it before you start dropping gold. Sometimes, there is a false indication of gold dropping. The gold drops locally, where you added the sulfite but, when you stir it, the gold re-dissolves. At some point, all the gold has dropped out. It shouldn't take much sulfite, if all the nitric was gone. Also, with no nitric, you should get no boilovers. Maybe, use about ounce for ounce, with gold or, a little more. There are some visual indications of this. Without the presence of platinum group, the foam (when stirring) will get white and the yellow color will disappear. With platinum, whose solution is also yellow, this is harder to see. Test the solution, with stannous chloride, for the presence of gold. Add a little more sulfite, stir, and test. Repeat until the gold is out. (25) Filter, leach and rinse the gold. This has been a controversial subject between Harold and I. I would probably settle first, then, - (a) Filter the tops - (b) Filter the gold in the same filter - (c) Rinse 5 times with very hot water - (d) Remove and boil in HCl - (e) Filter and hot rinse 5 times - (f) Check for the presence of chlorides coming out of the filter, with a drop of silver nitrate made from a little silver dissolved in a little nitric/distilled water - (g) Rinse until no more chlorides - (h) Mix up enough 25% nitric, diluted with hot water, to pretty well fill up the filter. With a vacuum filter, shut it off and bleed the vacuum, first. The slower it drains through, the better. - (i) When it is drained, rinse 5 times with hot distilled water. - (j) Add 50/50 household ammonia, cut with hot water, and put it in the filter. When it has drained through, rinse 5 times with hot water. (k) Rinse 5 times with hot distilled water. (26) Dry the gold and melt it. Look for instructions on the forum. Note: if the gold powder looks grayish, it has platinum in it. (27) Rework dirty gold If the melt, the ingot, or the powder looks dirty, it is dirty. Pt makes dirty looking powder and ingots. Sometimes, the Pt.Gp. produces a fern-like pattern on the gold ingot. Always melt and shot the powder before redissolving in aqua regia. Use a different precipitant. Learn to use ferrous sulfate.

65 GRAND SUMMARY ---In the filter papers, there is likely some precious metals. If you can, keep the gold, silver, and Pt group all separate. Even if the platinum group filters have gold, keep them in the Pt. group pile. You can burn the filters or, you can add some of the best aqua regia filters to the next batch, paper and all. Don't add too many papers, unless you have a lot of solution. The hot acid pulps the paper and aids in filtering. Commercial paper pulp can be purchased for use as a lab filteraid. ---The spent aqua regia solution. It contains platinum, hydrochloric acid, nitrates, chlorides, sodium, and sulfite. You could drop the platinum out as a black powder with copper buss bars (A trick. If it isn't cementing onto the copper, add a small shot of nitric and stir it in). Or, you could put it into Hoke's stockpot. ---The nitric solution It contains silver, palladium, some of the platinum, copper, zinc, and nitrates. How do you separate the silver from the platinum and palladium? Good question. You could drop the silver, Pt, and Pd, all together, using copper bussbar. You could then melt and run the silver through a silver cell. The platinum doesn't dissolve and stays in the cell's filter cloth. The palladium dissolves and eventually contaminates the silver cell solution. Another way would be to try and drop out the Pt.Gp., selectively, using something like hydrazine sulfate at a certain pH. Maybe, sodium borohydride would drop the silver without dropping the Pt and Pd. Anyone have any other ideas?

A person had this solution and solids from trying to refine dental gold
If there's anything you haven't told me about, if I've forgotten something, or if I'm mistaken about something, tell me. Stop and let me know if anything weird happens. You have the solution, the solids and the filter paper. The solution contains nitric acid (maybe), hydrochloric acid, gold, platinum, palladium, copper, NH4Cl, SMB, sodium chlorate, dissolved rust, and water. I don't think the chemicals you added will hurt. They've all been chewed up and simplified by the acids. There is likely no SMB left. Dissolved iron won't hurt. I would settle and then filter the solution. Then, treat it as a brand new solution. (1) Filter and rinse. (2) Take care of the nitric, if any. It sounds like there could still be nitric in there. I would dissolve some urea and add a little bit and stir it in. Normally, if you need more urea, you will get bubbles. After all the other stuff you've added, who

66 knows? If you have a way of measuring pH, add til the pH goes up to 1. (3) Drop the gold. You can use ferrous sulfate or a sulfite, such as SMB. Both Harold and I have only used ferrous sulfate a few times. However, Harold probably remembers more about it than I do. Neither of us like it much and, it is more complicated to use. The Hoke book covers it in great, great detail. Ferrous sulfate is more likely to keep Pt.Gp. out of the gold, thus producing higher purity gold. A definite advantage, in your case. Depending on how much Pt.Gp. was in the metal, the more likely you'll have to rework it again, if you use SMB. Make sure you dissolve the SMB first, in hot water. Add a little at a time and stir between additions. When all the gold is out, stop. (4) Filter, rinse, and leach the gold. (5) Get the Pt and Pd out of the solution. Put some lengths of copper bussbar in the solution. In your small lot, use pieces of copper sheet. The Pt and Pd should produce a black deposit on the copper. If nothing happens, after about 30 minutes, add a splash of nitric and stir it in, to get things started. I would leave it for a couple of days. With a lot of Pt.Gp. is present, the heavy black powder can slow or stop the action. Just scrape and rinse it down and put the copper back in. When finished, scrape down the copper and collect the black powder. There will also be some black powder on the bottom of the solution. I would save this powder up and do a Pt.Gp. aqua regia later on. The Solids. You have gold, Pt, Pd, Ag, Cu, and Zn in the metal alloy. You also have silver chloride and dirt. I would first rinse, dry, and get a weight on the metal left over. Then, calculate how much acids you'll need. See previous post. In the following, I am assuming that what you said is true, about no silver chloride building up on the metal. If there is and things slow down, you may have to remove it once or twice and boil it in household ammonia, to dissolve the silver chloride. (1) Cover the gold with whatever HCl you've calculated. You want a little excess. Put into a beaker that is at least 4-5" tall (2) Heat til slightly steamy. (3) Add some of the nitric (about 1/3) of what you've calculated and measured out. Drive it hotter. Heat is very important in aqua regia, when dissolving solid gold alloys. Don't boil. When the reaction stops, stir, add another 1/3 more nitric. Add the final 1/3 in smaller increments. You may not need it all. When a small addition produces no action, you should stop adding. If you didn't have enough HCl at the first, add a slight excess and see if it starts working again. If if does,

67 you're not finished. If it doesn't, all of the metal should be dissolved. (4) Dilute 3 times with water, cool and settle. (5) Filter, etc., as in (1) though (5), above, in this post. The Filter Paper You can save them up and burn to light gray ash, melt, shot, aqua regia. I have, before, dissolved the ash directly in aqua regia. Takes more acid and is a mess but, it works. After the metal is dissolved and, before diluting with water, you could add the papers to the hot aqua regia. In your present situation, I would definitely do this. You may need a smidgen more nitric.

DISSOLVING METALS
Avoid foamovers
One time, when I first got into this, I was dissolving out the copper from some real rich pins in nitric, for a scrap dealer in L.A. He didn't trust anyone, so I set up in his scrap yard. I was doing it in a 5 gallon bucket sitting on the ground. He stood over me the whole time. He made me nervous and I over added the nitric. It just sat there for a few seconds and then, suddenly, it foamed over the top, gold flakes and all, into the dirt. I thought it would never stop foaming. When it stopped, only about half of the solution was left. A very embarrassing moment. The guy wasn't happy. What did I learn from my screw up? Since then, I always put the container that I'm dissolving in, inside of another, bigger, container. A 55 gal. plastic drum, cutoff to about 10" to 12" deep, works great for stuff you don't have to heat. The easiest way to cutoff plastic drums is with a circular saw. Be careful. To cut accurately, measure from the top and make measuring marks all around the drum. Connect the dots and follow the line by rolling the drum slowly, in increments, towards you. For stuff that is heated on a hot plate, I put the beaker or pyrex coffee pot inside of a 5 qt., white, flat bottom, Corning Ware dish. I also keep a spray bottle full of diluted anti-foam handy. They sell anti-foam

68 where they rent carpet cleaners. The AF doesn't always work but it always slows it down. Also, a fine spray of water will often cut the foam.

How much nitric does it take to dissolve copper or silver?

I had a little problem following your math but it seems you came to the conclusion that it takes only a quart of 70% HNO3 to dissolve a pound of copper. The rest of the 1/2 gallon is made up with water. I don't understand why you said that I was correct. I guess you assumed that I meant 1/2 gallon of 50/50 nitric. I didn't. I'm saying that it takes 1/2 gallon (2 quarts) of 70% HNO3 to dissolve 1 pound of copper. This is twice what you calculated and also twice the amount I see posted around the internet. I also add 1/2 gallon of water, making 1 gallon of 50/50 solution, to prevent crystallization of the copper. This is probably more water than needed but, it provides a good safety net. The equation you gave is: Cu + 2HNO3 = Cu(NO3)2 + H2 This is not the applicable equation. You didn't consider the NO or NO2 gas that is produced. The actual working equation for concentrated nitric is: (Call this equation #1) Cu + 4HNO3 = Cu(NO3)2 + 2NO2 + 2H2O For very dilute nitric, the equation is different: (Call this equation #2) 3Cu + 8HNO3 = 3Cu(NO3)2 + 2NO + 4H2O Actually, in this last equation, the NO (colorless gas) immediately combines with oxygen from the air to form NO2 (red-brown gas). Here's the overall equation. 3Cu + 8HNO3 + O2 = 3Cu(NO3)2 + 2NO2 + 4H2O Now for the math - first for equation #1: One Mole of copper is 63.55 grams. Therefore, in one pound (454 grams) of copper, there are 454/63.55 = 7.14 Moles. One liter of 70% nitric acid contains about 15.4 Moles. A gallon is 3.785 liters. One half gallon is 1.89 liters. Therefore, 1/2 gallon contains 1.89(15.4) = 29.1 Moles.

69 In Eq. #1, the Molar ratio of HNO3 to Cu is 4 to 1. Therefore, for 1# of copper, 7.14 Moles, it would take 7.14(4) = 28.6 Moles of nitric acid. Note that this is very close to the 29.1 Moles contained in 1/2 gallon of 70% nitric acid. In Eq. #2, the ratio is only 8 to 3. This computes to 19 Moles of nitric for a pound of copper. This is about 1/3 gallon of 70% nitric. However, this equation is for very dilute nitric - maybe 1%. In practice, this very dilute nitric is not used because the reaction would be terribly slow. As I read somewhere on the net, the copper nitrate produced also acts as a solvent in very dilute nitric. This is similar to the copper chloride produced in the HCl system. This is probably one reason why the ratio is only 8 to 3 in dilute nitric. Evidently, this solvent effect doesn't apply in strong nitric. In practice, a 50/50 solution of 70% nitric/water is usually used. This mix is considered the most efficient. It prevents crystallization of copper nitrate, improves a slight bit on the nitric required, and is still strong enough to give good reaction speed. The amount of nitric required is somewhere between Eq. #1 and Eq. #2 - between 1/3 and 1/2 gallon of 70% nitric per pound of copper. The figure is probably at least .45 gallons of 70% nitric per pound of copper, when using 50/50 nitric. This is all theoretical. When the reaction produces fizzing, there is also some nitric loss into the air. All in all, in practice, it takes very close to 1/2 gallon of 70% nitric acid (1 gallon of 50/50 nitric) to dissolve 1 pound of copper metal. I have proven this to myself 100's of times. It never fails, although it can be plus or minus a bit. This is the first time I've actually calculated it and I'm not surprised that the math worked out with my experiences. Try it out and see for yourselves. The ratio figures for copper alloys and nickel will come out about the same as in pure copper above, when dissolving with nitric. For silver, one gallon of 70% nitric (2 gallons of 50/50 nitric) will dissolve about 7 pounds - 100 troy ounces. The equations for aqua regia, being a two acid system, are much more complex. There are several different ones, all probably happening, to various extents, at the same time. It is almost impossible to predict what is exactly going on. There are too many variables involved: temperature, acids ratio, metals involved, etc. However, for most base metals, including iron, the approximate ratio is the same - about 1/2 gallon of aqua regia per pound of base metals. This is based on my experiences. #3

70 I'm still here, Ralph. There just hasn't been much that I could contribute to lately. Were I to start refining again, I would never use any acids on plated materials except for those that contain gold bearing brazes. I would use cyanide to strip the gold plate away from the copper. I know this is beyond the reader's capabilities and that is why I haven't mentioned it before. To me, the cyanide is cheaper, safer, faster, more efficient, and the waste is easier to treat. I used it daily for about 20 years. I agree completely with Harold's last post. AR is not the way to go on pins. However, if you do happen to use "real" aqua regia for pins, there is an easy way to prevent it from foaming over. First of all, never premix the aqua regia. Use the acids separately. Cover the pins with HCl and heat. When you get a little steam coming off, add a little nitric. You should get an immediate reaction and some foaming. When the action dies down and the foam subsides, give it a slight stir and add a little more nitric. Repeat until the pins are dissolved. The size and frequency of the nitric additions is determined by the amount of foam produced. It may take more HCl. It takes 1/2 gallon of either nitric or aqua regia to dissolve 1 pound of copper or brass. You can do this at room temperature but, I prefer heating it, for this reason. At room temp., the reaction is somewhat slow in starting. This makes you think that not much is happening and you, therefore, add more nitric. The reaction generates heat. At some critical temperature and concentration, the reaction starts going at full speed and the solution foams over. By pre-heating the solution, the first addition of nitric goes full speed immediately and this will prevent you from adding too much nitric at one time. If you don't pre-heat, put the pins in a 5 gallon plastic bucket and put the bucket in a plastic tray (a safety net for foam-overs). The bucket gives you plenty of room for the foam. I wouldn't run over 2# of pins per batch. Cover with HCl and add a little nitric. Be patient and wait for this first reaction. Stir well when the reaction slows down. Repeat as above. You can also pre-heat the HCl to about 130 deg F before you put it into the bucket. I learned this stuff the hard way. I've had my share of foam overs and have lost gold in the process. However, the vast majority of these foam overs occurred by starting with cold solutions. Were I to use nitric acid only to dissolve the copper or copper alloys and leave the gold undissolved, I would put the pins in a bucket and cover them with very hot water. I would then start making nitric additions as above. Live and learn. Patience is a virtue. Look before you leap.

71

Using nitric on gold plated base metals

To quote my own post, "It takes 1/2 gallon of either nitric or aqua regia to dissolve 1 pound of copper or brass." This is the truth!! Also, this ratio includes such things as Kovar (it's magnetic), which is the base metal of many gold plated pins on ICs. If you're using AR, treat the processors the same way as pins in my post. Quote: I have some pounds of military pins which are fully coated. W ill the acid go through the plating?

Probably, the nitric will penetrate the gold plating. Try a few to see what happens. Always experiment with samples first. Heat will help tremendously. Most all gold plating that is less than 100 millionths is porous. The nitric penetrates through the pores. The military parts are probably plated with less thickness than this.

A patent for eliminating the brown fumes

I just discovered a terrific patent that could revolutionize this whole NO2 problem. I don't have it in front of me but I'll find the patent # tomorrow. Also, it would need some study and some math and lab work to make it usable. It basically consists of adding definite quantities of strong H2O2 to any dissolving solution containing nitric acid. This would include nitric alone, AR, or NaNO3 + HCl. According to the patent, the H2O2 converts the NO that is produced back to HNO3 - in the solution itself! In this system, ZERO NO2 brown fumes are given off. The HNO3 is, therefore, twice as efficient and the presence of the H2O2 speeds up the reaction. Killer Patent! Three birds with one stone - No brown fumes - Acid will dissolve twice as much metal - Faster reaction. To prevent the H2O2 from decomposing too rapidly, a small amount of ethylene glycol (antifreeze) is used as a preservative. The common 3% H2O2 won't work. Stronger stuff is needed. There's a similar patent that uses sulfamic acid, I think, for the same purpose. I've mentioned before that a guy I knew used H2O2 in a multi-stage NO2

72 scrubber. The H2O2 converted the NO2 to HNO3 in the 1st stage. The 2nd stage neutralized the HNO3 with NaOH. In Aflac's discussion of the machine he promotes, he said the scrubbers worked the same way, although he wouldn't say what the scrubber solutions were. All of this goes hand in hand. That's why I was excited when I saw that patent. I just found the Patent #'s. 3945865 and 3367874. There are probably more out there. I just found these and haven't really studied them yet.

EQUIPMENT
Pyrex containers
Only certain Pyrex containers can heated directly. They are always thin and the glass thickness is uniform. They include beakers, erlenmeyer flasks, and coffee pots. Pyrex measuring cups, battery jars, graduates, and kitchen casseroles, etc., cannot be used over a direct flame or hotplate. The glass is thick and uneven and it will exhibit thermal shock and will break.

Siphoning
There's no need for a gadget to get the siphon going. Use your hands. Double the hose so that the ends are equal and fill it brim full of water with a lab squirt bottle or at the sink. Make sure there are no air bubbles in the hose. Put your finger over one of the ends and lower that end to the lower container. With your other hand (your right hand, if you're right handed), put the other end of the hose about an inch into the solution. After about 1/10 of a second (almost simultaneously), release the bottom end of the hose. Practice with water containing a little sand. Allow the sand to settle first. Try to siphon off the water and leave the sand behind. For a small container, I use a small hose about the size of the one in Steve's video. For buckets, I use a 5/16" or 3/8" ID hose. For drums, about a 5/8" or 3/4" ID hose. The length of the hose is important. It must be long enough not to flop out of the lower container yet, not so long that it coils around in the bottom of the container. I like using a 5 gallon bucket at the bottom, no matter how small the

73 top container is. I also put the lower bucket in a plastic tray, just in case the hose flops out. When siphoning dark solutions, it's difficult to know how deep the tip of the hose is submerged into the solution. To solve this, I paint about one inch of the upper end of the hose with a red Sharpie. I don't paint the red solid. I paint it in stripes it seems like it's easier to see. When settling the solids in the upper container, I put a piece of wood under the back of the container. The solids then settle down to the front corner. This tilt makes the siphoning easier and more efficient. Instead of placing the upper tip of the hose in the center of the solution, I put it, at an angle, against the front surface of the container, about an inch deep in the solution. As the solution level goes down, I progressively slide the tip of the hose down. This is easy to see and do if the tip is colored red. As the solution level nears the bottom, I use my free hand and, very slowly and steadily, tilt the container even more towards me. When doing this, don't disturb the solids. Never allow the tip to come out of the solution. You'll lose your prime and will have to start over. I shouldn't admit this but, I rarely used gloves when siphoning. I do suggest that all of you use gloves, however. I preferred a "feel" and this is hard to get with bulky gloves. I siphoned about 20 times a day and got good enough not to get much of anything on my hands. When I did use gloves, I used thin latex ones. This is one of those easy operations that's very difficult to explain using only words.

More on Pyrex
The Pyrex coffee pot would work fine, but I wouldn't put it directly on the burner. If you can find a large (5 quart) Corning Ware dish, you can put it directly on the burner. Then, put the coffee pot inside the CW dish. This will catch the solution in case the coffee pot breaks. Look for a white, flat bottomed style, CW dish. Also, find a coffee pot that has a single, stainless band, near the top, that holds the handle on. On these, the plastic handle is short and won't get burnt. On some coffee pots, the big plastic handle, held by a band at the bottom, extends to nearly the bottom and this style will get burnt. Don't use this type.

A Mortar and Pestle for Ceramic Parts - With No Guarantee

I hadn't looked at the Action Mining catalog in awhile and they've sure come a long way. I saw the pulverizer you mentioned and I wonder if you noticed that the

74 material has to be 1/2" or less before you put it in the pulverizer. They actually recommend 1/4". Also, their prices seem high on about everything. If you're young, strong, and energetic, you can use a big, homemade, mortar and pestle that will probably do the job. I've used it to grind slags and they're about as hard to break up as anything. You could also probably use it for most ores. I think it would work fine for CPU packages and other ceramic IC's. I haven't tried it and I'm not guaranteeing it but, I think it would work, after I saw what it did with the slag. About the only other way to break them up is with a ball mill, which is actually the best way. I've also seen people break them up with a heavy sledge hammer. They held the hammer vertically and pounded with the top of the hammer head and, not the faces. In this case, it would probably be best to put the parts in a heavy steel tray, about a foot deep, to keep them from flying around. I'll give you the dimensions, as I remember them, from the last one I made. I'll tell you what each piece is for so that you can vary these dimensions a bit, depending on what you're able to find. The mortar is a piece of wide, heavy walled, pipe about 2 feet high with a plate welded to the bottom. The plate on the bottom should be thick enough to not warp when welding and large enough so you can stand on it. The pipe is heavy walled to withstand the banging and tall enough so that the pieces don't fly out while pounding. The pestle is simply a piece of thick steel rod that you pound with and is long enough to keep from banging your hands on the mortar while pounding. A tall person will probably get a sore back from bending over plus, the pestle is heavy. If the tall person is strong enough, make the pestle a little longer. The mortar is heavy and it would be nice to have a couple of handles when dumping it out. I would suggest making them in this shape, [ , from 3/8"rebar or rod. Make them about 2"X6". Weld one on the side of the pipe, vertically, and the other on one edge of the plate, bent up about an inch, or so, so you can get your hand under it. I've never done this but, I think the pounding would be easier if you had 2 similar handles near the end of the pestle. I'm thinking handles similar to those on the tool you use to pound steel fence posts into the ground. Here's what you need, besides the handles. (1) 6" to 8" dia. pipe with 3/16" to 1/4" walls, about 24" to 28" long. The ends don't have to be ground but, they should be cut off square. Most scrap dealers that sell steel have a big band saw for this purpose. (2) A 1/4" plate, about 15" to 18" square for the bottom.

75 (3) For the pestle. I think the one I had was steel rod about 1 3/4" to 2" in diameter and about 36" to 40" long, cut off square on the ends. That's about right for me and I'm 5'9". A 40", 2" dia steel rod will weigh 35#. Weld on the bottom plate and the handles on the mortar and pestle. Put some parts in, put some heavy leather work gloves on, stand on the plate, and pound away. You may need to take a few breaks.

EXPLODING COMPOUNDS
Beware of making PM explosives!
A company I worked for was making a 200 oz batch of sodium gold sulfite, in a battery jar on a heating source under a fume hood. One of the intermediate steps used ammonia and somehow the whole thing got dried out and produced gold fulminate or, fulminating gold, which blows up with very slight friction or pressure. The fire dept. evacuated the area for a 1 or 2 block radius. They then ran a fire hose down the fume hood exhaust, backed off, and turned it on. It flooded the fulminate and prevented it from going off. At the same company, a lab guy was weighing a few milligrams of gold fulminate. It went off and blew out a 12" chunk of the stone benchtop. At another place I worked, the guys were cleaning the plant. There were probably 200 buckets sitting around, each with something in them. One guy was condensing the bucket contents. One bucket contained nothing but a filter paper with about 50 grams of old dried up residue. Earlier in the day, I had seen this material and had even picked it up. Scary. When he dumped this stuff into another bucket, the residue exploded. It blew the bottom out of the bucket, blew one leg of his Levi's off, burned his leg, set fire to a 6' diameter spot on the ceiling, and these roman candle like things that shot out in all directions created about 20 spot fires around the perimeter of the room. After the explosion, I immediately came in the room to assist and saw the whole thing. We later figured the residue was a dried mixture of ammonia, silver, and sodium hydroxide - the ingredients for making silver azide. The common ingredients for these explosive mixtures are ammonia and a dissolved metal. Since then, the only thing I use ammonia for is a final leach for pure gold powder. It dissolves any silver chloride that is present. On the web, you will find PM refining methods that use ammonia. BEWARE!!

76

FILM
Film info
The first silver scrap I'll touch on is silver photographic waste. There are several types: film, silver flake, fixer solution, steel wool cannisters, etc. I have a little experience in dealing with this stuff. I'll talk about film on this thread. Today, I'll only give you basic information. If you want more, I'll go into more detail later. About 15 years ago, I had a small set up for running about 1000#/day of film, max. I used a stainless steel tumbler from a scrap industrial clothes dryer. My setup was in a scrap metal yard and, therefore, most of my equipment was cheap or free. For a tank, some farmer brought a 375 gal stainless milk cooler in for scrap. I think we paid him $9. It was perfect for the tumbler. It was a tank 6' long by 3' wide with a rounded bottom. Under the stainless, there were insulated cooling coils which we converted to heating coils by circulating water from a standard hot water heater. The solution was a non-toxic enzyme/baking soda mix that ran at about 100 degrees F. It smelled like a septic tank. You can also use a weak (3% -10%), non-odor, sodium hydroxide solution. The silver/emulsion came off as a black sludge. Every evening we stirred the solution and pumped it up to settling tanks. Next morning, we syphoned the solution, off the sludge, back into the strip tank. The same solution was used over and over. The sludge was treated and melted to a purity of 99.98%. Film silver is very pure to start with. If you don't contaminate it, you don't have to refine it. All you have to do it burn the sludge and melt it. A while back, I spent 4 years, part time, running film assays for a major film refiner. I ran about 30 assays a week, for a total of about 6000 assays. This represented about 50 million pounds of every type film under the sun. I know values. In order of quantity available: X-ray, litho, industrial, others. The X-ray and litho make up about 95%+ of all film. There is twice as much X-ray as litho. The medical is going digital so, these ratios probably have changed. In order of value: Industrial, litho, X-ray. When I left, the X-ray contained 0.1 ozs/# - today is $1.32/#. When I left, new, lo-silver X-ray started lowering these numbers. The best newspaper litho runs about 0.24 oz/# - $3.19/#. Average black Industrial runs about 0.25 - 0.3. These values are for black processed film. Green undeveloped film runs a lot more. There are about 20 common categories of film, each with it's own set of values. In a category, there are several quality levels.

77

Film on reels Processing film using nitric (not really recommended)

You've got your work cut out for you, Austex. Laborwise, doing film on reels is the worst, especially, when you don't have a shreader. That film is long! It won't even hardly burn, without unreeling it. Youll have to cut it up. If you have a band saw, you might try cutting the reel and film in half. That could save a lot of work. It might, however, weld the cut ends together and make the pieces harder to separate. Try it if you can. I can't think of any other type saw that might work. Any chemical that you use will make the gelatin all stick together. I wouldn't run much at a time - maybe, 1/2 pound in a bucket or plastic tray. You'll probably have to use gloved hands and work the strips of film in the solution, in order for the chemical to get in between the film. Ideally, you could use a long (or deep) tank, with the reel(s) of film at one end and a take-up reel(s) at the other. You would have to use a solution that would work fast. A little agitation will help. I think that some strength of nitric might work the fastest. Another advantage of nitric is that all the silver becomes dissolved. This makes the separation of silver and plastic simpler. Don't expect much from this type film. I wouldn't expect much over 1/2 to 1 ounce of silver on the 4#. Maybe less, depending on how much black is on the film. The only way to process this type of film, profitably, is to process it in tonage weights, in a full fledged process line. I have never used nitric to strip film. I have played with it and I know what happens. I had better methods but, for you as a hobbyest with a small amount of film, I think nitric would work the best. It's the simplest. 1) Concentrated nitric was a bad choice. To experiment, I would start with about 35% nitric, by volume. I think that it will be too strong but, when you start high, you can simply go lower by adding an increment of distilled water. It is my guess that 25% (and, maybe a little less - maybe only 10%) will be the best. You want a strength that is quick enough, yet not too strong to be uncomfortable to work with. Try to use the lowest strength that still strips pretty fast. The silver is stripped when the black is gone. 2) First off, try putting about 1/2#, in 6" strips, in a 5 gal. plastic bucket or about a 3 gallon plastic tray. Cover the film with about 3"-4" total of solution. Work the film with your gloved hands until the black is gone. Remove the plastic with your glove, shake it a bit and put it in some rinse water. 3) Add more film to the same solution. When it slows down too much or stops

78 working, add a little nitric and maybe about the same amount of water. You may have to sooner or later make up a fresh batch(s). 4) Collect all the solutions and rinses together in a bucket(s). Either allow the crap to settle and pour the clean solution off or filter the whole thing. 5) You can get the silver out in 2 ways. You can either make silver chloride or you make silver metal directly. In this case, the silver chloride will ultimately make much purer metal. The silver on film is quite pure. If you don't contaminate it with other metals, it will end up pure. To cement the silver metal out directly with copper, you will contaminate the silver, somewhat. If you choose the silver chloride method, add salt water or HCl, in increments stir after adding, until no more silver chloride drops out (observe white cloud). Keep the silver chloride wet at all times. Either use the Karo syrup/lye or aluminum method to convert to silver metal. It's all somewhere on the forum.

Info on film-part 2
As I mentioned before, I once spent 4 years doing some 6000 assays for one of the largest film refiners. During that time, they processed about 50 million pounds of film. Every type of film known to man was represented except for dental xrays. To me, the reason was obvious. Dental x-rays are so small in size that the labor, collection, and other costs would override any profits. This is an educated guess, but I would imagine it would take 10,000, or more, of them to get 20 pounds. Also, there is the paper problem. The 20 cents per pound sounds low. I haven't assayed any of them, but I would assume the silver content would be about the same as medical x-rays. They run about 0.1 troy ounce of silver per pound. At today's silver market of $13.28, the silver content would average about $1.33/pound. The more black that's on the film, the higher the silver. There are usually 1 or 2 sets of middle men in the film buying business and everyone has to make a profit. The last middle man has to go to the expense of collecting, storing, sorting, and shipping the material to the refiner. There aren't many film refiners around but, if you can find one, you will get a higher price by selling directly to them and avoiding the middle men. The company I worked for bought any sized lot at their dock. On the east coast, the refiners are mainly in South Carolina and Tennessee. I think there is a incomplete list of buyers and refiners on the Kodak website. The fixer/steel wool is not a good idea, especially in the small quantities you're talking about. It's impossible to just look at the steel wool and tell how much silver

79 is in it. It's never uniform and therefore it can't be simply sampled and assayed. Therefore, the buyer or refiner will pay you very little for it, just to cover their butts. There are also inherent problems in collecting all of the silver from the fixer, in the steel wool. There are companies that make canisters of steel wool and other metals for silver removal from fixer. The solution is pumped through the cannister at a fairly slow rate. Here again, though, you'll have problems getting a good value when selling them. Unless you get quite large, maybe several thousand pounds per month, you're better off selling the film. If you want to play with refining, you can strip off the emulsion, along with the silver, using a 5% to 10% sodium hydroxide solution, at about 100 degrees F for the 10% NaOH and probably about 150F for the 5%. Agitate the film while stripping. It will go slow because, when wet, the film sticks together and the solution has to work it's way between the layers. You might put the film in a small plastic bucket, with holes drilled in it, and bob it up and down in the solution. Wear a full plastic face shield and gloves - a drop of NaOH can blind you. Remove and rinse the clear film plastic (PET), when stripped, and let the sludge settle. Pour off the liquid and filter and rinse the sludge. Burn the sludge outside (it really puts off vile and, most probably, toxic fumes) to get rid of the emulsion. Melt the residue in a crucible furnace with borax and a small amount of soda ash. If you haven't contaminated it with other metals, the silver should end up about 99.95% pure. The sodium hydroxide method is the most common method used commercially. There is also a very safe enzyme/baking soda method that is sometimes used but, it makes the entire building smell like an outhouse.. You can also use dilute hydrochloric acid to strip the emulsion/silver. The silver will be converted to silver chloride. You can then use the Karo syrup method to convert this to silver metal. The hydrochloric method is not used commercially because of the fumes and it's corrosive properties. Also, silver chloride is a bear to work with, especially in large quantities. Chemically, the very best way to process film is in a cyanide solution. The film is stripped and the silver is directly plated out of the same solution. The same solution is used over and over. In the '70's or early '80's, if I remember right, some guy died in a film processing plant in Chicago. The TV show, 60 Minutes, did a blurb on it. Since then, no more cyanide is being used for film, at least not in the US. As far as I know, no one is collecting dental x-rays. If anyone was, I would have seen it at that place that I worked. It's one of those items that's probably thrown away, due to the expense of collecting it. If you can figure a way to collect it and handle it, profitably, you'll be a rich man. Every dentist has only a little bit of it but, there are a lot of dentists. Maybe you could guarantee to give half (or, ?%) of your profits to a good charity, if the dentists will separate it and ship only the film to you. Dentists may bite on that ploy.

80

Every post I make about film, I warn people to NEVER allow the film to get wet, if you plan on selling it. If you do, you'll get much less money for it. When it dries, it will be glued together and can't be easily processed. It can be incinerated (very dense toxic black smoke) to light gray ash and then the ash can be melted to get the silver. Before EPA, this was the main method (cyanide was probably #2) that was used for all film. During incineration, about 30% of the silver goes up in smoke. Commercially, the smoke was collected in a high dollar baghouse. You might also ask the dentists if they have any out-of-date undeveloped (green) film or scrap green film that has been accidentally exposed. Green film runs about double the value of developed film. You may find that more money can be made from just collecting the lead foil. You also should ask about their dental gold scrap after you learn how to buy it. Dentists will also have silver bearing fixer solutions containing about half of the silver that was on the film. They may dump it down the drain, although, if it contains silver, it is illegal to do so. The smaller dentists may use steel wool cartridges to remove the silver. Usually, they have an exchange contract with the cartridge provider. You may also find that large dental offices have electrolytic cells, with rotating cathodes, to plate the silver out of the fixer solutions. The resulting silver is called "silver flake." It will usually run from 60% (or, worse, especially when wet) to 98% silver. The lower value flake is black and slimy and the good stuff is hard and white in color. Before weighing the flake, it should be dried out. Heat drying produces a lot of stink, since the black slimy stuff contains a lot of sulfur.

Info on film-part 3
If they're modern medical x-rays, you can expect about 10 oz of silver, total, from your 100 pounds. If you run full sheets, you will find that the sheets will stick together, causing the stripping to go very, very slowly and complete stripping may be impossible. Since you're just playing around, I would suggest you first run the film, a sheet at a time, through an old decent paper shredder. This will make the stripping go much faster and you will be less frustrated. Some of the newer film may be Dryview, which is developed by heat instead of by chemicals. It will strip slower and you may find that you'll have to raise the temperature of the solution considerably. Dryview is detected by briefly holding a lighter underneath a non-black clear area of the film - maybe on the border. If it is Dryview, the spot will turn black. This has to be done right. If you don't leave the flame long enough, nothing will happen. If too long, even regular film will burn and turn black, although the black color is different - it's more like a very dark brown. A second or two or three should be long enough. Some big film refiners

81 won't buy Dryview because it's such a pain to process. Some Dryview requires special in-house secret solutions to get good stripping. Stripping is complete when all of the black has been removed and you're left with just blue (usually) plastic. Stripping time in a NaOH solution is a function of chemical strength and temperature. The weaker the NaOH, the higher the temperature required. A 3% solution requires about 200 F. A 10% solution, about 100 F to 120 F. With the 10% solution, you may get away with room temperature but it may go slow. Tumbling is always best in production. In your case, I would drill some holes in a small bucket, put some film in it, and slowly bob it up and down, every so often, in the solution that is contained in a larger bucket. After stripping, bob the film in a couple of buckets containing rinse water. Wear a full plastic face shield to keep drops of NaOH solution from flying into your eyes. After the silver/emulsion sludge has settled and been removed, the solution can be reused, over and over. If if slows down, you can add a little more NaOH. Never get NaOH under your fingernails or you'll be in pain for a long time. Don't ask me how I know this. Always wear good rubber gloves with no pin holes in them. Everyone uses tap water. You could lose traces of silver as silver chloride, however. Some of the chlorine in the water can be eliminated by filling buckets with water and, with occasional stirring, letting the water stand for a few days before using it. As Harold said in a recent post, the value of the silver lost is less than the cost of distilled water.

How film is processed

I would stay away from the chloride. I know that, due to the ease of stripping, it is enticing. But, you'll pay the piper down the line. First of all, silver chloride is a very difficult material to filter, especially when aged. It also tends to clump, over time, which can cause great inefficiency. If you're converting the AgCl to metal in a melt with soda ash, the converted silver will tend to coat the silver chloride clumps and will prevent the soda ash from contacting the AgCl in the middle. When you pour a bar, it will have three layers: silver on the bottom, silver chloride in the middle, and slag on top. It is extremely difficult to convert this silver chloride layer to metal. If you're using a wet method, such as a sugar plus lye, you end up with the same melting problem, since all silver must be ultimately melted. In this case, the clumps of silver chloride are coated by silver in the solution. When melted, its the same thing. I spent about 4 of the last 7 years working for one of the largest film refiners in

82 the US. When I left, we were doing about a million pounds per month. We used a 4% NaOH (lye, caustic soda, sodium hydroxide - all are different names for the same thing) solution at about 180 deg F for 45 minutes, in a tumbler. NaOH is a time/temp deal. When I had my own refinery, I used a 10% solution. If I remember right, it took about 5 minutes, or so, at about 100 deg F, here again, with tumbling. Gotta have tumbling. ALL major refiners use either NaOH or an enzyme/ baking soda combination. For the last 150 years refiners have practiced, what they call, "chloride avoidance" methods, when it comes to silver. The best way to chop film is to use equipment with a shearing action, so that the resulting pieces lay flat and give a decent bulk density. Although you can use a hammermill or a paper shredder, the resulting pieces get a little mangled and this produces a much lower bulk density. I have seen hammermilled material that only took about 30 pounds to fill a 55 gal drum. This severely cuts into your production.

The problem with chloride methods of processing film

When a chlorine containing chemical, such as bleach or weak muriatic acid, is used to remove silver from film, the silver is converted to silver chloride. Silver chloride won't dissolve in nitric acid unless it is first converted back into metallic silver. This is the purpose of using soda ash in the melt. In your original post, you asked if nitric acid could be used to dissolve the silver off of the film. The answer is yes, but the problem is, what do you do next? About the only thing to do is to drop the silver out with table salt or muriatic acid, thus forming the undesirable silver chloride, just like in the bleach method. Is the book that you refer to written by C.W. Ammen? Have you ever tried this method, from start to finish? Although Mr. Ammen's book has a lot of neat stuff in it, there are many things that just aren't practical. The method you describe is one of these. Although the method works, it is fraught with production problems, compared with the 2 above (my former post) clean methods used by real refiners. Mr. Ammen's expertise is in the mining industry, which is very different than refining scrap. If you're a miner, his information is excellent. If you're dealing with scrap, much of the info is very amateurish. I own the 1st edition and will someday buy the 2nd edition. The book is great but should not be treated as the gospel truth, when it comes to processing scrap First of all, it produces silver chloride, which is much more difficult to process than the silver oxide and silver metal produced by the other 2 methods. The melting of silver chloride with soda ash tends to eat holes in crucibles. This is

83 reduced somewhat by the use of clay crucibles. Also, the silver chloride tends to clump in the melt which prevents total contact with the soda ash. This results in low yields. The fumes coming off the melt are toxic. For these and numerous other problems, refiners have used so-called silver chloride avoidance methods, for 100's of years. The bucket method you describe can only strip one sheet at a time, since 2 or more sheets will stick together, when wet, thus making the stripping take forever. If I remember right, there are about 20 8X10 xrays per pound. Average black rare earth xray film runs about .105 tr. ozs. of silver per pound of film. At $7 silver, each sheet of film is worth about 3.7 cents. Pretty slow way to make a few pennies. If you do use the bleach method, I would suggest using a chemical method to convert the silver chloride to silver metal, instead of using a furnace. For example, if you combine 31.1 grams of silver chloride with 100 cc's of water, 10 cc's of Light Karo syrup, and 15 grams of lye (caustic soda), you will get about 23.4 grams of silver metal powder, which is filtered, rinsed well, and dried and then melted to a pure silver bar. The solution must be stirred often, and fairly vigorously for about an hour, or two. The honey appearance you mention sounds like, maybe, unconverted silver chloride. The silver contained in film is quite pure. Therefore, if you don't contaminate it with outside metals, there is no reason for purifying it with nitric acid at the end. I must admit that I, also, got sucked into the false glories of the bleach method, about 20 years ago.

More info on film processing

If you burn it, you can lose as much as 25-30% up the stack. Those few refiners that still burn, usually install expensive baghouses to catch the black, silver bearing smoke. There are big legal problems with burning. Most refiners use chemicals to break down the gelatin that holds the silver onto the PET plastic sheet. The gelatin and silver fall off and form a gunky, black sludge, which must be filtered, burned, and, finally, flux melted. A common method uses a 3% to 10% lye (caustic soda, sodium hydroxide) solution. The handling of the lye, in large quantities, can be quite dangerous, if you don't know what you're doing. A much safer method uses an enzyme and baking soda (sodium bicarbonate). Twenty years ago, I bought the enzyme from either Miles Laboratories or Morton-Thiokol. It's expensive, but it doesn't take much. The

84 problem is the smell - the enzyme ferments the gelatin. I've always thought that Rid-X (for septic tanks) and baking soda might work, but have never tried it. The fixer method is expensive. You have to buy the fixer and then, you have to plate out the silver onto a rotating stainless steel cathode. Processing film is a high-volume, low-grade operation. If you don't have at least 1000# per day, plus enough equipment to make it a one-man operation, forget it. As JoeM said, the best way is to sell it outright. In this business, there is a daisy chain of buyers, each of which must make a profit. If you're lucky, you are located near a film refiner, who will give you the best price (avoiding the middle men). There are very few refiners. There are several in South Carolina, one in CA, and Petag Corp. in Houston. I highly recommend Petag. I worked there for several years and never saw any dishonesty. It is generally more profitable to buy litho film (newspapers, printers, etc.) than medical (hospitals, mainly). You have to pay more, but litho has, on the average, twice as much silver per pound as medical. Also, many newspapers will sell to the first guy in the door with money, whereas hospitals will only sell to the same guy they've been selling to for the past 12 years. If you can find a buyer, get him to educate you, as a potential customer, concerning the various types of film and their values. There are about 6 or 8 common types and about 20 others.

FILTERING
A simple filtering setup
Buy a standard plastic filtering funnel from Wal-Marts auto department. I prefer about a 6" dia. one that I can use for everything. For good refining filter papers, my favorite (and fairly cheap) is S&S 596. They may not make them any more. If they do, you'll have to order them from the factory. Second best and, the cheapest paper around, is S&S Sharkskin. Don't buy Whatman #42 or another company's equivalent. They're OK but, are expensive and, slow as molasses. A perfect size paper is twice the depth of the top part of the funnel. If you use coffee filters, you can buy big ones cheap from a restaurant supply. You can also buy big stainless spoons, for things like stirring stuff while burning small amounts or, for uses while working around nitric acid. Leave most of your money at home when going to a restaurant supply. Get a very clean or new bucket. I don't like using soap to clean buckets, except

85 to remove oils or grease. I use a Scotch Brite pad and water. Soap residue can generate much foam when doing reactions that foam even without using soap. One time, I filled 7, 7 gallon plastic trays with foam from 2 gallons of aqua regia. To get those heavy gold powder residues off of the inside of a bucket and into the filter, first cut about a 3/4" square of Scotch Brite. Put a squirt of water in the bucket and scrub the bucket with the wet pad. Rinse the pad and fingers into the bucket with water. Using a lab type squirt bottle - all others are worthless - tilt the bucket towards you and rinse down the inside of the bucket. Still maintaining the tilt, move it to the filter and rinse the gold from the bucket, into the filter. It doesn't all come out easily. Get a square piece of 1/2" or 3/4" plywood, sized to cover a bucket. In the middle, cut a hole so that the funnel will sit in it with an inch or two sticking out the top of the board. Most of the funnel will stick out the bottom. Instead of plywood, you can cut a hole in the top of a bucket lid. If you're using coffee filters, open them up flat. Fold the circle in half. Fold it again but, this time, don't fold it all the way - stop about 1/2" short on a regular size coffee filter. Open up the paper so that it's cone shaped and place it in the hole in the bucket. Put it all on the bucket. Before filtering, wet down the paper, slightly, with the squirt bottle. Pour in whatever you are filtering to near the top of the paper. Keep it filled. When filtering most things with a lot of volume, like aqua regia solutions, it's much easier and faster to let it settle, siphon off as much clear solution as you can, and then filter only the remaining residues. When you learn how to do it, siphoning can eliminate 90% of your filtering time. Filtering is always the bottleneck in refining operations. There are many tricks to speed things up. When you first start filtering things like aqua regia solutions or gold mud, some of the solids will almost always pass though the paper. After a while, the paper will start clogging and the solution coming through will run clear of solids. You can tell when it runs clear by observing the drips at the tip of the funnel. When the drips are running clear, transfer the board and funnel to another clean bucket and re-filter the stuff in the first bucket. If you don't do this while filtering aqua regia, your final gold will be off purity. It's a good habit to get into, no matter what you're filtering. I always have 6 or 8 of these bucket/funnel setups going, for the various things that always seem to require filtering. They're cheap and are easy to make. I've owned several vacuum filters in my lifetime but, for most things, I prefer the filtering setup like I've described above. Vacuum filters are expensive and are a pain to use. They pull the solids down tight on the paper and seem to clog fast, especially with things like solver chloride. With certain plastic vacuum funnel designs (Bel-Art comes to mind), it's almost impossible to get the paper to seal.

86 But, when you're filtering very large volumes of unsettled solutions, vacuum filters can speed things up. A friend of mine had a unique way of filtering large volumes. He put about 15 restaurant coffee filter papers into a plastic kitchen colander. When the top filter paper became clogged, he would carefully remove it, exposing a fresh paper. It was messy but, it worked pretty good.

Buckets vs. glass Miscellaneous info

I'll argue till our dying days about the merits of white plastic buckets. They're cheap, unbreakable, and safer to handle. You can even heat their contents (aqua regia) hot enough to dissolve karat gold, if you put them in a hot water bath. My first 10 years in the business, the companies I worked for all used Pyrex. After that, in my first refinery, we used Pyrex. In all these cases, we found the biggest beakers available, the 4 liter size, too small, so we used big Pyrex 5 gallon and 7.5 gallon battery jars. These cost, at the time, about $100 each. The glass thicknesses on their bottoms were very uneven and, therefore, they would break easily and often, especially with direct heat. The first company put the jars into a tray made of 1/4" sheet lead, to catch the solution when the jars broke. They heated the aqua regia with a titanium steam table. In my refinery, we heated the jars on a 6' gas restaurant grill. We put a very heavy asbestos cloth between the jars and the grill to distribute the heat. Still, there was breakage. I can't tell you how much gold solution I have seen on the floor. The last place I worked, during my first 10 years, found a local glass fabricator, who made us up about 20, 3.5 gallon Pyrex jars that were actually very hard to break. These took the heat, were easier to handle than the bigger battery jars, and were generally terrific. In 1980, I found enlightenment, when I was the technical guy for a refinery in California. The owner was the best refiner I have ever known. I credit him with much of my knowledge. He ran a lot of karat gold and had at least 12, 4 liter aqua regia beakers set up, on individual hot plates. Each beaker had a lid with tubing running out of it and the fumes ultimately went through a fume scrubber. All dropping of gold was done in white plastic buckets. The operation was smooth, efficient, and produced an amazing amount of very pure gold. Don't forget, 1980 was the year of the giant gold and silver boom. We always had people waiting in line, to sell us scrap, when we opened up in the mornings. Louie was also the world's champ when it came to cleaning dirty gold in the furnace. He also had big rolling mills to roll out the karat gold bars very thin. This made the aqua regia operation go very fast. We rarely had to shot the gold. We had 12 silver cells that produced a total of about 5,000 ozs. per day. Even with all

87 this, we had enough scrap to keep the cells going for several months. Before the boom, we charged $0.25 to refine an oz. of silver. During the boom, we got $7.50 per oz. The good old days. White plastic buckets and de-lidded plastic drums were the mainstays of Louie's operation. I'll never refine without them. Different strokes for different folks. There's more than one way to skin a cat. And, of course, you should always look before you leap.

FUME HOODS
Fume hood info
Aqua Regia is about the only method, for the small refiner, to purify gold to 999.9 Fine - no matter what anyone says. Not only does this method work on most karat golds, it is also the final re-fining step that is used to purify the gold collected from all types of scrap. Once you learn the steps for karat gold, which is the most difficult, you can easily adapt to gold from most other sources. It's not easy to get 999.9 fine gold. In that purity, there is only one part of impurities to every 9,999 parts of gold. Not much. Everybody learns to do it a little differently. Many small refiners never learn to do it. Since reaching this goal is foremost in my mind, I have begged, borrowed, stolen, and invented tricks, in order to achieve this purity. It's sort of a pride thing, with me, to be able to to produce beautiful 999.9 bars. Also, I get more money for the very pure gold. It's not that hard to do. The most important things are: (1) Keep excess nitric out of the aqua regia. I have a good way to do this. (2) Rinse the final gold very well. Have a plan. To do aqua regia, you almost have to have a fume hood. You can do things outside but, you then must deal with the weather and other problems. When it comes to automobiles, metal buildings, lungs, etc., aqua regia fumes are one of the most corrosive things around. Also, aqua regia fumes are heavy and tend to cling to the ground in inverse weather conditions. It's best to not have any neighbors nearby. When you are very small, you can probably get away with exhausting the fumes into the air. When you get big, you'll have to get a fume scrubber. Besides the corrosive nature of the fumes, one other problem is the high visibility of the red/brown nitric oxide fumes that are produced. Commercial fume hoods are expensive. I usually build my own. The last fume hood I built, a 10 footer, was made as follows. I first built a bench 10 feet long with a 2" X 4" framework, 4" X 4" legs, and a 3/4", 3 feet wide plywood top. The top was about 36" high, a height that is good for siphoning the solutions out of

88 buckets. The room I installed it in was in a metal building with 10' ceilings. I then built a frontless plywood box to enclose the bench with full sides, a full back, and a full top. I built it about a foot, or so, short of the ceiling, in order to mount the blower motor on top of the box and keep it away from the fumes. I ran a piece of plywood across the top front of the hood. I made the bottom edge of this strip of plywood about 6' off the floor, to keep from bumping my head on it. I then got 2 blowers, mounted in tandem, out of the junk yard. I think they were of 10" size. I mounted them at the top, back, center, inside of the hood and ran them to the motor above with a belt. I exhausted the fumes from the blowers through large fiberglass ducting to the outside of the building. I didn't have a complete front on the hood or, sliding doors. You can add a series of 3 or 4 sliding, overlapping, plywood doors, on wooden tracks, that you can close when the blowers are shut down at night. They get in the way and I worked around the shutting down problem in other ways. I kept all acids under the hood in containers with lids, such as buckets, that I sealed before leaving at night. I never left open containers when the blowers were off. If I had a dissolving reaction going on that would work overnight, I left the blowers on. Also, I had the hood in a fairly small room, in which the walls and ceiling had been covered with low grade 1/2" plywood. I also had a couple of light bulbs, in PVC receptacles, covered with fume proof globes, mounted inside of the hood. This is hard to explain. If anything is unclear, please ask questions. Constructing the hood only took a day, or two. It's really pretty simple. For a smaller hood, you can use the same basics. In 40 years, I have never seen a fire in a fume hood. I have probably been using wooden hoods for 30 of those years. You are right about the combination of nitric and cellulose becoming more flammable. When using these hoods, I was aware of this possibility and, thinking back, I always did things to prevent a fire from happening. I never, ever, used an open flame under the hood. The hot plates were electric and were always sitting on a piece of Transite or sheet metal. If you don't feel comfortable with acids soaking into the bench top, coat the top with polyester boat resin. You can also use a pre-made kitchen Formica counter top. The Formica will soon stain but, who cares? It you don't mind the expense, you can have any type plastic coating you want chopped onto the entire hood. The absolute best fume hoods are the industrial ones but, they cost from $5000, for a small one, to about $20,000. A stainless hood soon gets ugly and starts corroding away. A Transite hood would be great but, asbestos products are nearly impossible to get. A sheet plastic hood would be OK if you used plastic at least 1/4" thick, to keep it from buckling - not cheap. I think they have nonflammable fiberglass. All in all, if I ever build another hood, it will be from plywood.

89

GOLD LEAF
Thickness of gold leaf
Harold, real gold leaf even weighs less than that. It runs from about 10 gms to 30 grams per 1000 sheets, which are 3-3/8" X 3-3/8". If my math is right, that's about .15 to .45 grains/sheet. Average 23KT leaf is about .23 grains/sheet. The gold doesn't disappear, of course, but when you ball up a sheet in your fingers, you have to look carefully to find the speck of gold that results.

Beware of EBay much fake gold leaf being sold as the real stuff
I saw the exact same thing you bought. I looked up Schabin and found they make both faux and real gold leaf. There are very few precious metals deals on eBay. The $1500 to $2200 worth of gold for $75 should be a clue. Extremely false advertising in calling it gold leaf flakes. Only gold goes into making gold leaf. The guy should go to jail or be fined big time. Nowhere in the ad does he say imitation gold leaf, as it does on the Schabin website. Sepp, that owns Schabin, is a big company and I'd bet they'd go ballistic if they knew this guy was was defrauding people using their name.

GOLD PLATING
Gold plating purity
Actually, most of the electronics gold plating isn't pure. They intentionally add alloy metals to the plating bath to make the deposit harder and more wear resistant. The most common metals used are nickel, cobalt, and indium. The resulting gold plating runs from about 96% to 99+% pure, depending on the application. The most common baths, of this type, plate about 99.0% pure. These alloy golds are usually very bright and shiny. There are also many specialty baths, such as the white Au/Pd gold that is used on things like reed switches. On parts that require heating for such things as die attachment, very high purity

90 gold plating is required. CPU packages fall into this category. Anything less than 99.99% purity will discolor when heated and the oxides produced will cause problems with the brazes. Pure gold plating is usually not as bright as alloy plating.

GOLD PURITY
Determining gold purity
When your gold gets purer and purer, it gets more difficult to get meaningful fire assay numbers. On 99.99% gold, fire assay completely fails. Even though, according to a respectable source on the internet, fire assay is still the most accurate direct method (within .02%), on the planet, for assaying gold. For pure gold, the best method is an indirect one. You send the sample to a lab that determines, not the gold itself but, all the percentages of the impurities. These are added up and subtracted from 100% to get the gold percentage. This is expensive and the results are slow in coming. If your gold is not very pure, fire assay would work but, it would cost around $2000 for a semi-decent setup. This seems a lot but, any other halfway accurate method would probably start at $50,000. The touchstone is cheap but, at the hands of an expert, is only accurate to about 1% - 2%. The cheapest way is to simply look at your gold button or bar. Starting at what seems to be about 99.9%, squarish crystals start forming on the top surface, along with a squarish hole, usually in the center, which is called a "sink" or a "pipe". This is where gases are expelled when the gold solidifies. As the gold gets purer, the crystals become more defined and visible and the "sink" gets deeper. At very high purity, the crystals seem to crack and separate, a bit, near the sink The crystal appearance I just discussed is somewhat subjective and I've never seen anything else on it on the web, other than what Harold and I have said. However, any refiner that is capable of producing high purity gold or any buyer worth his salt, has seen it and knows what I'm talking about. When I have sold gold with good crystal and sink to a knowledgeable buyer, I have always gotten top dollar. If the crystal and sink aren't evident and, if it's a small lot, the good buyer will just pay a lot less. If it's a large amount, he will want to remelt it and, guess who pays for that. He might also run it through jeweler's rolls to check for brittleness (usually lead) and look for fernlike crystals, which

91 indicates platinum group. If the crystal still isn't evident, after remelting, you receive less money - enough less for the buyer to cover his butt. After all, if it isn't at least 99.95%, somebody will eventually have to re-refine it and this costs money. If the bad signs of impure gold are evident and, it is a large lot, the buyer will want to assay it. You pay for this, also. Instead of trying to assay your refined gold, I would try to produce at least 99.95% pure. It'll save a lot of hassle.

GOLD TESTING
Gold and silver testing solution formulas
Here are the formulas that came with a test kit I once bought. It came with empty glass bottles and gave the formulas to make up the solutions. 10K - 3/4 ounce, by volume, nitric acid - 1/4 ounce distilled water 14K - 4/5 ounce nitric acid - 1/5 ounce dist. water - 10 drops of hydrochloric acid 18K - 1/5 ounce nitric acid - 1/5 ounce dist. water - 3/5 ounce hydrochloric acid Silver test soln. - Dissolve 20 grams of potassium dichromate in 3/4 ounce of nitric acid mixed with 1/4 ounce of distilled water. A drop of this on a silver alloy will turn red, the higher the silver, the redder the drop. You have to see it I have seen other different formulas. I had problems figuring out what you guys meant. The formulas are in fluid ounces, not weight ounces. There are 29.6 mL in a fluid ounce. I just copied it off the instructions. Please not that I have never mixed these up. I always used the various pre-mixed solutions that I bought from companies that sell jeweler's supplies. I also see them on eBay. They also have 22KT. They're cheap. If you can measure mL, milliliters, that would be the easiest. Here are the exact numbers. You can probably round them off. Just measure them as accurately as you can. Fluid ozs. don't convert to mL that evenly. 10KT - 22.2 mL nitric - 7.4 mL distilled water 14KT - 23.7 mL nitric - 5.9 mL distilled water - 10 drops hydrochloric 18KT - 5.9 mL nitric - 5.9mL distilled water - 17.8 mL hydrochloric Silver - 20 grams potassium dichromate - 22.2 mL nitric - 7.4 ml distilled water

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Using a touchstone
When you apply the acid to the streaks on the touchstone, you are looking for the amount of attack, the rate of attack, and the color produced. Stronger or weaker nitric will effect these. It's a visual thing. You compare these unknown streaks, side by side, at the same time, with streaks made with gold of known karats, usually from gold testing needles or from gold objects that you know the karat of. It's really pretty simple, once you get the hang of it. Play with it. Make streaks with different things and try all the acids on them. Be very careful not to cross contaminate the acids.

Acids used in testing solutions

The formulas I gave are based on reagent grade or technical grade nitric acid, although, the technical grade is a little weaker. Since this is a comparison thing known karat vs unknown - slight variations in nitric strength shouldn't make that much difference. When I use the commercial test acids, there are slight differences in strength. When I buy a fresh one, I have to get used to it's differences. Also, the acids containing hydrochloric will get weaker over time. The main things are that your 10KT acid doesn't dissolve a 14KT streak or the 14KT acid doesn't dissolve an 18KT streak. I should say dissolve quickly. If you let them sit long enough, there could be some attack. For this reason, I usually cut my observation off at, say, 10 seconds.

Eraser thickness test

The simplest test is to take a pencil eraser and use it to try and erase the gold off in a spot. If it comes off at all, it certainly isn't gold filled. As thin as Steve says it is, it will be gone in from 1 to 5 medium pressure strokes. Erase until you can see the underlying metal. If the metal underneath is also yellow, you will have to look closely but, there will be a difference. The most likely is nickel, which is easy to see. Don't erase the nickel. Go 2 strokes and look - 2 strokes and look. Once upon a time, I got pretty good at this and could gauge thicknesses. Play with it. I like the yellow pencil erasers.

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My way of testing for PMs in acid solutions with stannous chloride

Although it doesn't make much difference, I've always preferred using stannous chloride. I use a clean eyedropper (drug store) and put 2 drops of the solution to be tested on a piece of filter paper. I then get a few crystals on the tip of my knife and put them onto the drops. Then I add a drop or two of water. The water remoistens it and makes it work faster. Notice the color. Gold is purple or nearly black. Palladium is yellow-brown. Platinum is yellow. The only other thing that I know of that will produce a color, besides some of the other platinum group metals, is cobalt. Sometimes, it produces a light blue. The type filter paper is important. The drops of solution are absorbed by the paper and the colors spread out. The various precious metals spread out to different distances. You can tell what, and how much (if you're good at it) of each of the metals you have by noticing the color and intensity of each color ring. You want a fairly hard paper that won't allow the colors to spread too quickly. There is a common analysis method called paper chromatography. You simply hang a strip of filter paper (sometimes, treated) down into a small container of the liquid sample. The solution climbs up the paper and separates into it's individual chemicals. Interesting stuff. By running and comparing standards, you could get a pretty good idea of what and how much is in the solution.

ICs
Aluminum bonding wire
Aluminum wire bonding has been widely used at least since the early '70's. On this forum, some have said that the silver colored wire is silver. It's not. It's aluminum.

Traces
The traces running between the ceramic layers used to be molybdenum manganese thick film. I assume it's still the same. Also, the leads on side braze IC packages are silver soldered to plated moly-manganese pads.

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Gold values on an IC
Much of the gold value will be under the chip, if it's attached with gold/silicon solder. I believe the solder makeup is 96Au/4Si. About the only thing that will dissolve it is true hot aqua regia. The acid can only dissolve the solder starting at the edges of the chip. It can literally take take days for the hot acid to completely undermine a large chip. The main reason for breaking up the CPU is to break up the chip. This provides much more chip edge area for the acid to penetrate. It will still go slow. When the gold is gone, you'll be able to slide the pieces around on the pad. We used to speed this up on all-gold side braze packages by heating the part up to the melting point of the solder, on a heating block, and removing the chip with a vacuum probe. A sharp pointed knife, like an Z-Acto will work. We then put chip and package in the aqua regia. I think the solder melts around 700-800 F. There are several possible sources of gold on these parts. The percentages are educated guesses and only apply to all-gold parts - gold in every category below. High value: 60% - Gold(80%)/Tin(20%) eutectic braze used to attach the gold plated metal lid to the ring - Gold(~96%)/Silicon(~4%) eutectic braze used to attach the chip to the pad Medium value: 30% - Gold plating on the legs - Gold plating on the metal lid Medium Low value: 10% - Gold plating on the inside fingers - Gold plating on the inside pad - the flat square area where the chip is is mounted - Gold plating on the bottom of the chip - Gold plating on the ring where the lid is attached Very Low value: 2% - Pure gold bonding wires going from the chip to the fingers - about a mile (1 mil dia.), or two (.7 mil dia.), of wire to the troy oz. This figures out to $.005 to $.01 per inch of wire.

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IODINE
Homick patent - 3957505
It's been 30 years ago, in the Silicon Valley. Homick worked for a man that later became my partner. Homick's background was in printed circuits. I have never met him. I have recovered the gold from many iodine strippers used in electronics manufacturing, but I've never used the stripper, itself. I was very satisfied with cyanide. One of the beauties of cyanide is that you can destroy it. Until today, I hadn't read the iodine patent in 30 years. A fume hood would be adequate. A good fume hood requires at least 100 cfm per sq.ft. of open area. Since iodine and chlorine are both halogens, I would expect a similar strong odor. Just a little bit would probably notify your nose that you were breathing the fumes. You're right. The best things about this are that you can reuse it and that it's reasonably non-toxic. You might have trouble using this on placer gold. Unlike plated gold, it always has some Cu, Ag, and other stuff alloyed with it (usually from about 2% to 35%, total). I2/KI is quite selective towards gold. It may, or may not, dissolve the particular alloy. Test with very small experiments. Also, rinsing would be critical, in your loose materials. Poor rinsing loses I2. You probably should save your rinses for I2 recovery. The buffer thing is vague. It, as buffers do, mostly eliminates the need for pH adjustment. However, you have to start somewhere. Maybe, 1 or 2 ozs/gallon for start-up. A buffer is a buffer. Between certain concentration limits, you will get the same pH buffering (stability). He says the best pH is between 6 and 8. Check it after adding the buffer. You probably need a meter. He also doesn't tell you how to extract and collect the iodine, for making up a fresh solution, when the Cu, Ni, etc., gets too high. I would guess you use distillation.

MANUFACTURING SCRAP

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The best gold bearing electronics scrap

There are two main sources of scrap. I'm speaking primarily of electronic scrap, but some other types can fall into the category. First, there is the type that you're all familiar with. This is scrap mainly generated from equipment that is no longer used: computers, auto parts, etc. For the sake of this discussion, let's call it Used Scrap. The second type is more hidden to you. This is scrap that comes from the manufacturers of these items. Let's call this Mfgr. Scrap. There used to be an axiom that, of all the gold purchased by electronic manufacturers, to make their parts, only 60% of it went out the door. The other 40% ended up as scrap - rejects, trim, etc. I have no reason to doubt that these numbers still hold true today. I still have a flow chart I made, some 25 years ago, that shows the 15-20 basic categories of scrap that they generate. There's surely a lot more Mfgr. Scrap than there is Used Scrap. Where does this scrap go? Mainly to medium and large refineries. Local scrap metal dealers get their fair share. Some is landfilled and lost. Some is stolen by employees. The beauty of the Mfgr. Scrap is in it's form and it's volume. Take pins, for example. Instead of getting pins, here and there, off of used boards, a manufacturer might generate 6 drums of nothing but gold plated pins in a month. That's quite a sight, especially if you dump them out to make sure you're not paying $8 a pound for rainwater. Instead of having to trim silver off of relays from Used Scrap, a contact point manufacturer may generate several buckets of nothing but loose silver/gold/Pt points. Most Mfgr. Scrap is simpler and more concentrated. Instead of stuffed boards, they have the individual components. To the amateur, the volume of scrap generated by manufacturers can be overwhelming. Several years ago, I visited 4 small circuit board manufacturers in a very small city in Missouri. One of them had 10, pallet size, Gaylord boxes, full of decent circuit board trim. Each piece had some gold on it. Electronic manufacturers are everywhere. Often, small towns donate land to manufacturers so they will locate there. Most refiners don't mess with Used Scrap unless the stuff comes to them prepared. They certainly don't hustle Used Scrap. They go for the Mfgr. Scrap, the easy, huge volume stuff.

97 Manufacturers aren't in the scrap business. They're in the manufacturing business. Scrap takes up space and they like to get rid of it. Most, especially the smaller companies, are very friendly and will talk to any buyer that seems serious. In small towns, especially, the local scrap metal dealers get the stuff. They often pay one flat low price for everything, no matter how many types are represented. The PM scrap is gravy. In the old days, there was a lot of hankypanky by the employees that managed the scrap, especially in the huge companies. I imagine some of that still goes on. One type of scrap that the manufacturers get real serious about is scrap that contains toxic materials, such as lead solder or cadmium in points. Since the EPA set up the "cradle to grave" responsibility act, manufacturers watch this scrap real close. They inspect the facilities they sell this stuff to. Also, some scrap parts are company secrets and some they don't want getting on the second hand market. For this type scrap, the buyer has to sign a "certificate of destruction" and they will inspect his facilities. Sometimes, they sign contracts (usually 1 year) with a refiner. Other than these exceptions, most all scrap is up for grabs. Most manufacturers send their stuff to refiners. They have to wait for their money and they all know the refiner's reputation for stealing. I've always thought that many would rather sell the stuff outright and avoid the hassle. Getting scrap from manufacturers isn't for the small thinker. You have to think big quantities and get all your ducks in a row. You have to study the subject, know something about sampling and assaying, and know your scrap. I've only touched the surface of this lucrative subject and, if there is interest, I'll write more later. Much of my 40 years experience is in dealing with electronics manufacturers, although I haven't done it much in the last 10 years. I imagine everything is still about the same.

MELTING
Gas furnace info
I really don't think you'll be happy with an electric furnace. Some of the stuff you'll melt can corrode the elements. After the first heat, the elements become brittle. You will have spills. Unless you have a hi dollar controller, you can have a melt down. I would definitely build a gas furnace on the order of the link on jimdocs post: http://www.backyardmetalcasting.com/hmkit.html

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This lid arrangement, though, is too complicated. The easiest is to use a pivot pin, at the back, where the metal lid ring meets the body. Instead of lifting the lid, you pivot it to the side. Very simple. You weld two pieces of pipe, about 3" long. Weld one flush to the top of the body and the other to the lid. Weld about 1/2 of the bottom of the body pipe closed. You put the lid on the body, line up the larger pieces of pipe, and insert the pin. The pin should not be too loose but definitely not snug. For the large #70 furnace, I used 1" to 1 1/4" and 3/4" pipes, I think. Try various sizes for fit. Make the pin long enough so that it sticks up about an inch above the lid. That way, if you want to remove the lid for relining, you simply pull the pin. Don't seal the bottom of the body pipe completely. If you leave a gap, you can clean dirt, etc., out of it. Weld a [ shaped handle, from rebar, to the front of the lid. Use refractory cement - about $50/bag. Plan on a 2.5" - 3" bottom, sides, and lid thickness for a small to medium furnace. I prefer large diameter pipe for the body and lid - about 1/8" thick - from a scrap yard. Have the pipe cut accurately and grind very flat. Weld a plate on the bottom. Weld 4 short lengths of rebar inside the lid to support the refractory. Use an empty can as a mold for the hole in the lid. Use a soup can for a small furnace and a 1# coffee can for a large furnace. You'll need something round as a mold to cast the walls. Use something you can get out after casting or, something you can burn out. For a small furnace, you can use collapsible stove pipe. For larger furnaces, they make sturdy cardboard tubing of various sizes. I prefer natural gas over propane because, small propane tanks freeze up, especially in cold weather, and stop working. But, if the furnace is outside, you'll probably have to use propane. Propane is hotter and I've run #20 furnaces on 3/8" copper tubing. You can use an old upright vacuum cleaner as an air supply. I can talk more about the burner later, if you're interested. I need to get up my Adobe Illustrator. A #4 silicon carbide crucible holds 4# of aluminum. Although that sounds big, it's about right for 50 oz of gold. Go to a foundry supply, on the web, and find the dimensions of the size crucible you want. Plan on a gap of about 2" between the crucible and the walls. This way, you can determine what diameter the furnace should be. A #12 crucible is about the biggest that can be handled with 1 man tongs. Above that, you need 2 man lifters and pourers. I would build a bigger furnace than you think you need. For 9999 gold, you need a small dedicated furnace. If you melt less pure gold, silver, or any other stuff in it, you'll contaminate the very pure gold. If you want to blow up a furnace, leave it outside in the rain, unsheltered. The one on wheels, in the link, might be a good idea. I probably haven't give enough info or, explained well enough what I did give, to

99 build a furnace. I need drawings. Another subject. You mentioned plating out copper and nickel from the sulfuric after evaporating the water from the dilute sulfuric. I question whether this will work but, it depends on how strong you get it. You will have more luck plating out of the dilute sulfuric before evaporating. Use a lead anode.

Kerr Electromelt
This is to answer the old post, at the top of this page, about the Kerr Electro-Melt. First off, there are other brands out there besides Kerr. They are all expensive. The last time I looked, they started at about $800. http://shorinternational.com/MeltFurnace.htm I owned one of these gadgets about 25 years ago and didn't care for it. It just sat on the shelf. It seemed to take forever to heat up. Like induction furnaces, you couldn't really flux the metal to clean it up, or you would screw the crucible up. I would much prefer a small home-made gas crucible furnace. Cheaper and better. It all depends on what you use it for. Not too long ago, we had the idea of using one to buy scrap karat gold, etc., from jewelers or pawn shops. We were going to melt the gold, stir it, pin sample it, and pour it into a bar, in front of the jeweler or pawnbroker, in his own shop. We would keep half of the sample, give him the other half, mark or stamp and weigh the bar, and let him keep it. When we finished our assay, we would go back and do the deal. He could have his sample assayed, in the meantime, if he wished. We figured the customer would like this approach because it kept everybody honest. I still think it's a good idea. This is the only good application I have seen for the Electro-Melt. You could also maybe find one handy for doing some jewelry castings. For the refiner, I don't think so.

Advantages of a gas furnace

Do you want a box furnace or a pot (crucible) furnace? IMHO, the only thing a box furnace is good for is fire assaying. To me, when melting gold or silver, you need to be able to chemically flux the metal, in order to improve the purity. This is very inconvenient (if not impossible) to do in a box furnace. It is very easy to do this in a pot furnace. Also, in a pot furnace, improving purity is probably 10 times more efficient than it is in a torch melt. With a pot furnace, you can also see what's happening.

100 If you do want a pot furnace (which I think is what you need), why, oh why would you want to go electric? Building a small gas pot furnace is much more simple (and cheaper) to build than an electric furnace. You also don't have corrodeable elements or expensive controllers to worry about. You can use natural gas, propane, etc.

Gas furnace info part 2

Are the bricks the light weight, soft, insulating type or the heavy, hard, refractory type? If they are the soft type, you can't use a flame directly on them. You can line them with about 1", or so, of refractory cement. I always liked to have 2 furnaces. A small one, about a #4 or #6, for only pure metals and a larger one, about a #16, for whatever. A #16 is about the largest that one man can safely handle with only a standard pair of crucible tongs, without breaking the side out of the crucible.

Gas furnace info part 3

I just found about 6 commercial crucible furnaces, for copper, gold, and silver, on the net. All of them used a hard firebrick lining with a 2" insulating (probably soft firebrick) layer underneath it. Every furnace I made was out of mixed refractory cement. I have never used firebrick. A number of pros have told me never to line a furnace with soft insulating firebrick. They said it wouldn't stand up to the direct flame and, I definitely know that it won't stand up to the fluxing chemicals or molten metals. On this forum, there are two threads that prove this. In one case, someone was melting and fluxing metal, in an electric box furnace, that somehow escaped into the soft firebrick lining. Everywhere it landed, the flux and metal ate big holes in the soft firebrick. The guy posted photos of it. In another thread, someone was trying to flux melt metal, with a torch, in a dished out area on a soft firebrick. The flux and metal melted down through the firebrick and he had to dig it out. No matter how good you are, you will always get flux spills in the furnace. Crucibles will wear thin and get holes in them. Melts will foam over, especially when using stuff like standard hydrated borax. Most all furnaces have clean out holes at the bottom for this purpose. Soft firebrick is called insulating brick and that's what it is used for - not lining high temp corrosive melting furnaces.

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Propane fired furnaces

My main complaint about propane is that the tanks freeze up and will eventually shut down. Even a 100# tank can shut down in a couple of hours, in a cold climate, if you are running a large enough furnace. You can tell how much propane is left by observing where the freeze line is.

Furnace temperature colors

APPROXIMATE FURNACE TEMPERATURE COLORS Lowest red visible in the dark.......... 470 C ..... 878 F Dark red, blood-red....................... 550 C ..... 1022 F Dark cherry.................................. 625 C ..... 1127 F Cherry-red, full cherry................... 700 C ..... 1292 F Light red....................................... 850 C ..... 1530 F Orange......................................... 900 C ..... 1652 F Light orange.................................. 950 C ..... 1742 F Yellow........................................... 1000 C ... 1832 F Light yellow................................... 1050 C ... 1922 F White.................................... 1150-1200 C ... 2102-2192 F

MEMBRANES
Membrane cells for nitric
I spent a couple of years experimenting with ion exchange membrane cells. They are basically ion traffic controllers. You can buy membranes that only pass negative ions or, those that only pass positive ions or, those that pass no ions, etc. In the Shor refining machine, I think he uses one of these membranes. It's in one of his patents. I've worked out a way to make pure nitric plus water with a membrane cell. It's basically 3 or 4 inline plastic chambers, with membranes in between, and electrodes in the end chambers. The chambers all contain liquids.

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Sodium nitrate is in one chamber. The nitrate part of the sodium nitrate is pulled into another chamber by the current. The hydrogen ion generated at the anode is also pulled into the same chamber from the opposite direction. The result is H+NO3 - Nitric acid. They use these things for desalinization. The Na+ and the Cl- are pulled out of the water, to other chambers, in different directions. I know that this will work from past experiences. No doubt. It can be made to any strength. The longer it's on, the stronger it gets. The problem is in finding a membrane that will stand up to strong nitric. I'm still looking. I may be able to use a flower pot with the hole sealed up. The old fizzer cells, which were membrane cells for making gold chloride with strong HCl and current, used unglazed clay pots as the membrane. This would be very cheap to set up. The biggest cost would be the power supply. I spent a couple of years experimenting with ion exchange membrane cells. They are basically ion traffic controllers. You can buy membranes that only pass negative ions or, those that only pass positive ions or, those that pass no ions, etc. In the Shor refining machine, I think he uses one of these membranes. It's in one of his patents. I've worked out a way to make pure nitric plus water with a membrane cell. It's basically 3 or 4 inline plastic chambers, with membranes in between, and electrodes in the end chambers. The chambers all contain liquids. Sodium nitrate is in one chamber. The nitrate part of the sodium nitrate is pulled into another chamber by the current. The hydrogen ion generated at the anode is also pulled into the same chamber from the opposite direction. The result is H+NO3 - Nitric acid. They use these things for desalinization. The Na+ and the Cl- are pulled out of the water, to other chambers, in different directions. I know that this will work from past experiences. No doubt. It can be made to any strength. The longer it's on, the stronger it gets. The problem is in finding a membrane that will stand up to strong nitric. I'm still looking. I may be able to use a flower pot with the hole sealed up. The old fizzer cells, which were membrane cells for making gold chloride with strong HCl and current, used unglazed clay pots as the membrane. This would be very cheap to set up. The biggest cost would be the power supply.

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Types of membranes
Unglazed clay flower pot might work if you can plug the hole. We once discussed it on the forum. A porous cup (Coors) would work. Dupont makes a positive (will only pass positive ions) membrane, of teflon, called Nafion, in sheet form. There are lots of commercial membranes that pass only +ions, only -ions, or only +1 ions. A + and - pair is commonly used for desalinization. It takes the Na+ out through one membrane and the Cl- out the other. One can dream up tons of applications for these various electrodialysis or ion exchange membranes ganged together in various ways. I used to fill notebooks with diagrams.

MISCELLANEOUS
Selectively stripping gold plating
A lot of you have been around long enough to realize that one of the most important things would to be able to strip gold off without dissolving the base metal. That way, it would be faster, cheaper, and would produce less waste. You would not only have gold to sell, you also would have copper. If you ever come up with a new, cheap, safe method for doing this, don't tell anybody and quickly get a patent on it. About the only things that have been found to do this are cyanide/oxidizer, iodine/iodide, and bromine/bromide. It's also maybe possible to use hypo (sodium thiosulfate). As Sue suggested, somebody should experiment with hypo. I used cyanide every day for about 20 years. Sometimes, I worked around 5000 gallon tanks. It is cheap, efficient, safe, fast and, most important of all, it can be completely destroyed. It's formula is CN and it can be broken down to CO2 and N2. The following is a secret, never told, so don't tell anybody. I'll probably never do anything with it. One day, in L.A., I got the idea of using abrasives to remove the gold. I put some pins in a rock tumbler along with some silicon carbide powder. All the pins got was dirty. I did no more work on this. I think it will work with the right abrasive. The problem is in separating the gold from the abrasive. Probably something like a separating table or a spiral wheel.

104 The Wheelabrader. I think that's what they call them. This is a vertically rotating, cage like, wheel with small holes in it to prevent the parts from falling out and to let the sand fall through. It is designed for small parts. Inside of the wheel is a sandblasting nozzle. The wheel is inside of a sandblasting booth. The parts are put into the wheel, the nozzle is turned on, and the wheel is rotated. The metal wheel is coated with a rubbery plastic to prevent the sand from eroding the wheel. Eventually, every part is completely sandblasted. It gets in all the holes and the cracks. There's really not much to them and they could be made. I spent about 4 hours, one day, doing experiments in a company that sold Wheelabraders. I had lots of bags of different types of parts, including rhodium plated jewelry. I tried several abrasives that worked so-so. However, the problem of getting the gold out was always on my mind. I finally tried some glass shot and steel shot peening media. This stuff worked great and fast on everything. Instead of abrading the gold off, the shot peens it off. During peening, the plating layers are peened thinner. This stretches the gold sideways and it just pops off (along with the nickel). Some of the steel shot Wheelabraders have built in magnetic separators to clean the shot from the garbage. Gold flake collection should be easy with one of those.

More on stripping
Dissolving all the copper or both the copper and gold may be great, when you're just playing around but, when running large amounts, it will always lose money. Besides using tons of chemicals, you generate tons of waste. Also, you convert valuable copper metal to waste. There are 3 ways to chemically approach gold plated copper scrap. You can either (1) Dissolve everything (2) Dissolve only the copper (3) Dissolve only the gold. The pros, unless they use cyanide, simply melt everything and ship the bars to a copper smelter By far, (3) above is the very best choice. The sulfuric stripper will only strip gold but, you have to make electrical contact. The very best non-electrolytic system for stripping gold was cyanide but, the EPA virtually eliminated this wonderful and safe (believe it or not) chemical. If I still had a lab, I would put a lot of effort experimenting with new nonelectrolytic systems that would dissolve the gold and not the copper. There are certain chemicals that will inhibit the attack on copper and other metals. Maybe one of these would work for copper, yet will allow the gold to be dissolved.. I just googled for copper inhibitors in HCl solutions and the name benzotriazole came

105 up often. I think I would start there. I have never used this chemical but, it seems to be cheap, fairly safe, widely used, and it doesn't take much. I would start at about 1 gram per liter. I would probably try the HCl-bleach formula first. I even saw it on eBay, but the quantities were small and the prices were high - typical eBay

Electrowinning and electrorefining

A very common statement, when discussing the recovery of metals from solutions, is to simply "plate it out." I have seen or heard this phrase used endless times on the internet and probably a dozen times on this forum. In theory, this is sort of possible. In practice, it is nearly impossible. In most any metal solution, something will plate out onto the cathode. The trick, however, is to get a "sound" deposit on the cathode. By "sound", I mean a deposit that will stick (adhere) to the cathode and also produce the deposit in a solid, non-spongy form. In order to do this, the solution can only contain the metal in question, copper, for example. If any other metals are in the solution, the deposit will usually be "unsound." Also, if there are contaminants in the solution, such as organics or unnecessary chemicals, the deposit will be unsound. The formulas for plating solutions are very precise and sensitive. As an example, here's a standard formula for plating copper from a sulfate solution that I took from the Metal Finishing Guidebook. The formula for electrowinning copper is very similar. Copper sulfate - 26-33 oz/gal Sulfuric acid - 4-10 oz/gal Chloride - 50-120 ppm If the chemicals are out of the above ranges, the deposit will be unsound. If there are iron, nickel, or most other metals involved, the deposit, most probably, won't stick to the cathode. It will also produce a spongy deposit (looks like turds) that will float and produce a short between the anode and cathode. Also, the other metals will co-deposit and you'll end up where you started. This deposit will nearly be impossible to collect and recover. The copper system is more simple that most. The other metal systems are more complex and, in most cases, even more sensitive to contamination. The least sensitive systems are those that use a cyanide matrix. When dissolving metals electrolytically, several systems solve this problem by using membranes or porous cups, as barriers, to prevent the dissolved metals from coming into contact with the cathode. The dissolved metals are kept confined in an anode chamber. The Shor Simplicity system is an example of this.

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When someone says, "just plate it out", I put it in the same category as when someone talking about refining gold says, "just melt it down." In the past 150 years, or so, electrowinning systems have been developed for refining metals that came from ore. The systems (formulas) took many years to develop and many are covered in patents. The constituents in ore, however, generally run the same ever time and, if you fiddle with them long enough, you can come up with a system. In our case, the constituents are different every time we do it. This is a complex subject that I have barely touched upon.

List of scrap items that contain precious metals

Scrap Items that contain precious metals. 1) Jewelry and Dental a) Karat Gold b) Sterling Silver c) Gold Teeth and Plates d) Platinum - Pt/Ir, Pt/Ru, etc. e) Gold-Filled f) Buffing Dust g) Filings h) Floor Sweeps i) Carpets j) Traps or Settling Drums and Sludges k) Dental Amalgam l) Cyanide Bombing Solutions 2) Coins a) US 90% Silver b) US 40% Silver c) US War Nickels d) Silver Bullion Coins and Bars e) Old US Gold Coins f) Gold Bullion Coins and Bars g) Canadian 80% Silver h) World Silver Coins 3) Consumer a) Gold Filled Eyeglass Frames b) Silverware, etc.

107 4) Electronic a) Personal Computers b) Circuit Boards c) Fingers d) Circuit Board Trim e) Router Dust f) Backplanes g) Mainframes h) Gold Lids i) Old Gold ICs j) CPU ICs k) Hybrid Packages l) Hybrid Circuits m) Plastic DIPs n) Ceramic DIPs o) Lead Frames and Trim p) TO5s and TO18s q) TO3s r) TO92s and LEDs s) Relays t) Thick Film Circuits u) Thin Film Circuits v) Pins w) Connectors x) Platinum Group Scrap y) Silver Plated Wire z) Silver Capacitors aa) Palladium Chip Capacitors bb) Gold Backed Silicon Wafers and Chips cc) Switches, Etc. dd) Tantalum Capacitors ee) Silver DMSO Solutions ff) Solder Preforms usually Au/Sn or Au/Si 5) Plating and Coatings a) Gold Plating Solutions b) Silver Plating Solutions c) Other PM Solutions d) Drag Out Solutions e) Gold Ion Exchange Resin f) Wipes g) Danglers and Nodules h) Liquid Gold Containers i) Plating Salts j) Filter Cartridges k) Gold Stripping Solutions

108 l) Reject Plated Parts m) Silver Anodes 6) Electrical a) Large Silver Contact Points 7) Telephone a) Wire Relays Palladium points b) Other Relays c) Copper Sticks with heavy gold plating every few inches d) Cell phones Cool Brazes, Pastes, and Solder a) Circuit Board Solder from Wave Solder Pots b) Braze and Thick Film Pastes c) Silver Solder and Brazes d) Gold Solder and Brazes 9) Photographic a) Medical X-ray Film b) Industrial X-ray Film c) Litho Film d) Miscellaneous Film e) Silver Flake f) Hypo Solutions g) Steel Wool Canisters h) Ion Exchange Resin i) Emulsions 10) Jet Engine a) Gold Brazed Stators b) Gold Brazed Stator Segments c) Gold or Gold/Palladium Brazed Twin Rotor Blades d) Gold/Platinum Pitot Tubes e) Gold Fuel Manifolds f) Gold Fuel Plumbing g) Silver and Silver/Palladium Stators h) Silver Brazed Stator Segments i) Miscellaneous Aircraft Parts 11) Automobile a) Headlamps b) Oxygen Sensors c) Spark Plugs d) Catalytic Converters 12) Catalysts

109 a) Catalytic Converter Catalysts b) Ethylene Oxide Silver Catalysts c) Petroleum Catalysts 13) Mining Materials a) Gold Nuggets b) Gold Dust c) Gold Ore d) Gold Amalgam e) Dore Bars f) Black Sand 14) PM Refinery Scrap a) Silver Chloride b) Slags c) Crucibles 15) Miscellaneous a) Evaporating and Sputtering Chamber Scrap b) Silver Plated Copper or Brass c) Button Batteries d) Military Silver Batteries e) Military Salt Water Conversion Kits - Silver f) Silver Heat Exchangers g) Platinum and Pt/Rh or Pt/Ir Thermocouple Wire h) Platinum Lab Crucibles i) Gold, Silver, or Palladium Leaf j) Solid Silver Wire k) Sputtering Targets l) Costume Jewelry Gold or Rhodium Plated m) Memory Disks Gold and/or Rhodium Plated n) Computer hard drives

SO2 water
I worked with a guy in Oregon that made SO2 water to drop gold. To use it, he just poured it into the gold solution. He saturated ice water with SO2 and put it into sealed gallon jugs. You would think that the jugs would pop their lids but, they never did. I couldn't see much sense in it but, the guy loved using it. A fume hood was a must. The same guy made a vacuum pump with a sump pump sitting in a 5 gallon bucket of water. It had an aspirator plumbed onto it and the water circulated back into the bucket through a pipe. The pipe formed a handle, so you could easily lift

110 it out of the bucket. It worked amazingly well. The head ratings on the pump and the aspirator had to be matched. The only problem was that the water got so hot after an hour that the pump stopped. This was always solved by putting in fresh water. The guy had been using the same pump for years. Never wore out

Nickel silver
There is no silver in nickel silver. Another name for it is German silver. It looks sort of like silver. Thus, the name.

The Electromotive Series

This is a short electromotive series list that only contains the common metals. The list could be expanded to contain every element and alloy. The rule is that a metal will drop out of solution any metal below it in the list. The metal used also must be soluble in that particular solution. The metal used actually trades places with the metal(s) that it is dropping. It dissolves into the solution and the other metals drop out, as metal powders, usually. The metal will not drop out any metal above it or, itself. The general dropping out process is called cementation. For example, you have an HCl solution containing copper, nickel, gold, and palladium. You can first drop out the gold and palladium using metallic copper. The copper will not drop the dissolved nickel or copper. After collecting the gold and palladium, you can use aluminum or iron (steel) to drop out the nickel and copper, as metallic powder. The end result is much less toxic. The greater the surface area of the metal, the faster the other metals will drop out of solution. Sometimes, the metal doing the dropping gets completely covered with the metals being dropped and, the reaction slows down. Scrap it to expose fresh metal. If you drop silver from a nitric acid solution containing excess nitric acid, using copper, the excess acid will, at first, only dissolve copper. When the excess acid is used up, the copper will start cementing silver. Here's a simplistic way of looking at the EM series. The metals at the bottom want to be metals. The metals at the top don't want to be metals - they want to be metallic compounds. In nature, gold is often found in metallic form, copper is

111 sometimes found in metallic form, and aluminum is never found in metallic form. A long time ago, aluminum metal was more valuable than gold because no one could reduce aluminum compounds to aluminum metal, except in small quantities, at great expense. They used such super powerful things as metallic potassium to do this. It was so valuable that some king or queen (British, I think) had a crown made from aluminum. http://en.wikipedia.org/wiki/Aluminum

Magnesium Aluminum Zinc Chromium Iron Cadmium Nickel Tin Lead Hydrogen Copper Silver Palladium Mercury Platinum Gold

Refining suggestions
If refining were easy, everybody would be doing it. Some suggestions. Know all the numbers. At all times, know where the precious metals are located. Learn what different chemicals do to different metals and other materials. Learn what heat does. Know what's in the solution and in the solids. Weigh and measure everything until you know more. Keep records. Add acids, precipitants, and urea in increments. Study. Know your options as how to process materials. Don't re-invent the wheel.

112 Look before you leap. If something goes wrong, don't go any further, until you've figured out what is wrong. Never get cocky.

An offer
In L.A., we had a big placer miner customer from Alaska. He did 30,000 ounces during each 3 month summer and we refined it. His business cards had an 1/8" nugget glued to it, He offered me a high paying job to helicopter in to mining camps, with a lot of cash and a couple of guards, and buy gold. Give me a break! Sounded a little scary, to me.

Fluxing with soda ash?

I disagree with your idea that soda ash will reduce base metal oxides to metal. It doesn't work out chemically, as I will prove. You are aware that we disagree on the use of soda ash for fluxing pure gold. Your contention, as I understand, is that soda ash reduces the base metal oxides to metals, thus re-contaminating the gold. A question is, Do you assume this because soda ash reduces silver chloride or, did you read it somewhere? Hoke? I sure don't remember it in Hoke. Easiest reading technical book I've ever read, BTW. I've probably read and studied Hoke from 10 - 20 times, cover to cover. If fact, the first time I ever heard it was from you. You did make me think about it. It kinda made sense, seeing that it reduces silver chloride to silver metal or, does it? Soda ash is used widely to help clean gold. I have met about 100 pro refiners that use it. I have never seen the reduction thing in print and, I have read a lot of stuff. I have found that the silver chloride is not reduced by the soda ash. The soda ash does not act as a reducing agent in this melt system. The soda ash (Na2CO3) converts the silver chloride to silver carbonate. The HEAT reduces the Ag2CO3 to silver metal, not the soda ash. In the 1st equation, below, the silver valence is +1 on both sides of the equation. If reduction had occurred, the valence would have gone from +1 to Zero, like in (3), below. This is a quote from the silver chloride chapter in the yellow IPMI notebook that both of us own, page 9. Verbatim quote.

113 Quote: This high temperature technique proceeds as follows: (1) 2AgCl + Na2CO3 = Ag2CO3 + NaCl (2) Ag2CO3 = Ag2O + CO2 (3) 2Ag2O = 4Ag + O2 Reaction (2) and (3) occur by thermal composition. The silver carbonate of reaction (2) completely decomposes at 225 deg C. The silver oxide of reaction (3) completely decomposes at 340 deg C.

I conclude that soda ash does not act as a reducing agent in the melt What if copper, nickel, etc., went through the same 3 equations? In the CRC Handbook, it gives the decomposition temp. of silver oxide (equation 3) as 644 deg F. There is none given for either of the val.+1 or val.+2 copper oxides. Valence +1 copper oxide has the lowest melting point of the two, 2255 deg F. Maybe, it decomposes at 3500 deg F. It doesn't say. You find very little copper metal in nature, BTW. For nickel, etc., their positions are even higher, than copper, on the electromotive series. They want to be metals even less than copper. Nickel oxide melts at 3614 deg F. And, the metal oxides must melt before they can become reduced. The soda ash could easily create carbonates with the base metals, which decompose to oxides at low temps. However, the reduction temperatures of the base metal oxides (equation 3) are much higher than that of the gold melt. The metal oxides will stay in the slag and will not contaminate the gold. The use of soda ash will not contaminate the gold, period. I conclude, without a doubt, that soda ash will definitely not reduce any base metal oxides in the gold melt. Gold is more efficiently cleaned using soda ash, along with borax and niter.

Tantalum and Ta/silver electrolytic capacitors

About 20 years ago, I found tantalum electrolytic electrolytic capacitors to be commonly found on circuit boards. On this link, a discussion of a newer variety of these is found about halfway down the page.

114 http://www.ami.ac.uk/courses/t.....index.html It's been a long time but, there were several types. Some contained Ta foil and some a Ta slug. They were all quite heavy compared to to the Al type. They looked the same as the Al type (round metal cans with a lead coming out each end - mounted parallel to the board) but, they could easily be distinguished by their color. The Ta type were much darker gray colored than the Al type. As mentioned in the link above, some Ta capacitors had shells made of silver to prevent leakage of the chemicals (sulfuric acid?) inside. These were very white in color, since silver is the whitest metal on the planet. I remember 2 silver types. One had a red plastic plug on one end and the other had a green plastic plug. One (if I remember right) ran 40% silver (I think the red ones) by total weight and the others ran 25% silver. I could be off on this. It may be 25% and 15%, respectively. I may be thinking of the silver button batteries, which ran 40% silver. Nitric acid can be used to dissolve the silver capacitor shell. The tantalum will be unaffected. Don't attempt to dissolve or melt the tantalum (5463 deg F. melting point) Only the metal itself, as is, is worth money. If you dissolve it (sodium hydroxide), it will be impossible to convert it back to metal and it will be worthless. Also, if you heat the entire capacitor, it will explode, due to the liquid trapped inside. Back then, Ta metal scrap was worth $12/pound. I think it went as high as $200 several years ago and then dropped back down. I found on the net that it was worth around $70, sometime in 2005. I wasn't able to find a current scrap price. As common as these were in about 1990, there still should be a lot of them around.

Gold plating
You can plate crappy gold out of any matrix that it will dissolve in - a gold chloride solution, for example. The problem is to get good plating that will stick and is bright and shiny. As far as I know, the only gold salts that will produce sound deposits are potassium gold cyanide, sodium gold sulfite, and sodium gold sulfate. I have also seen phosphate and ferrocyanide systems used, with less success. The other chemicals, and their amounts, needed in the solution are also critical. I stand behind everything I said in my previous post. I was once the head chemist for a company that, at the time, was the world's largest manufacturer of gold plating systems and, I also owned 2 hi-tech electronic plating shops in L.A. I know what I'm talking about. Almost anything different than that listed above has, over the last 150 years,

115 been tried and rejected. I know you want to experiment and, that's good. However, what you want to do is much more difficult (or, impossible) than you think. It's sort of like the unknowledgeable person thinking that, in order to refine gold, all you have to do is "melt it down." Think about plating gold directly on aluminum. If you look at the electromotive series (check my post in the Glossary category on this forum), you'll see that aluminum is near the top and gold is near the bottom. If fact, when both are in a solution, there is over 3 volts produced. This immediately makes the gold cement onto the aluminum, in the form of a non-adherent worthless powdery coating. This is the reason for the absolute necessary, intermediate zinc/nickel coatings. You could, I think, evaporate or sputter gold directly on the aluminum. Most gold plating solutions operate at about 3 amps/square foot and about 2 to 3 volts. Anything higher and you'll "burn" the deposit - produce brown powdery, non-adherent gold. There are some low gold (1/10 oz per gallon), proprietary jeweler's color golds that plate at 6 volts. Like it says, these are only thin "color" golds. The part is only kept in the solution for about 15 seconds. After that, the deposit starts plating dark and powdery. They don't provide any real protection, especially on something like aluminum. For a thicker sound deposit, a one ounce/gallon bath is needed, made up with very exacting amounts of other certain chemicals.

Migration of gold plating

Copper or silver, underneath the gold plating, will migrate up through the gold. This happens slowly at room temperature but, the migration rate is accelerated at higher temps. The surface will then corrode or tarnish. Nickel is normally used under gold to prevent migration. You must also consider that all gold plating, thinner than about 100 microinches, is porous. This is what allows the acids to penetrate and attack the base metals underneath the gold.

Recycling IC packages a business

A long true story. In about '72, I invented a method and formed a company, with a money partner, for the service of recycling all-gold plated, old type CPU, side-braze packages (mainly 40 lead) for reuse. These were rejected parts, in various stages of production. Most were rejected on final testing, after sealing.

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I went to the Silicon Valley to hustle business. I hit about 10 huge electronics concerns, cold, and showed them before and after samples. Every company I went to was very eager to talk to me and they all gave me samples of their rejects. I also found out that Fairchild Semiconductor had spent a lot of money trying to do this same thing and had failed miserably. There were also a couple of smaller companies that had worked on this, but their methods were Mickey Mouse and they produced unacceptable parts. I think they were the ones who got the patents that are mentioned below. Purple plague was one of the reasons for rejection. My biggest customers were Intel, AMD, and AMI. At the end, we were doing about 100,000 packages per week. We (1) Removed the lid and chip with heat and a vacuum probe and removed the bonding wires; (2) Chemically stripped (electrolytically) the gold plate and gold alloy brazes selectively without attacking the base metals (the crux of my invention). These base metals were Kovar legs and sealing ring, plus moly-manganese chip pad, internal traces, bonding fingers, and pads to braze the legs to. Also, silver/copper braze was used to attach the legs. There was also nickel plating under all the gold plating. I should mention that cyanide (the first thing I tried) wouldn't work because it attacked the copper and silver; (3) Replated the gold; and (4) Returned them to the companies for new chip attachment and reuse. Our recycled packages had a higher yield than new packages. We charged half the price of a new package. The new price of these same packages now is about $4 or $5, although there are far fewer of them used today. The extra gold we removed from the gold brazes (80/20, Au/Sn for the lid; about 96/4, Au/Si for the chip) nearly paid for our processing. At that time, when the companies put out a new chip, the early manufacturing reject rates were as high as 98% The business ended in '74 (I think) when Nixon devalued (10%) the dollar twice and there was a 6 month dock strike. The electronics industry died. No parts could then be shipped to or from from the overseas assembly facilities. Right before the strike, a company in Texas promised us 100,000 parts per day. When the strike hit, they went down to 5,000 per week. We shut our doors. Oh well. The same process can be used for high dollar ($10 to $1,000), all-gold, hybrid packages, which are used widely today in specialized applications. The process costs are about the same as on the cheaper packages and the 50% charge still applies. Lower volumes, lower setup costs, much higher profits, on the hybrids. I set up a small hybrid process in '80. We rented a booth in a ISHM show (International Society of Hybrid Microelectronics). We laid out about 20 different before and after packages on black velvet and got over 100 electronic companies that were interested in our wares. However, at that time, my main business was

117 gold and silver refining. 1980 was also the year that the PM prices went through the roof. We sometimes had 20 people waiting in line, when we opened the door, to sell us gold and silver scrap. There just wasn't any time to concentrate on the packages. As far as I know, no one else has ever come up with viable process to rework these packages. There are a couple of patents out, but they require a lot of hand work and are far slower, much more expensive, and inferior to mine. I didn't patent my process but it's still in my head (and in my head only, I think). My process is still very viable. About once a year, I feel a need to rant about this. If only that frigging dock strike hadn't happened! Oh well.

Electrolytic copper
Your experiments with electrolytic copper must have been brief. Unless zero base metals were being added to the copper, the deposit would, over time, become unmanageable. Since it would be foolish to do this on a one-shot basis, you would need a system that could be used over and over Let's say your bars are 98% copper/2% base metals. At first, the Cu in solution is much higher than the base metals (BM) and the cathode deposit will be smooth and adherent. The rate at which the various metals deposit is mainly dependent on their concentration and their individual electrical characteristics. Therefore, at first, there is very little deposition of the base metals. They build up and their deposition rate increases. At some point, the deposit turns to crap, no matter how much grain refiner (thiourea; iron-free molasses, etc.) is used. For a 30% base metal, copper alloy, the deposit may turn to crap in only 5 minutes. The number one problem in electrolytic refining systems is to maintain a sound, manageable, cathode deposit. You can't do that when base metals reach a certain level in the solution. You can only delay it, briefly, through the use of additives. I see no gain though the melting of PM scrap into copper. At best, you would convert solids to a powder, for easier dissolving.

Silver plating on boards

Silver plating, when used on traces, has a tendency to migrate through the board material, under certain conditions, thus creating dendrite silver shorts between the traces. For this reason, you will rarely see silver plated traces, or fingers, for that matter.

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In 40 years, I have never seen silver plating on traces or fingers.

Oscilloscopes
If the CRT, on Tektronix o'scopes, has a ceramic body, it is most likely completely coated on the inside with gold plating.

Anaconda copper
I once spent a week at the Anaconda Copper electrolytic tankhouse in Montana. If I remember right, they purified 1,000,000# of copper per day and, as a byproduct, they recovered 30,000 oz of silver and 3,000 oz of gold per month. These are only ballpark figures from my memory. They had 2,500, 400 gal cells. If you do the math, you'll see that the Ag and Au are present in the copper only in parts per million. All of the Au and silver end up being concentrated into what is called, "tankhouse slimes". These are the anode insolubles that are collected in the electrolytic cells. They are probably black in color and become quite slimy in a little water. Therefore, although there are PM's in any metallic copper that you may find, the levels are most probably so low that you would have to dissolve about 100,000 oz of copper to get an oz of gold. This would take about 3,500 gallons of nitric. Not feasible. The slags are also very lo-grade in PMs. However, the tankhouse slimes are another story. They are fairly concentrated in Ag and Au. They also contain Se and Te, both of which can be toxic under certain circumstances. Somewhere, I think I have a write-up on refining tankhouse slimes - I'll look. Also, there might be some info on the internet.

Freezing circuit boards

There are patents using liquid nitrogen and then grinding the scrap. In the early '70's, the refiners talked it up and played with it, but I don't remember any big operations. I think someone had a setup on a truck.

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Silverplate thickness on flatware and hollowware

Here's the list - for teaspoons only. These specs are supposedly well established in the industry. I don't know whether they are stamped, as such, or not. I also don't know the numbers for other types of pieces. Half plate - 1 tr oz Ag/ gross (144 pieces) of teaspoons Standard plate - 2 tr oz/gross Double plate - 4 tr oz/gross Triple plate - 6 tr oz/gross Quadruple plate - 8 tr oz/gross Federal specification - 9 tr oz/gross The silver thicknesses, on these, range from .000150" to .001250". The Fed. spec. ones figure out to 1 tr oz/sq.ft. of surface area. Here are similar plating standards for plated hotel hollowware. A dwt. (pennyweight) is 1.555 grams. There are 20 dwts in a tr oz. Light plate - 2 dwt/sq ft Medium plate - 5 dwt/sq ft Heavy hotel plate - 10 dwt/sq ft Extra heavy hotel plate - 15 dwt/sq ft Federal specification plate - 20 dwt/sq ft

Reed switches
When I was into plating, we sold Au/Pd alloy plating baths to reed switch manufacturers. They produced a white deposit on the reeds. Something else to look for.

Gold prophets
I read many newsletters by gold gurus in the early '70s that predicted that gold would soon hit $1000. It took 35 years. I made a good living for 40 years in the gold scrap industry. The best lessons I learned was to never listen to gold gurus and to never play the market.

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Relay contact points

The small gold plated points on relays usually have a silver base.

Connectors on backplanes
I once was involved with a company that generated semi loads of scrap backplanes - mostly Burroughs, if I remember right. There were 3 basic types of connector pins. The lowest value pins were those that were spot plated on only the contact surface. Of much higher value were those that were gold plated overall. The highest value pins had no plating. Instead, they had a small, round, 18K gold contact point. At the time, the gold price was about $400. The spot plated connectors, including the plastic connector body, ran less than $1/pound. The complete connectors with the contact points ran about $7/pound.

Gold precipitants
When you use zinc or any other metal to drop gold, the resulting gold powder will always be contaminated with that metal. This will have to be removed and that requires extra steps. For this reason, I prefer some sort of non-metallic precipitant. The most common are the sulfites: sodium metabisulfite, sodium sulfite, sodium bisulfite, and SO2 gas (more dangerous than the other 3 sulfites). Also, there is ferrous sulfate, oxalic acid, hydroquinnone, etc.

Transistors and ICs

The TO5's are the common "top hat" metal transistor packages about 1/4" big and are mounted with bottom lead wires. The TO18's look the same except they are only about 1/8". The TO3's are diodes and are about an inch long and are usually mounted with nuts and bolts or, are plugged in. The TO92's are black plastic about 1/8" in diameter with one side flat. The term "TO" means Transistor Outline and there are many more TO's than these four. There is a possibility of gold being in any of them. You have to open up a few of them and take a look. Especially with the metal packages, there are great variations of gold value. Take the TO5 as an example. On very old boards, they are sometimes painted black. Usually, if you scratch off the paint, you will find that they are completely gold plated. These are are of the highest value. Many TO5's have gold plated headers and wires with a non gold top hat (usually made of Kovar). These are of medium

121 value. The header is the flat bottom part where the chip and the leads are attached. Some newer ones have aluminum tops with non gold headers and wires. These can be worth nothing. All in all, the gold value of TO5's (and, TO18's) can range from zero to about $100 per pound, or more. The TO3's are very heavy and are, therefore, basically worthless unless the header and the pins are gold plated. In all types of parts containing chips, one of the greatest variables is the method of the chip attachment. The chip can be attached with either gold/silicon braze, silver braze, or epoxy. Only the Au/Si braze has value. Open up a part and look for braze that has oozed out around the chip. Scratch the braze slightly to remove any tarnish. If the resulting color is yellowish, you have Au/Si braze. You may need an eye loupe. Since the thickness of braze is about 20 to 50 times thicker than gold plating, most of the value can be in the braze.

Miscellaneous tips
A few things: 1) Arsenic was used as a fire retardant in the board material. I believe that it was replaced by antimony some 30 years ago. 2) In the old days, the gold was plated directly on copper. It was found that, over time, the copper will migrate into the gold, which is very indesireable. In the last 30 or 40 years, nickel plating has been used as a barrier between the copper and gold. You will find that stripping gold off copper is much more difficult than stripping gold off nickel. 3) Looking at an Electromotive Series chart, you will see a list of metals with aluminum near the top and all the precious metals, including silver, at the bottom. An approximate order of some common metals, starting at the top and going down, are Aluminum, Zinc, Iron & Nickel, Copper, PM's. The rule is that any metal above will knock any metal below out of solution. A chunk of copper will only knock PM's out of solution. Aluminum will knock out everything below it zinc, iron, copper, PM's, etc. Put an iron nail in a copper solution and the copper will plate out on the iron. Put a copper wire into a photo hypo solution and, if there's any silver in the solution, the wire will be covered with silver. All of this plating out or knocking out (as I call it), is called reduction. Reductions opposite is oxidation and reduction can be overcome by using oxidizing agents, such as strong hydrogen peroxide. There are lots of different metals on a circuit board. When you immerse the whole board, all these metals come into play. Unless you have a strong oxidizer present, all of the gold (and, silver) that you have dissolved will be be plated back

122 out (reduced) on the other metals probably present, such as aluminum, iron or copper. This plated out gold wont look like gold, but will be a black smut. I have made many thousands of dollars by buying gold plated copper pins that others have stripped. If I saw a black smut on the copper, I knew it had to be gold. I simply re-stripped the stuff. For these reasons, Im thinking that maybe the reason you coulnt get the gold out of the solution is that there is NO gold in the solution have you tested it? The weak mining leaches arent strong enough to leach boards. There is a good chance that it all plated back onto the other metals contained on the boards. Another possibility is that, if you were using a commercial cyanide gold stripper, the opposite might happen. The large amount of oxidizers that these contain might prevent you from being able to extract (reduce) the gold. All chemistry is push and pull, which is especially evident with cyanide systems. For all these reasons, you must be more selective as to what you put in the cyanide solution. Remove ALL aluminum and as much exposed iron and copper as you can before stripping. Look for black smut. Reality, dont give up on cyanide so soon. If done right, it is the easiest, safest, cheapest, fastest, and most efficient method of treating gold plated scrap. As soon as I get my second wind, Ill write up my barnyard cyanide process. If I were in Brazil or any other country where I could get away with using cyanide, it would be my first priority.

Copper from motors

Some of the most common items in a scrap yard, everywhere in the world, are small motors and other electrical things with armatures on steel shafts. The Bureau of Mines came up with a great method for melting the copper away from the steel. I don't remember whether they dealt with the windings, or not. This was published in one of their Reports of Investigation. These are out of print but exist in the files at the libraries of places like the Missouri School of Mines at Rolla and the Montana School of Mines. If you call them, they will probably be able to find it and send you a photocopy. This Report is very detailed and complete - they even tell you how to remove the cases, I think. We became very interested in this process and bought the stuff we needed to play with it, but never got around to actually doing it. As I remember, this is the way it generally worked. A chloride salt, such as barium chloride or calcium chloride was melted in a crucible to a little above the melting point of copper but below the melting point of steel - they ran it about 2200 deg.F. The armatures were removed from the case and burned to get rid of the organics. They were then put in a steel basket and dipped into the molten chloride. The copper melted and went to the bottom of the crucible, where it was

123 tapped off, cast into ingots, and sold. Very simple, interesting, and potentially profitable process. I also remember that the main danger was dragging moisture into the molten chloride - just a drop could cause the 2200 deg. chloride to splatter out of the pot. For this reason, the armatures were dried in an oven immediately before they were dipped.

Gold and silver bearing jet engine scrap

Does anybody know which jet engines have gold braze on some of their stators? I know that the JT3D, JT4D, JT8D, RB211, and, maybe, the JT9D do, but am not sure of what others have gold. I've refined a few semi-loads of them, but received them mixed and never knew what engines the stuff came off of. There are other types of gold-bearing parts on jet engines, also. Jet engine scrap with gold on it is mostly real rich stuff and I'm surprised no one has mentioned it on this forum. Jet engines are o'hauled all over the country, parts are replaced, and scrap is generated. Some pitot tubes are worth several hundred dollars a pound in Au and Pt. I used to get my scrap from scrap metal dealers specializing in Superalloys. Be careful of this aircraft stuff - there's a lot more without gold than there is with gold. You've got to test it - at first glance, it all looks the same. There's very, very little information available on this subject, outside of a couple of patents and what a few of us have in our heads. In the late 80's, a guy used to sell a list of which stators had gold, for about $200. Never buy a whole scrap jet engine, unless you're a jet engine mechanic. Never buy a crashed jet engine. In order to get the gold parts out and make the Superalloys sortable, the engine must be taken apart, bolt by bolt. There is also LOTS of, easy to do, silver-brazed, 410 stainless, aircraft scrap laying around out there. The silver runs about 1%-2%, by weight - about $.93$1.86. It's not unusual to see a 25,000# pile. Some silver-braze on stators runs 10% palladium - stuff called PaCuSil. I should tell you what a stator is, in case you don't know. When you look into a jet engine, you've all seen those fan-looking affairs with a lot of blades on them. Those are stators. If I remenber right, there are 21 of them in a JT3D (707, I think) engine. In the very hot compressor section, some stators, on some engines, use 81%, Au/Ni, called NiOro, to braze the vanes (blades) on. At hitemps, the gold attacSome stators have 200 vanes

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MOBILE REFINERY
Refiners Paradise
The photo of the fingers that Steve recently posted reminds me of a story. Please indulge an old man's nostalgia. Actually, there should be a separate category for stories, both tall and true. This one is 100% true. About 25 years ago, my partner came up with the idea of building a mobile refinery. The idea was to work a deal with big companies to do their refining on site. He felt they would trust us more if they could watch us. We bought a 24' box truck and spent a couple of months outfitting it. It was done quite professionally. We had a pot furnace, an assay furnace, atomic absorption, a cement mixer for cyanide stripping, etc., plus the 100, or so, vessels and tools needed to refine. We had single outlets for gas, water, and electricity. It was probably the only mobile refinery past or present. It's still a good idea. All we needed was a customer. One of the largest electronic manufacturers, with plants all over the world, decided to consolidate their scrap in one location, not only manufacturing scrap but, also, unsold, out of date equipment and computers. They rented a huge, one story, building - I'm thinking 750,000 sq.ft. - and started receiving all the scrap from all of their plants. Every day, they got at least one semi truck full. They hired about 50 people to do nothing but disassemble and sort. Gold was everywhere. It got so crowded that there were only fork truck aisles between the scrap, which was stacked to the ceiling. They had 3 girls, on each of two shifts, doing nothing but trimming fingers off of circuit boards. They used power scissors. Somehow, my partner worked a deal with these people. We drove across country, set up shop on their loading dock, and hooked up to their utilities. We started cyanide stripping fingers in the mixer, doing aqua regia, and producing about 100 oz per day. There were enough fingers stored to keep us busy for several months. When we caught up with the fingers, there were many other high grade items we could work on. Once, at the end of the day, I was drying about 100 oz of pure gold powder in a dish on a hot plate. The gold powder was dark brown. I was stirring it with a big stainless spoon. Every once in awhile, the spoon would burnish a bit of the powder which produced some bright shiny gold, which really showed up against the brown powder. A plant employee walked up, pointed to the bright shiny piece and said, "There's one."

125 All went great for about two weeks. Suddenly, the FBI came in and shut down the entire plant. It seems the manager was doing some crooked things. He had a relative on each coast that he was shipping everything to. One was getting all the scrap and the other was getting the out of date computers that had been carefully disassembled. The guy was reassembling them and selling them.

MOLDS
Types of molds
If you want ingots that are flat on all sides, you need a graphite book mold. This is a two part mold. One part has the cavity and attached to the cavity is a groove continuing to one edge. The other part is just a flat graphite plate. The two parts are clamped together and set on edge so the groove is facing upward. The gold is poured into the groove and fills the cavity and at least part of the groove. When the gold is removed, attached to the bar is the gold that filled the groove. It is sawn off, flush with the end, leaving a bar with 6 flat surfaces. The groove is called the sprue, I believe. I used book molds for many hundreds of 10 and 100 oz silver bars that I produced. To me, the most beautiful gold bars are open faced with crystals and sinks. Of course, they won't look so great if they're not pure. I wouldn't buy a supposed pure gold bar unless it were open face and I saw crystal and a sink.

PLATING THICKNESS
Gold plating thickness and how to estimate values
Part 1 I'd like to talk a little bit about gold plating thickness. First, a history, as I saw it. One of the main purposes of gold plating is to protect the part with a noncorrosive coating. In the '30's and '40's the electronic companies were still experimenting with how much was needed to provide this protection. As a result, they overplated, just to make sure. Gold was cheap back then and the parts were expensive. Also, the gold plating technology was not very advanced. The old

126 cyanide based gold coatings were very porous and it took more gold thickness to seal the pores. I haven't seen much scrap from that era but, one memorable case sticks out in my mind. We used to have a customer that had a buried cache of old stuff, mainly pins, somewhere near the Texas/New Mexico border. Once or twice a year, he would load his pickup with scrap and bring it to us for refining. The pins ran an ounce of gold per pound. They took forever to strip. When I got into the business, in the mid '60's, new innovations in gold plating had already reduced the needed gold thicknesses and the manufacturers had settled on how much gold was necessary. The government had studied the problem and had written Mil-Specs, which spelled out gold thickness and the types of gold required for specific types of military parts. Although they didn't have to, most manufacturers followed the Mil-Specs and, still do today. And, even though the gold was controlled at $42/oz., it was still expensive and the manufacturers didn't waste it. Believe it or not, these thicknesses still basically hold true today. There are other reasons why gold scrap is worth less. If I remember my dates, the government allowed the gold price to float in 1972. The price immediately started climbing and the manufacturers started thinking of ways to cut their gold costs. They did so using two main methods. First, they looked for gold substitutes on less vital parts. Sometimes, they redesigned the parts to fit a substitute. Second, the equipment makers came up with selective platers. Instead of plating the whole part, they only plated the portion of the part that required plating. For example, on backplanes, you'll often see pins that are plated only on the contact areas. Look around and you'll see a lot of examples of selective plating. The value of gold scrap started going down. In 1980, the gold price skyrocketed and, again, the manufacturers started looking at the gold costs. This brought about even more innovations. The value of gold scrap suffered another hiccup. Today, with the gold price high again, I'm sure the manufacturers are figuring out devious ways to reduce the values of our precious gold scrap. In one way, though, they have helped us. Today, there's a lot more platinum group used in electronics than ever before. The problem is that working with the platinum group is much more difficult than working with gold. And, it's harder to spot. Gold sticks out because it is yellow. There are only two metallic elements with color, copper and gold and their alloys. All others are white or some shade of gray. Silver is the whitest metal. German silver, also called nickel silver, is an alloy made to look like silver. It contains no silver. Gold plating thickness is measured in microinches - millionths of an inch. You can't tell the gold thickness by looking at it. However, very thick gold is usually matte in appearance. Thin gold can reflect the brightness of the shiny nickel underneath it. The thickest normal electronic plating is usually found on parts that require heating further along in their assembly, such as those that use a

127 gold/silicon braze for chip attachment. Examples are side braze, CPU, or hybrid circuit packages (Google). They run about 50-60 microinches of gold. There are parts that require thicker gold (as much as 500 microinches) but, most are military and are rare. The thinnest electronic gold you will probably find is about 12 microinches. Some cheap costume jewelry only has 5 microinches. Much electronics is intermediate between these two extremes, about 20-30 microinches. This intermediate level is usually found on parts that require multiple insertions, such as fingers or connector pins. These figures apply to products that the manufacturer wants to last a long time. On cheapo products, the thickness will vary but, always on the low side. The above is only a average guide. You'll notice that I always use vague terms like: often, generally, sometimes, usually, etc. The only way to absolutely know values is to assay or refine the parts. I have seen fingers that run from $10/# to $150/#. The gold on packages, however, usually runs constant. Although not always reliable, due to the internal stress of some hard gold deposits, one way to estimate relative thicknesses is to put the part in a 25-50% nitric solution. Hard gold is used on insertion parts, such as fingers. As the copper and/or nickel, under the gold, dissolves, the gold flakes. Generally, the smaller the flakes, the thinner the gold. Also, thinner gold is more porous than thick gold. Since the acid penetrates through the pores, the metals under thin gold generally is attacked faster than that of thick gold. If you do play around with the nitric, it is best to run stuff side by side, to get a comparison. If you refine the items, make notes so everything is more meaningful. Another way to estimate plating values is to calculate the surface area (number of square inches) of the plated part. This is the way that parts are plated. The plater calculates the area of the load and then sets the amperage based on the type plating bath that is being used. Gold bath current densities usually range from 3 to 10 amps per square foot (asf) of surface area. The thickness depends upon how long the parts were in the plating tank. It usually takes about 15 minutes to plate 100 microinches thick. For 60 microinches, it takes 9 minutes. The measurement of surface area takes a little math. Here are some surface area formulas: http://math.about.com/library/blmeasurement.htm Take the present gold market price, say $650, and move the decimal point three place to the left. This equals 0.65 or, 65 cents. This is very close to the value of one square inch of 100 microinches of gold. If you had 60 microinches of gold, the value per square inch would be .65 X .60 or, 39 cents per square inch. For 25 microinch gold, .65 X .25 or, about 16 cents. This is especially handy when you have a lot of identical parts, such as those boards with 1000, or so, 1" long pins. Determine the surface area of one pin and multiply by 1000 or, whatever. For more accuracy, use calipers, micrometer, or an optical comparator to make the measurements. Write down the measurements and make the calculations.

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This isn't rocket science and nothing is exact. And, there are numerous exceptions. However, I know from experience that the above info can put you in the ballpark. Even with ballpark figures, you will probably know more than the seller. In this business, more knowledge of the material always puts you ahead in the buying/selling game. And, it is a game. No one really knows the true value except for the one who refines the material. That's why the refiner is called the "Last Liar".

Part 2 You've done a lot of good work on these thicknesses, I see. You can't take these figures for gospel truth, however. The decorative FTC thicknesses are probably the most reliable, now days, since they are consumer goods and the thicknesses have to do with labeling and markings. The FTC numbers are minimums for specific labeling. The others are not so reliable unless, maybe, they are military parts. The Mil-Specs were originally used for the military, but a lot of electronic manufacturers starting using them also. In recent years, most manufacturers use the ASTM standards, I think. I don't think there's any law making electronic mfgrs. adhere to any of these. They are used a lot because they are easy to spell out. These Thickness Specs are more commonly used today than in the past. Even today, however, there are lots of parts that fall outside of the specs. Use them as a guide only. There are two ways of plating. You can plate by voltage or you can plate by amperage. Much decorative plating (costume jewelry, e.g.) is plated by voltage. In other words, the plater sets the voltage (say, 3 volts) and starts plating. He examines the parts several times during the plating, to check for such things as color and brightness. When it is done to his satisfaction, he pulls the parts out. The thickness depends on the time in the tank plus lots of other variables. This type of plating is more of an art than a science and the thickness will vary a lot more. All electronic parts are plated by amperage. The plater measures the surface area of the parts and from this he calculates the exact amperage for the load and the thickness desired determines the length of time the parts remain in the plating tank. Since it is the amperage that determines the total weight of gold deposited, per unit time, this type of plating is very scientific. However, the amount of time in the tank only gives the average thickness of the parts. Many parts are plated on racks. There may be 300 parts on a rack and the plating thickness on each part is dependent on the part's position on the rack. For example, the parts on the perimeter locations will plate thicker than those located in the center of the rack, since the perimeter is a higher current density area than the center. Also, on each individual part, the perimeter of the part, itself, will plate thicker than it's center - sometimes, 3 times thicker on the perimeter. Therefore,

129 every part will vary, somewhat, both on it's overall average thickness and on the various areas of the particular part. All in all, this says that, when assaying any type of plated parts, it is not reliable to test only one part. You have to either run several parts in one assay or several different assays. I know this is confusing and I haven't explained it very well.

Part 3 My method and Catfish's method, of calculating the gold value of plated objects, only vary by about 1.5%. Pretty close. I hope that I don't confuse everyone but, I would like to alter my method a little bit. I think that my new method will make it easier to understand how it works. Here's the whole thing. The only change is in (3), below. Why would you want to go through this rigmarole? I use it mainly for buying and selling, when I don't have an assay. I've used it a lot to estimate the value of stuff on Ebay. When dealing scrap, knowledge is king. Although the method is only ballpark, it's better than having no idea of the value. (1) Make measurements and calculate the total gold plated surface area. You want to know how many square inches or, how many square centimeters of surface you have. You need to break the plated part down into it's geometric shapes. Fingers are easy because they are rectangles. You just measure the width and length of one finger, multiply these together, and multiply this answer times the total number of fingers. If you have 50 sets of identical fingers, multiply that answer times 50. All this gives the total surface area on these particular 50 sets of identical fingers. For a round thin pin, you multiply the diameter times pi (3.1416) times the length. For a thick round pin, you also have to calculate the area of the end. For a square thin pin, multiply the width of one side times 4 times the length. Type in - surface area formulas - in Google. Some sites will give drawings of the different geometric shapes and their surface area formulas. I will look for a good one and post it in the Glossary section. You can measure in several different ways. The cheapest way is to use a triangle shaped plastic architect's ruler. You can get plenty of accuracy using one of these rulers. Get the one that measures in tenths of an inch and learn to estimate reading it in between the lines (marks). Don't ever measure in 1/16ths, 1/8ths,

130 etc. This would make the calculations much more complicated. For small measurements, you can place the ruler on the object and use something like a 10X eye loupe to read it. My favorite is a cheap set of calipers that measures in a decimal part of an inch and, not in 1/16", 1/32", etc. If you can pay more, you can get one that has a dial for the last digit. The cheaper ones have a vernier and that is a little more difficult to get used to. Probably, the best is a comparator. This is an eye loupe that has a scale built into it. You can get a variety of screw-on scales for it. You could use a micrometer but, they are cumbersome. (2) Estimate the gold plating thickness. This may be the most important factor. You have to have an idea of how much is needed for different types of parts. Gold plating is measured in millionths of an inch. Another name for this is microinches. I will refer to them as micro". First of all, you must understand that this is a pure educated guess. You must understand that the thickness of gold plating has changed over the years. Also, the plating on such things as fingers or pins can run all over the map. I have seen fingers that ran from 15 micro" to 80 micro". It depends on the usage requirements and which company made the parts. On the average, Catfish has been using 30 micro", with very good success, for things that plug into other things, whether male or female, or for those things that rub against other things, such as those tiny gold plated balls in small multiswitches. This includes such things as gold plated connector pins and many fingers. This has also been pretty well confirmed by lazersteve's yields. For things that have to be heated, in order to solder an integrated circuit (chip, die) to a package, you can figure 50 (40 to 60) micro". This includes many CPU's, sidebraze IC's, etc. It also includes hybrid packages (microwave, etc) that often contain hybrid circuits. The gold thickness on all these types of packages have run quite consistent over the years, unlike fingers. For everthing else, you are on your own. There are hints, however. For things that just sit there, on run-of-the-mill electronic equipment, figure 15-20 micro". The gold is there only for mild corrosion protection. It doesn't need wear resistance. If you run across some rare, high tech, military part that has to withstand high current flow or a highly corrosive environment, the thickness could be out of sight. Most common modern items run between 12 micro" to 35 micro". Two ways to really know the real gold thickness, on specific parts, is to assay them or to refine them (the whole batch or, just a few of them, as a sample). You can then measure and calculate the surface area. From this, you can calculate

131 the gold thickness. There are specific types of equipment that measure plating thickness. The Microderm and Betascope utilize radioactive isotopes to do this. The Kocour machine actually dissolves a small spot of the plating. There is also X-ray thickness measuring equipment. Most all of these need standards in order to set them up. You can also plate backup nickel on the gold plate, make a metallurgical mount, polish and etch it, and measure the thickness using a metallurgical microscope. I have lots of experience using all of the methods and equipment (except for x-ray) covered in this paragraph. If you want more info on any of these, let me know. A special category is gold brazes. They probably run from 500 to 1000 micro" thick. A 80/20, gold/tin braze is used around the edge on gold plated lids used to seal IC packages, such as some CPU's, side braze packages, or all-gold plated hybrid packages. Also, on many of these same parts, a 96/4 (I think), gold/silicon braze is used to attach the chip. The mil specs and other official thickness charts, concerning electronic parts, aren't that helpful unless you know what thickness Class Number was called out when that exact part was manufactured. If you assayed parts, you could probably get some correlation between the data, however. The official decorative gold plating charts are a little more helpful, since some plated jewelry is marked. If you see a marking of H.G.E., e.g., you know it should be 100 micro" thick, when new. (3) Calculate the gold plating value. First, for us in the US, who have measured things in square inches. (a) Get the spot market price of gold, in dollars per troy ounce. Divide this number by 100,000 (ten thousand) on the calculator (Note: This is the only change I made in my method). This gives the dollar value of one square inch of gold plating, one micro" thick. Let this sink in your brain. For example, if the gold price were $660 per tr.oz., the value of one square inch of one micro" thick gold, would be 660 divided by 100,000 or, $.066. Please note that this was a little discovery of mine and you won't find it anywhere else. I just noticed that, when I calculated the value of one square inch of one micro" thick gold, using the density of gold, etc., it just happened to be within 1.5% of dividing the spot price by 100,000. Pure coincidence. (b) Multiply this times the gold thickness in micro" and multiply this times the number of square inches you have. Dollar value of gold plating = Spot price divided by 100,000 X thickness in micro" X area in square inches. Example: The gold spot is $650. You have 9.58 square inches of gold plate that you estimate to be 30 micro" thick. 650 divided by 100,000 X 9.58 X 30 = $1.87.

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For those measuring in centimeters and calculating area in square centimeters: Spot price in US dollars divided by 100,000 X thickness in micro" X area in square centimeters divided by 6.452. You'll have to convert other currency values on your own. Play with this. It's easier than I've made it sound. As you probably know by now, I'm a detail guy. Just remember it's limitations. At best, it's a estimate, which will often (but, not always) be a bit on the low side. Chris NOTE: I originally made an error in this post. Instead of dividing the spot by 100,000, I divided by 10,000. The correct number is 100,000. I have edited this post to the correct value.

Part 4 I've changed my formula a little bit. I now move the decimal place 4 places or, divide by 100,000 - same thing. I covered it in detail, here: http://srv.maia1.com/~goldrefi......php?t=809 Here's the bottom line: Dollar value of gold plating = Spot price divided by 100,000 X thickness in micro" X area in square inches. Example: The gold spot is $650. You have 9.58 square inches of gold plate that you estimate to be 30 micro" thick. 650 divided by 100,000 X 9.58 X 30 = $1.87. There is no answer to "why" this works. I was playing around with the math one day and just happened to notice the similarity between the two. Pure coincidence. Actually, there is a mathematical answer but, it's not worth worrying about. The method is about 98.5% accurate. Plenty accurate for what we're doing. The accuracy for the thickness estimate is far worse. NOTE: I originally made an error in this post. Instead of dividing the spot by 100,000, I divided by 10,000. The correct number is 100,000. I have edited this post to the correct value

133

PLATINUM GROUP METALS

Rhodium plating solutions
It's been about 35 years since I recovered the rhodium from plating solutions. At that time, a company I worked for, in L.A., formulated and sold several different types. I would imagine that the formulas are the same today. Here's what I remember. We sold two different strengths. For industrial or electronic applications, there was a 5 gm/liter rhodium solution. For jewelry uses, the solution was 2 gm/liter of rhodium. The stronger solution allowed for thicker deposits and was used for such things as PCB fingers or memory disks. By far, the most common solution was made up with rhodium sulfate and sulfuric acid. If I remember right, there were no other additives. Another formula (I think this is right) used rhodium phosphate and phosphoric acid. Here again, I seem to remember that there were no additives used. The L.A. facility where I worked also had very large gold refinery, but we didn't do any PGM refining there. Before doing anything, we would determine the quantity of rhodium in the solution, using atomic absorption or precipitation. We would then precipitate the rhodium as metal powder, using a cementation method, and ship the powder to our N.J. facility for refining. Here's where my memory fails me. I'm thinking we used zinc dust to precipitate the rhodium but, I'm also thinking we may have used magnesium to drop it. If the solution you have is unused, you could have about $4,000 to $10,000 worth of rhodium, depending on the initial make-up. If the solution has been used, it could be worth far less. The solution color is an indication of the value. Rhodium sulfate is a red-brown color. In general, the darker the solution is, the higher the value. As an amateur, I wouldn't try to refine the rhodium yourself, considering the potential value. It's a very complicated method, requiring special equipment, and the odds are that you would lose much of the value. Your best bet is to sell it to a refiner. I would pick a big one that specializes in PGM, such as Matthey Bishop - they are all over the world. However, before doing this, you must plan carefully and not do anything that would diminish the value of the material. You must determine the rhodium content before selling it. Otherwise you're

134 leaving yourself wide open. The best scenario would be that the solution is in sealed (by the manufacturer) bottles. If this is the case and, if there is a label on the bottles, don't open them. The rhodium content should be listed on the label. If not, contact the manufacturer and ask them the rhodium content. More likely, the solution is not in sealed bottles. If not, I would combine the solutions together, mix well, remove about a 20 mL sample, and put it in a small, clean, dry plastic bottle. One way to get the solution analyzed is to call around and find a lab with an atomic absorption (AA) unit. They must have a rhodium lamp for the AA. Pay to have them analyze the rhodium content. There are more accurate methods for analyzing the rhodium but, they will be more expensive. Probably the most accurate way is to precipitate the rhodium, as metal, from a 5 mL sample, using zinc or magnesium. The excess Zn or Mg can be removed with weak HCl or H2SO4. If the solution was contaminated with other metals, they will be mixed in with the powder and will also have to be leached out. When all the Rh has dropped, the solution should be pretty much water clear. After rinsing, drying, and weighing the powder, the Rh content of the main solution will be known. I wouldn't do this yourself unless you are a chemist and have a well equipped lab. Let a commercial lab do it. Once you know what you have, I would take all the solution to the PGM refiner. I would have the refiner take a sample, give half of it to you, and then have him seal the main solution with a numbered seal, so it can't be tampered with. If the refiner agrees, I would take the solution home with me. When he finishes analyzing his sample, you can decide whether or not you want to sell it to him. If you don't like his numbers, take the solution elsewhere. All in all, I would definitely sell it in solution form. Solutions have a very low gray area. They are homogeneous and are easy to sample. I would NOT treat the solution and try to sell the solids. You would then have a material with a very large gray area. These are just some ideas. I could make more specific recommendations if you would give much more detail about what you have.

Palladium contact points on telephone scrap

I've run many tons of palladium point scrap. When the telephone switching offices and large plant facilities went from relays to digital, there were millions of pounds of pure Pd contact relays coming into the scrap market. This stuff is still out there. A few years ago, I discovered about 5000# installed in the attic of a 750,000 Sq ft manufacturing plant. Palladium points are usually about 1/8 long, and skinny. They are gray/silver and

135 usually are tapered on the edges. The cross section kind of looks like half a hexagon or octagon. They have a nickel backing and this is attached to a copperbase blade or wire. We once ran a 50,000# batch of this material. This gross weight included the shelving, relays, sockets, wiring, and everything else. It took 2 men, 2 months, in and out the door. We pulled the relays, learned how to disassemble them, and cut close to the points with a small, reciprocating alligator shear. At today's prices, the batch would be worth about $6/gross pound, in palladium. There's also lots of copper. Instead of dissolving everything in the clipped point and dropping the Pd, I decided to selectively dissolve the nickel and the copper base, leaving the very pure palladium untouched. I found that a very dangerous (maybe, the most dangerous combination of chemicals I have known), hot, very strong solution of chromic acid and sulfuric acid dissolved the copper-base (with great relish and foam!) and nothing else - please don't try this at home - the problem is, what do you put it in, that won't break or be attacked - iron or steel might work. The nickel backing was then dissolved in hot full-strength muriatic acid. The result was a very pure Pd - with no loses - sold very close to spot. We didn't even melt it. We got top dollar in point form. If a precious metal, especially when pure, is layered onto base metals, it often pays to dissolve the base metals away from the PM, rather than dissolve everything. In the case of the Pd points, I would wager the Pd would lose purity if you, the reader, were to attempt to refine them. It's already pure - don't mess with it! Most, but not all, telephone relays are just like other plastic box relays, except they are long and skinny and, instead of short blades, the points are mounted on long, round wires. They are called "wire relays." More rarely, pure Pd points are used for other applications. In every case that I have seen, however, they all looked the same.

Testing platinum thermocouple wire

The quickest and most common method is to first scrub a piece of the wire to remove all extraneous dirt. Next, heat the wire with a torch (preferably with an oxidizing flame) until it is red hot and then remove the torch. If it is Pt, the wire will remain bright and shiny, with no discoloration. If anything, it will look cleaner. If any other common thermocouple metal, it will oxidize or sputter or melt. Another simple way is to first calculate the volume of a piece of wire by

136 measuring it's diameter and length. Then, weigh it and calculate the density. Use a micrometer or calipers for the diameter. For example, assume a 6" length of wire with a diameter of .06". The volume is the length times the diameter squared divided by 4, or (6 X .06 X .06) / 4, or .0054 cubic inches. Convert this to cubic centimeters by multiplying by 16.39, or .0054 X 16.39 = .0885. Next, weigh the piece of wire, in grams, and divide the weight by the volume, or .0885. If pure Pt, the density will be approx. 21.45 grams per cubic centimeter. For 90% Pt/10% Rh, it is about 20.5. All of the other thermocouple metals, that I can think of, will be 9, or less. This huge difference makes the detection of Pt quite obvious.

REFINERS
Pin samples
The term refiner can be used in 2 different ways. First, a refiner can be any person that re-fines gold or, makes it Fine again, using chemical, or other means. Using this definition, the re-finer can be anyone, including a hobbyist. The second definition of a refiner is a person who re-fines gold, as a business, for other people. Most people on this forum re-fine their own material, for their own entertainment. Some of us have done refining as a business, myself included (40 years), but, no longer. So, we know there are thieving refiners out there. We have known them. In some cases, we have worked for people that have been them. What is a pin sample? Until about 20 or 30 or, whatever, years ago, a refiner would melt the customer's impure gold, cast it into a bar, weigh it, drill it, assay the drillings, and pay the customer. Some small refiners still use this method. This method had problems. When the bar solidified, the impurities stratified into layers. Parts of the bar was richer than other parts. The accuracy of the sample depended on where you drilled the bar and how deep. Old mining books even gave schemes for where and how to make multiple drillings of the bar. One guy I worked for had me drill the bars on opposite corners and the middle on one side and the other corners on the other side. The depth of the drill press was set to drill half way through the bar. The drillings were melted, poured into water, and the resulting shot was assayed. It was a big job to do all this. We still, sometimes, got strange assays.

137 The invention of the pin sample changed all of this. For quite a few years, pin samples have been the state of the art. Nearly every refinery uses pin samples. They are much simpler to perform. They are much more representative of the entire lot because they are taken on stirred molten metal. It's much easier to stir the melt than it is to stir the bar. Here's what a vacuum tube, which is used to take the pin sample, looks like http://www.lmine.com/Merchant2.....gory_Code= These are sealed glass tubes with a vacuum in them. On the right hand side of the tubes in the photo, you will notice a small bubble near the end of the tube. This bubble is very thin compared to the rest of the tube. To use this, the slag is preferably removed first, with a carbon rod, and the melt is stirred. Then, with special tongs gripping the sealed pointed end (the left end in the photo), the bubble end is plunged to the center of the melt. The thin bubble immediately melts and the vacuum sucks the molten metal into the tube. The tube is immediately withdrawn. In-Out. If left too long, the tube will soften and sag. The pin solidifies, the glass is broken away with a hammer, pieces are cut off the pin, and the pieces are assayed. I noticed than one of the refiner links in the thread required that the pins have a 2mm diameter, or less. Also being an assayer, I agree. The smallest dia tubes in the link above are 3.5mm. I don't like these because they are too big to be easy to cut to a proper size. The 2mm ones are much easier. I might mention another accurate sampling method that is used by some refiners. It is also very simple. The slag is removed with a carbon rod, melt is stirred, some of the melt is removed with a ladle, and shot is made by pouring the metal into water.

Dealing with refiners

You can't assume every refiner is honest, Some are and some aren't. You don't know who. For this reason, you try to eliminate doubt in what you are selling them. Here are some possible things you can do. Take Charge. (1) Don't send loose gold to them. Melt it into a bar and drill it or pin sample it. Tell them you pulled the samples. (2) Tell the refiner not to process your material until the assay is complete and he OK's the numbers with you. You will have to pay the assay charge. All the refiner has to do is cupel it and part it and $40-$50 is probably the minimum he'll charge. If he wants more, tell him that all he has to do is cupel it and part it. Know the assay charge before you ship. If you don't like the assay results, have him return it to you.

138 (3) Split the lot and send half to one refiner and half to another. Tell them both that you are doing this. Don't tell them who the other refiner is. The motto of many refiners, "You can shear a sheep many times but, you can only skin him once." Don't put yourself in a position to be skinned. Nobody can protect you from a totally dishonest refiner. If they want to take 90% of your gold, they will. You will probably have no recourse. All I can do is tell you things to do to maybe avoid getting taken. Just think of all ways you can get taken and try to do things to prevent them or, at least, minimize them. Except for the fly-by-nighters, refiners rely on word of mouth and repeat business. If you prepare your lot correctly, they know that you know and will tend not to steal or, to steal less. To most refiners that take a little, the amount taken depends on what the traffic will bear. If you've done things right, they will see this and will take less. If you send them a pile of non-homogeneous material, they will know that you have no idea of it's value and, they will be temped to take more. Most people that own gold tend to evaluate it on the high side. This can make you unhappy with any refiner's settlement. The guy in the forum thread you gave did no preparation and he overvalued his gold. He also left himself wide open. There are some refiners out there that quote very low charges, in order to get the business. They intend on stealing a bit to cover their expenses and profit. I remember a cartoon in a recycling magazine, where the refiner told the customer that he was such a good customer that he would do the refining for free. This causes problems for the honest refiner, trying to quote honest charges. If he does, he won't get much business because potential customers compare charges before choosing a refiner. Charges are meaningless with a dishonest refiner. Just remember, though, that you have to allow the refiner to make a fair profit, whatever that is. I tend to know these things because I've spent a lot of time on both sides of the counter. Not every refiner is honest. Under certain circumstances, maybe, no refiner is totally honest. I say this after spending some 40 years in the refining industry. Until the material is refined (purified), there is always a doubt about the gold content. This is the "grey area". If you are sending in karat gold scrap in lots of little pieces, you may have a 20% grey area. The batch that you think is worth $2000 could be actually worth somewhere between $1600 and $2400. To determine what the number actually is, the refiner will melt everything together, stir it well, cast it all into an bar, knock any slag off, weigh it, drill the bar, and, finally, assay (analyze) the drillings. The refiner senses, by the condition of the material you sent him, what this grey area is. If he desires, when he settles with you, he can say he only got $1600 worth and still get you back as a repeat

139 customer - with a little BS. There's an old saying in the refining business, "You can shear a sheep many times, but you can only skin him once." The way around this is to reduce the grey area. If you were to melt, cast, drill, etc. your gold, before you shipped it, the grey area might only be 1%, at least in the refiner's mind. When he sees the bar, with a hole it, he knows that you know and he is more likely to give you a fair shake. You always have the drillings which can be sent out for assay, if necessary - about $50. A decent little melting furnace can be built, in a couple of days, for about $50-$100

SAFETY
Gloves
To me, the choice of chemical proof gloves is very important. I've probably tried every type of glove there is and have come up with favorites. The gloves I like best cost about $7 a pair. They are common and are mainly available at good hardware stores and farm stores. They are usually 2 tone green in color and have a white cloth lining. I have also seen 2 tone blue ones. The lining is important, because you don't sweat like you do with the black gloves. These gloves are rougher on the finger area, so they won't slip as easy. They are more durable than the common, unlined black variety that most of you use. When new, they are fairly stiff but loosen up quickly. They come in sizes. You want them a little loose. If you want them off quickly, you simply shake them off. The best ones, although a little more expensive, are called anhydrous ammonia gloves and are available in farm stores. Whatever gloves you use, rinse off any strong sulfuric that is on them. If allowed to remain, it will damage them. Turn up the cuffs on your gloves an inch or so. This catches the solution from your gloves and prevents it from running onto your arms. If the gloves get wet, from solution, on the inside, rinse them well, inside and out, uncuff them, and hang each one to dry on something like over the tip of a broom handle, stood vertically. Don't handle sharp parts with your gloves, such as some types of pins and the legs on IC's. You'll put holes in the gloves and make them worthless, and dangerous, for working around solutions. If you must handle sharp parts with gloves, do it loosely and gently. I also keep a pair of long, heavy, shoulder length, black unlined gloves for working around solutions that require putting my hands and arms into.

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A few comments about diluting acids with water

I have often wondered why they tell you to always pour the acid into the water. When "they" say this, they include ALL types of acid. They make it a blanket statement. When it comes to sulfuric, phosphoric, glacial acetic, and certain other acids, this rule is very important. If you pour the water into the sulfuric, the mixture, at the point of combination, instantly heats up and can easily produce splattering. When diluting sulfuric, ALWAYS pour the acid into the water. I also might mention that both water and acid should be at room temperature when doing this. About the only other acids we use are nitric, hydrochloric (muriatic), or a combination of the two (aqua regia). When diluting these, it is very safe to pour the water into the acid, whether hot or cold. Only a few degrees of heating will occur, if any. When working with nitric and hydrochloric, it is probably safer, in many cases, to pour the water into the acid, rather than having to handle and pour the strong acid itself. Either way works, with these acids. If I'm pouring these particular acids from a plastic jug with a handle, I'll pour the acid into the water. If one of these concentrated acids is in a bucket, beaker, or jar, it's safer to pour water into the acid. I imagine that the reason that "they" set up the general rule was so that water would never be tragically poured into sulfuric acid.

Cyanide safety
I knew the son of a guy that died from cyanide inhalation or ingestion. He was dissolving the silver solder that held the carbide tips on scrap coal mining bits. He was running several drum quantities and working inside with no fume control. A few rules for cyanide are: Don't get it in your mouth. Don't mix it with acids, even something as weak as coffee. Don't work in a confined area. Don't smoke or drink around it. Don't work over hot cyanide - your skin will break out with "cyanide itch". Wear gloves and a face shield. Get an excellent fume hood Your friend didn't know or obey the rules. You must obey the rules with cyanide.

Sulfuric drain cleaner

141 Many years ago, a guy that worked for me in L.A. had an accident with sulfuric drain cleaner. He was in a hardware store and picked up a jug that was sitting on the floor. The jug was wet, for some reason, and it slipped out of his hand. When it hit the floor, the lid popped off and sulfuric splashed all over his face. He got to water fast enough to prevent most permanent scarring. He was blessed because the acid didn't get in his eyes. He sure looked awful for a month or two. Be careful out there, guys and gals.

Osmium
I think the most important thing is to treat and handle the waste chemicals legally and properly. There should be many more threads concerning this subject. I once heard a real horror story about one of the osmium compounds - some form of osmium chloride, I think. It evaporates at room temperature and the fumes can deposit a metallic osmium coating on the lens of your eye. Scary.

Silicon wafers
I have these silicon wafers (lots of them), that have a lot of gold on them. Like the whole backside of them and in between. How would I process something like that? And get rid of all the silicon?

I don't understand what you mean by "in between" - please explain. A refinery I worked for got these gold backed silicon wafers by the drumloads from companies in the Silicon Valley. I think the gold is evaporated or sputtered onto the silicon. I don't remember the gold thickness but I don't think it is very thick. It would certainly add up in quantity. I also don't remember how we processed them. We probably used cyanide, since it was common back then. It was also cheap, fast, safe, and efficient. Since the government has taken away the marvelous cyanide, you are stuck using some form of acid chloride. This would include the standard aqua regia, HCl/bleach, and HCl/peroxide processes. None of these should attack the silicon. They should only attack the gold. You would then drop the gold from the solution, as normal. The problem with working with these wafers, when whole, is that they tend to stick to each other when wet. The acid then has to penetrate through the edges of the stuck together wafers and, this can be a slow process. This can be sped

142 up by first breaking up, or grinding up, the wafers. If you grind up the wafers, there may be a potential health hazard with the dust, if you don't wear a proper mask. I would read the stuff on this link. http://www.msha.gov/S&HINFO/SILICO/SILICO.HTM When you breathe silica (silicon oxide) dust, there is the possibility of getting silicosis, a lung disease. Although we're talking about pure silicon and not the silicon oxide covered in the link, I think I would take the same precautions, were it me. Better safe than sorry.

Hydrofluoric acid
Unless you are a chemist, I would not use HF. Too damned dangerous if you don't know what you're doing. I've used it for certain applications, but certainly don't recommend it for the amateur.

Chemical safety
Just because you use a toxic chemical, it doesn't mean that you will pollute. It is usually very easy, if you know what you're doing, to totally not pollute. All it takes is knowledge, ingenuity, and, maybe, a few bucks. I spent about 10 years in the plating industry in the '60's and '70's. For about 4 of those years, I spent a lot of time traveling around, designing and troubleshooting our some 1500 customer's plating facilities. I was in 100's of plating shops. Most had very large tanks of such things as 40 oz/gal chromic acid, chrome plating solutions or 10 oz/gal sodium cyanide, copper plating solutions - on opposite sides of the room, of course! Some tanks were as large as 5000 gallons. There were many 100's of plating shops in L.A., at the time. Most were manned with smart Mexican workers. The point is, in 10 years, I only heard of 2 or 3 accidents. I don't even remember anyone getting sick. People were immediately trained how to work around this stuff, safely. There was adequate equipment to eliminate hazards. The equipment was designed for safety. If any industry has mastery over the proper use and disposal of some of the nastiest chemicals on Earth, it's the plating industry. You can work safely and responsibly with any chemical, if you know it inside and out.

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More chemical safety

I agree with you totally in the dangers that these chemicals possess. This forum greatly profits from your reminders of the dangers involved. I, for one, appreciate these reminders and learn from them. However, I see my function in another light. Almost everything on this forum is dangerous and potentially polluting, if you don't know what you're doing. I see, as one of my jobs, keeping people safe and legal, no matter what they're doing. I also want to spell out every option available. I do 100% advise against, and won't discuss, the use of such things as mercury, HF, or combinations that can create explosions. One day, when I give my treatise on the wonderful selective cyanide stripping of gold plating, you'll probably go ballistic. Just joking, kinda. You can read my posts and find nowhere that I advocated the use of chromic acid. Quite the contrary. I said it was the most dangerous chemical combination I had ever used. But, I don't agree that just mentioning something advocates it. If anyone has clipped Pd points and is thinking about trying the chromic acid, I will post the complete safety, handling, dangers, waste, and usage instructions, in great detail, as I know them. All one needs to do is ask. A trick, as in all setups, is to always start small - 200 to 300 mLs, in this case? Learn before leaping. Don't get it on your skin, don't breathe the fumes, and don't eat it. Your set up and technique must protect against these things. A problem with chromic acid usage is the waste. You might convert it from the hexavalent to the much less toxic trivalent form, although all of that sulfuric might not allow the conversion. Chromic acid might precipitate out if you could evaporate all of the water off of the H2SO4/chromic. But, no matter what you do, you still have toxic waste that has to be legally disposed of - but probably only slightly more critical than the common heavy metals acid wastes being generated by all. And, finally, there are probably other more genteel ways to selectively dissolve the copper without hitting the palladium. When I found the H2SO4/Chromic acid, I stopped researching - it worked so damned well. You probably could substitute potassium or sodium dichromate for the chromic acid. It's on Ebay: http://tinyurl.com/2v85kr Looking back, the inherent dangers and the subsequent conquering of them, is one of the things that attracts me to this profession. I'm a "green" refiner, also.

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Graphite
Be careful with graphite powder. It's not good to breathe it. I've heard horror stories about the health of people that machine graphite.

SAMPLING
Sampling bars and molten metal
We don't disagree often. When we do, it's usually because of our very different experiences. In most cases, both ways work. Concerning our above posts, we agree on everything except the stratification of bars. I don't know if that word is even the right one to use. Whatever happens when a bar cools, the gold content varies a slight amount in different areas of the bar, no matter how well the melt was stirred before pouring. Since I both drilled and assayed the bars, I could see repeatable differences, especially if the bar cooled slowly. It didn't seem to have anything to do with density. The bars didn't seem to be richer at the bottom. A bar doesn't solidify all at once. It starts on the outside and, the last to become solid is the top center. The differences I saw were in those areas that solidified at different times. I always thought it had something to do the melting points of the alloys formed. It was, though, a chicken and the egg thing. Which came first? It was very hard to pin down. It seemed like, if you could solidify the bar all at once, these assay differences wouldn't show up.

1) For small bars, I use about a 1/8" drill. The standard way is to first remove all slag by tapping it with a small steel rod or a small hammer. You don't want any slag in the drillings - plus, the presence of slag makes the value of the bar in doubt, which can give the refiner Then, drill 3 holes on one side - 2 near opposite corners and one in the middle. Next, flip the bar over and drill the other 2 corners. When drilling all holes, go halfway through the bar. Cut the drillings in small pieces. Mix them well together and pull out about 1 gram this is enough for 4 assays. You can put the leftover drillings into the next shipment. An easier way is to melt the material and then suck a sample up into a special glass tube. The glass is then broken, leaving a gold wire, from which you can clip off a few 1/4 gram samples for assay. They are basically small glass tubes sealed with a vacuum inside. On one end, a very thin bubble has been

145 blown in the glass. The tube is held by tongs and dipped quickly, bubble end first, into the molten metal. The thin bubble melts first, releasing the vacuum, which sucks the metal up into the tube. These tubes are available from legend-reno.com - you may have to call them, since I couldn't find the tubes in their internet catalog. 2) Some of the best info on small furnace building is on the Yahoo group at: http://groups.yahoo.com/group/castinghobby/ You have to join (easy) the group to read the threads. I, somewhere, have a cutaway drawing I made of a furnace. I'll look for it. 3) If you can produce enough heat to melt everything into ONE bar, you can use a torch. However, if you can only melt small amounts and end up with two, or more, small, different-valued bars in the same shipment, you have introduced a gray area and have defeated the whole purpose.

SCAMS
A common con game
All of this leads up to the Con. The Con is very old and is worked mainly worked on the wealthy. I have also seen investment packages made up of small investors. The Germans even had a name for this con, although I can't remember it. The Con involves finding investors for the transmutation of base metals or chemicals into gold, through the use of a special secret process. When it's time to show the goods, there is sleight of hand and there are "processes that cannot be shown" or " processes that are too dangerous to witness." The key phrase in this con is, "The gold and other PM's contained in this material are not assayable by conventional methods." The PM's are supposedly in an immature form and must be prompted along. I've seen it on a large scale twice. First, a guy that had invested his life savings into a process that got gold and silver out of well water in Arizona. I assayed the water for him about 5 different ways. When nothing showed, he didn't believe me because he was conditioned that traditional assay methods wouldn't work. The other time is pretty well covered in this post I put on 49ermike several years ago. This is almost exactly how it went down. Quote "I hope you haven't put ANY money into this. This is an ages old big-money con,

146 which I think started in Germany. The Germans even have a special name for it, which I can't remember. Here is one the many possible ways it is promoted. THE PITCH ---"In nature, a brand new chemistry of metals has been discovered. Dr. A has been working on it, in secret, all of his life. He found that such metals as gold, silver, platinum, and palladium exist, in many naturally occurring materials (ores, etc.), in an immature form. This baby gold can't be assayed by conventional means, but, after 42 years of research, Dr. A has perfected a fluxing process which matures it to the regular visible gold (or platinum, etc.) form. The process is very expensive - the flux mixture itself contains 27 ingredients, some of which are regular precious metals - like begats like. Only Dr. A knows the formula. His partner, Dr. B, was murdered last year by the CIA. The governments are very concerned about us dumping a lot of gold on the market - it would ruin the world economy. That's why we closely restrict our number of investors and require secrecy. It must never become public - we would all be killed. See this ore? A conventional assay reports only .03 tr ozs per ton. Through special processing and fluxing techniques, Dr. A has proven it to contain 29% gold, 41% platinum, and 4% rhodium, in conversion from it's immature form innate in many common materials. I know it's hard to believe, but we have extensive documentation proving it. With only a few drums of material, we all will be wealthy. Come over tomorrow and we'll show you how it works. Some of the steps are confidential, of course, but when you actually see the gold that is produced, you'll know that it works. Blah, blah, blah" Certain types of people really get sucked into this. Many still believe it after losing all their money. Every once in a while, you will read in the paper of someone losing millions in this same scam. It can be very enticing. In recent years, a new version of the con has cropped up. If you type monoatomic gold - in a search engine, you will see words like ORMUS, or WHITE GOLD. You will also find the "white gold" inventor's name, David Hudson. If you dig, you'll find the same keywords - immature gold, incomplete gold, can't be assayed, monoatomic, etc. Many of Hudson's followers believe that this material is the Philosopher's Stone (or, an intermediate in the process), the material that will give eternal life and change base metals to gold. The solutions are sold on the internet. People drink them. Information is sold also, I think." Well, Ralph, thats the way I see your post. Who nows, though, maybe he found the key. Right. I've got this bridge.......

SCRUBBERS

147

Fume scrubber info

The standard ones I worked around were basically large round plastic or fiberglass cylindrical tanks set vertically - about 15'-20' high and 6'-8' in diameter. The top was sealed except for the blower which pulled the fumes though the scrubber. At the very bottom was a reservoir of not too strong sodium hydroxide, which was pumped to a series of spray nozzles at the top. The NaOH from the spray nozzles ran back down into the reservoir. As it neutralized the acid fumes, the sodium hydroxide got weaker. A pH meter in the NaOH sensed this and, at a certain pH, some 50% (6.25# of NaOH/gal) caustic soda (NaOH) was pumped from a drum outside of the scrubber into the reservoir of dilute NaOH. The pump shut off when the pH reached a certain level. The solution was continually pH adjusted. Once or twice a year it became saturated and was exchanged for fresh solution. The only other thing in the scrubber was a platform, with a lot of 1" holes in it, mounted about 2' above the NaOH reservoir. On the platform was about a 6" layer of high surface area pieces of plastic. Some company makes high dollar, mathematically maximized high surface area plastic pieces called Tellerettes. Maybe, Teller developed them for the A bomb project. These are the most common. In our refinery in Hong Kong, we used reject plastic flowers from a plastic flower factory. The fumes are sucked through plastic pipe from the refinery into the gap between the NaOH and the plastic pieces and travel upward through the 6" plastic layer and through the spray and out. The Tellerettes condensed some of the gases. The caustic spray neutralized the rest. The math of the chamber volume vs the blower cfm is very important. The gases have to remain in the chamber for 9 sec. (I think that's right). Therefore, our approx. 6' X 15' scrubber only had a 275 cfm blower, mounted on top. It is obvious you can't have air dilution of the fumes. No open fume hoods. In the refinery in L.A. we had about 12, 4 liter beakers for aqua regia. On each beaker was a lid with a small tubing in the middle sucking the fumes out. These went to a manifold and then to the scrubber. We also had a 50 gal glass-lined, steamjacketed kettle for dissolving large quantities of stuff. The kettle also had a lid with a tube that sucked the fumes out. The kettle and the beakers pretty much used up our scrubber capacity. Scrubbers are big but simple. They are totally made of plastic and/or fiberglass. There are lots of big fiberglass tanks lying around, for cheap. Commercial scrubbers are expensive. They could be made much, much cheaper. They are very cheap to operate.

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SHOR
Shor patents, chemicals, and equipment
You can pretty much tell what the Shor secret ingredients are by reading Peter Shor's patents. I think he has 6 of them. You have to study them. Then compare them with the descriptions of his processes and equipment on his website. His website is quite good with tons of information but, you have to thoroughly search for it. I have only skimmed the patents. He seems to like ammonium chloride. It shows up often in the patents. Here's the patent numbers. There are 5. The other was another Peter Shor. He may have more under another name. To read them, go to Google/more/patents and type in the number. 5997719 5269912 4895626 4612093 5009755

According to a seller of chemicals on eBay, the Storm precipitant is sodium metabisulfite and Subzero is sodium nitrate.

Shor patents part 2

What you're talking about are the Shor patents. I haven't read them in awhile but, if I remember right, there are 2 different formulations of ammonium chloride covered in 2 different patents. The stronger formula dissolves everything, including the gold. The weaker one dissolves everything except for the gold. In both, the silver is kept in solution as an ammoniacal complex If you don't use the semi-permeable membrane in the weaker formula, what happens at the cathode? Do the base metals plate out or, are they prevented from doing so by the complexes formed? If the base metals do plate out, you would have a mess that you couldn't live with. If this happens, the membrane would isolate the cathode from the metal solution so nothing plates out. In the case of the stronger solution, you have to have the membrane to keep the gold

149 from plating out. I have also wondered, for a long time, about using an unglazed flower pot for this. The problem is, how do you seal the drain hole? I think I would try fiberglass cloth and the waterproof 2-ton epoxy from WalMart - about $2. Don't get the 5 minute epoxy because it's not entirely waterproof. Also, the putty type waterproof epoxy would probably work. In any case, the membrane wouldn't hurt. Probably, the first application of using a membrane for this sort of thing was a "fizzer cell". This was a cell using a "porous cup" in the production of gold chloride for use in a Wohlwill cell. The Simplicity cell uses a porous cup (Google). In one of the Shor patents, I believe that it is mentioned they are available in up to a 1 gallon size Like I said, I haven't read the patents in awhile. When I get the chance, I'll read them and post a summary here. I have been planning, for awhile, to post a complete breakdown of the patents and the secrets of the Shor Simplicity machine but, I haven't gotten around to it.

Shor patents part 3

The Shor patent of the ammonium chloride electrolyte that dissolves the gold also is #5,009,755. It has 1 to 2 pounds of ammonium chloride per gallon, 2 to 4 ozs of NaCl per gallon, and .25 fl.oz. of hydrogen peroxide per gallon. The anode is bagged and the anode solution is separated from the cathode by a membrane. I think this patent is what the Simplicity machine is based on but, I need to read the Simplicity instructions again to make sure. I may be wrong. The Shor patents are quite confusing and I haven't spent that much time analyzing them. The catalyst is probably the peroxide. The gold can be dropped with any of the common sulfite compounds. The Pt group metals stay in the anode bag.

Shor and Wohlwill cells

Let's define some terms to avoid confusion. The Wohlwill cell is a specific type of gold purification cell, using a specific type of solution and originally invented and patented by Emil Wohlwill. Every Wohlwill cell solution is made up of gold chloride and HCl. The starting gold content of the solution is about 1 to 1.5 troy ozs. of gold per liter and the free HCl runs about 5% to 7%. The anode is the impure gold, which is bagged. The starter cathode is

150 thick pure gold foil. That is a Wohlwill cell. Including the pure silver bussing that is used, the precious metals needed to set up a 1 gallon cell would cost about $5000. This doesn't include the cell and the rectifier. All electrolytic cells based on ammonium chloride, that I know of, are covered in the patents of Peter Shor. He has 5 patents, 3 of which has been offered as pdf's somewhere, recently, on this forum. One of the patents dissolves only the base metals and the silver, but not the gold. Another dissolves the gold also. In the latter, a membrane is needed to prevent the dissolved gold from plating onto the cathode. The Shor Simplicity machine is an example of the latter, I think. The modified ammonium chloride solution, covered in the latter patent, is about the perfect electrolyte. It dissolves the gold, silver, and base metals. The platinum group metals and all the dirt are left as a sludge inside of the anode bag. I would suggest that, if you want to use ammonium chloride, you either download and study these patents or spend $600 for a Simplicity Cell. One of these days, I'll do a study of Shor's patents and his cell.

Shor cell
How strong is the saltwater that you are using? Does it dissolve every thing gold, copper, etc.? You get no chlorine fumes coming off the anode? Your rig is very similar to the Shor patent, #4612093. He puts the anode in a .5 micron ceramic porous cup. A big difference is that he is dissolving solid karat gold. He needs much stronger solutions to do this - either full strength HCl or a saturated table salt solution (about 370 grams of salt per liter = 3 pounds per gallon). He starts either solution off with a catalyst of hydrogen peroxide - the equivalent of about 10 drops to 50 drops of 3% H2O2 per gallon of solution. He then drops the gold with sodium bisulfite. I would think that using the stronger solutions, especially the conc. HCl, would produce lots of chlorine gas.

SILVER CELL
Silver cells part 1

151 A traditional silver cell is only used to process solid silver that is at least 90% (sterling silver, e.g.) pure to 99.99%. Like aqua regia is for gold, a silver cell is the final purification step for most silver recovery operations, no matter what items are started with. Most all silver plated materials have copper or copper alloys underneath the silver. I know of no common cell that will selectively remove silver plate from copper based items, except the strong sulfuric cell that you are presently using. However, what do you do next, economically? Silver stripping was included in the original sulfuric patent but, I've never played with it. The patent holder was a plater and stripping faulty plating was the original intention of the patent I once developed a cell using cyanide plus a large amount of sodium hydroxide that didn't eat the copper and worked quite well but, you had to keep the parts moving in a tumbler. The silver (or, gold) that stripped automatically plated out on the cathode. The coinage metals, gold, silver, and copper, are found together in nature and have many chemical properties in common. All can be dissolved in cyanide, for example. The high sodium hydroxide in my cell slowed greatly the attack on the copper. This system is, obviously, beyond your scope. In the books, about the only method given is the super nasty, super dangerous hot concentrated sulfuric plus a little nitric - I think they say 5% for the nitric. No electrolytic cell. All you have to do is immerse the parts. For thin plating, heating isn't necessary. Here again, this process doesn't work economically. It's designed to strip faulty plating off so the parts can be replated. Most refiners don't want silver plated items. Basically, silver plated copper is considered as contaminated copper. Most silver plated copper only runs 1% silver. Some silverware is higher. Don't buy it unless you pay a lot less than copper price. If you do have a bunch of it, look for a refiner that burns boards, melts all the resulting metals into ingots that run about 65% copper, and then ships the ingots for further refining. He might, just might, pay you a small price over copper market. He always needs cheap copper and can add the stuff to the melt. He often needs extra copper to lower the melting point of hi-temp melting items containing lots of iron and nickel. The big smelter he ships to will pay him for the silver.

Silver cells part 2

I wrote the post below before I saw Harold's post but I wasn't able to post it yesterday. The traditional Thum cell I'm speaking of looks nothing like Harold's. When I first saw Harold's, I was taken aback, since it looked so strange. On closer examination, I can see what he had in mind. His cell eliminates the need for sliding the basket back and forth in order to remove the crystals. Also. the

152 entire cell is the cathode and will probably last forever. Actually, pretty darn ingenious. At 10 amps, his cell probably produced about 20 to 25 ozs in 24 hours. Most books suggest using unbleached muslin as a filter cloth. I bought mine from WalMart and used a double thickness. It's only problem is that there's sizing in it and it takes an hour or two before the solution penetrates the sizing and there is maximum current flow. The cloth is used once. The muslin cloth also burns well. I never used only gasoline for burning but often used a safer 50/50 blend of gas and diesel. The 30 gallon cell mentioned below consists of an flat bottomed outer tank about 30" X 60". It was made from 2" X 10" lumber with a 3/4" plywood bottom. It was coated with several coats of polyester boat resin. The last one I made was coated with PVC that was applied with a chopping gun. A sheet of 1/8" 300 series stainless laid flat in the bottom. The stainless had a 90 deg. bend at one end and protruded out of the tank in order to make electrical contact. The inner basket (also coated) was about 28" X 28". The sides were 1" X 6" lumber. Instead of a solid bottom, there were 19 removable 3/4" OD PVC pipes sealed with pipe caps on each end. A length of 3/8" or 1/2" rebar was put into each pipe for rigidity. Each pipe rested on a support on the sides of the basket. The muslin cloth was laid on the row of pipes and the 21 impure silver bars (about 30-35 oz each - about 600 oz total) were placed on the cloth. The bars were all touching each other. The solution level was adjusted so it touched the bottom of the silver bars. To make contact to the bars, I used a 3#, 60/40 copper/silver bar attached to the power cable. This contact bar was simply placed on the silver bars. A protruding wooden cross member was attached to 2 ends of the basket. They rode across the top sides of the outer tank and allowed the basket to be slid from one end of the tank to the other. The drawing in the attachment is a cutaway side view of a standard silver cell. I once made a 5 gallon cell, using a 7 gallon plastic tray as the outer tank. The stainless was the same as in the 30 gallon tank. The basket was made from one of those plastic carrier boxes, with diamond shaped holes, that are used to carry 4 gallons of milk. I cut off the top 1/3 of the basket and ran 2, 3/8" stainless rods through the holes in the basket. These rode on the top of the tray to support the basket. This little cell made about 75 oz. per day and worked great. It was very cheap and fast to build. In both these cells, the size of the stainless cathode must sit very flat on the bottom. It must also fit fairly snug and the corners must be slightly rounded to fit without cutting into the tank coating. It must be professionally bent and professionally cut with a large shear. .

153 The silver in the cell must be harvested at least every 4 hours. If allowed to run too long without harvesting, the silver piles up under the basket and shorts out with the silver bars. This invariably burns a hole in the filter cloth and allows all the grunge collected by the cloth to co-mingle with the solution. Then, the entire 30 gallons has to be filtered and the tank cleaned and re-setup. One doesn't make this mistake twice. If one has to leave for awhile, the power is shutdown or reduced. To harvest the silver, the power is shut off and the crystals are pushed to one end of the stainless cathode. The basket is slid to the other end and the crystals are removed. I always used a stainless BBQ spatula, with no holes in it, to remove the crystals. The power is then turned back on. The crystals are filtered and rinsed very well. Then they are melted and cast into 9999 bars. Yesterday's Post I'm quite familiar with the Hunter patent you linked and I remember the interest it created when it was first released. It is not a patent for a silver cell but, it is a patent for removing the build up of copper from the solution, using solvent extraction. However, the cell solution parameters given (1.5 pH, 60 gm/l silver, 30 gm/l) are valid. There are two basic types of silver cells, the Balbach-Thum (horizontal) cell and the Moebius (vertical) cell. The Moebius cell is usually used for large volume because it takes up less floor space and doesn't need the nearly 24/7 attention that a Thum cell needs, for maximum production. The Thum cell is easier to set up and use. Both are fairly complicated to build. At least, you have to understand what is required. The dimensions are fairly critical. A standard 30 gallon Thum cell will produce about 500 ozs of 9999 silver in a 24 hour period. The books don't come close to telling the entire story. Also, the info in the books is based on mining operations where the composition of the impure bars run the same, day after day. For us, running scrap silver that is different every batch, the situation is much, much more complex. To adequately cover this subject, it would take at least a 30-50 page report, with drawings. There are lots of ins and outs and lots of variables. Each metallic contaminant may require a little different approach. Just as aqua regia is the final purification step for much of the pure gold that is produced, the silver cell is what finally purifies the silver. With gold, there are other methods available besides aqua regia. To get pure silver, the silver cell is about the only game in town. I got 5 years of hands-on experience working in a place that had 12 Thum cells and produced about 5000 ozs per day. Two of the cells were, what we called, breakdown cells. We used them to breakdown silver bars that contained lower amounts of silver. Instead of making up the starting solution with pre-mixed copper and silver nitrates, we started it with only a certain amount of nitric acid and water. As the impure bars dissolved electrolytically and silver crystal was

154 produced, the nitric re-dissolved the crystal and formed the silver solution. This stuff isn't covered in any books. In almost all impure silver, copper is the main contaminant. For example, sterling is 7.5% copper. As the bars dissolve in the cell, the silver plates out as beautiful loose crystals and the copper remains dissolved in the solution. When the copper dissolves, the silver content of the solution decreases. The copper goes up and the silver goes down. At a certain point of either, the crystal purity suffers. The standard way of solving this problem is to remove cell solution and replace it with silver nitrate solution that contains no copper. Thus, the great interest in the Hunter patent mentioned above. This system continuously removes copper from the solution. Before even thinking about a silver cell, you must have a pot furnace with all the associated equipment, in order to produce bars from the impure silver: furnace; crucibles; tongs; molds; fluxes; safety equipment; exhaust; etc., etc. Also, you have to melt and cast the crystal. You also need a variable rectifier to power the cell. For a full size 30 gallon cell, you need at least a 250 amp, 4 volt rectifier. You can run cells in series off of the same power supply (PS). A 250A, 12V PS (approx $2500) will run 3, 30 gal. cells. For smaller cells, the PS needs are proportionally less.

Silver cells part 3

No heat. No agitation. Ideally, the starting solution should be 30 gm/l copper and 60 gm/l silver. You can fudge a little on this but, not much. The purpose of the copper is to make the crystal denser. Without it, the crystal will be fluffy and stringy and will climb all over and soon short out the electrodes. For the copper, I would dissolve solid, clean (no solder) house wire in 50/50, nitric acid/distilled water. You can dissolve about 120 grams in 1 liter of 50/50 nitric. For the silver, use pure silver coins, US 90% coins, silverware, other types of sterling, etc. You can use US 40% silver coins but, not exclusively. You can also use silver that has been cemented out of nitric with copper, if there's no palladium in it and if it's been very well rinsed. Whatever you use, make sure that the only contaminant is copper. Many other metals will create problems. You can dissolve 420 grams of pure silver in 1 liter of 50/50 nitric. When calculating the nitric needed for silver alloys, you'll have to take into consideration the amount of copper in the alloy (s), using the figures above. Also, when calculating the copper wire needed, consider the amount of copper in the silver alloys you're using.

155 After dissolving the metals, it is best to not have any free nitric left in the solution. It doesn't really hurt anything but, until it's used up, the silver crystal produced will be re-dissolved. After dissolving everything, dilute to final volume with distilled water. Never use tap water in any part of this process. It contains chlorides and the silver chloride produced will create a cloudy solution and contaminate the crystal. When the cell is operating, for every gram of copper dissolved in the solution, from the impure silver, the total silver content in the cell will decrease 3.4 grams. If the silver in the cell goes below about 15 - 20 gm/l or the copper goes above 100 gm/l, the crystal purity will be affected. Try to keep records and keep track of how much copper is being dissolved. Usually, you know this by the type of materials you are running. When the silver in solution approaches the danger level, you can build up the silver content in 2 ways. First, you can calculate how much silver you need and add the equivalent amount of nitric acid. This will re-dissolve some of the crystals. This method will obviously cut into your production. Second, you can remove some solution and replace it with silver solution that contains little or no copper. When I ran cells, I analyzed the solution silver content with a simple titration method. One of these days, I'll post how to do it. Then, I measured the specific gravity of the solution with a hydrometer. From this info, I calculated the copper content using a graph I had created. The impure silver you run through the cell should be at least 90% pure. Otherwise, the silver in the cell decreases so fast that you can't keep up with replenishing it. The easiest silver to refine in the cell is silver that has been cemented from a nitric solution and melted into a bar. It runs about 98 - 99% pure and the silver replenishment is not needed nearly as often. At 100% efficiency, you will produce 4.025 grams of silver crystal per amp-hour. However, no electrolytic system runs at 100% efficiency. Therefore, at 5 amps, you produce about 20.125 grams per hour. It is best to not go over 4 volts. If you're using a battery charger, use the 6V setting. It may or may not work at 6V. The crystal density could be severely affected and the crystals may grow all over the place. Never use 12V. If you're handy, you could rig up an adjustable shunt, with a voltmeter, to drop the excess voltage. When running vertically, the crystal will fall off of the stainless cathode and pile up on the bottom of the container. The worst thing that can happen is if this pile grows to the point where it makes contact with both electrodes and shorts them out. I would suggest that you use a 5" separation between anode and cathode.

156 Keep the electrodes about 4" off the bottom of the container. When the crystals build up to a certain point, you'll have to disassemble the entire cell and pour off the solution to collect them. A way around this may be to also bag the stainless cathode. Leave a couple of inches of empty bag below the cathode so there will be enough room to catch the crystals. If you use a bag, you'll probably have to figure a way to hold the bag a little bit away from the cathode surface. If you don't, the crystals may grow through the cloth. I've never used a bag for the cathode but, for some reason, I think this might happen. Since you're running vertically, you'll need some sort of wire to suspend the electrodes. Stainless is the cheapest choice (gold also works). Just remember that stainless is only about 1/35 as conductive as copper. The wire should be heavy enough to not overheat. You can make S-hooks from the wire. Vertical is not the best way to do this. I think that, after you read this, you will see that horizontal is best. It should be easy to design a very small horizontal cell. I once made a horizontal one, in a one liter beaker, for my nephew's science fair project. Ill try to remember how I did it. It's been 20 years. I love silver cells. They're fun and very easy to run, once you get setup and learn the ropes. Pure gold is about the most beautiful thing on earth. Pure silver crystals come in second.

Silver cells part 4

A standard natural gas and air furnace will go to about 2400 F, or so. Until Irons mentioned it, I had never heard of or considered using a silver cell for dissolving silver inquarted karat gold scrap. Interesting. Great idea. I think it could easily be done, at least for yellow, green, and red alloys, which contain only gold, silver, copper, and a little zinc. White gold, with its nickel or palladium, may cause a problem. After silver inquarting, on an average of 50% gold - ballpark numbers: Au = 25%, Cu = 20%, and Ag = 55%. A silver cell contains AgNO3, Cu(NO3)2, and a little nitric acid. In operation, it dissolves the Ag and the Cu and other base metals. It plates out only silver (until the copper and other metals rise too high in the solution). The gold doesn't dissolve but is trapped in a cloth filter. According to Rose, the gold can be as high as 35% for the cell to work.

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Silver cells part 5

I have run many, many thousands of ounces of sterling through a silver cell. It's less efficient than when running purer silver, but it will still work. It's all in the math. Each ounce of copper dissolved will reduce the silver in the cell 3.4 ounces. When the copper exceeds 12 oz/gal or the silver drops below 4 oz/gal, the final purity will be affected. The silver can be built up (or, the copper lowered) by dissolving silver in a minimum amount of nitric and replacing some of the solution with it. You can also add some free nitric to the solution. This will dissolve some of the crystal and build the silver up. It takes about 38 mL of nitric to dissolve a tr.oz. of silver. One amp applied for one hour will, at 100% efficiency, dissolve 4.025 grams of silver or 1.185 grams of copper. The efficiency won't be quite 100%, but it will be pretty close. Continually do all the math and adjust accordingly.

SILVER REFINING
AgCl and cement silver
I'm not familiar with silver bronze. I Googled it and found no listing. I assume you're talking about a silver copper alloy, such as sterling silver, coin silver, etc. Do you know exactly what you have? It could make a difference as to advice. To do what you want to do, I think you should keep things as simple as possible and try not to introduce any new things to the mix. To start with, you only have copper, silver, and nitrate, assuming you're starting with one of the common silver/copper alloys. Of course, there is water and hydrogen ion (H+) but, you really don't have to worry about these last two. There are 3 basic ways to drop silver but, only one doesn't introduce anything new. (1) You can use NaCl, common table salt, to form silver chloride - AgCl. To me, this is the worst choice. You are adding sodium, Na, which is unnecessary. Also, it is almost impossible to drop all of the silver chloride without adding too much NaCl, even with practice. Therefore, you are adding Cl to the mix, which I think would track over during the distillation. You would end up with nitric contaminated

158 with a little hydrochloric, a weak form of aqua regia. Unless you're using the distilled nitric for aqua regia, Cl is one of the worst contaminants you could have. (2) HCl = hydrochloric acid or muriatic acid. This will drop silver chloride the same as table salt. The key ingredient is Cl, which is common to both. This would be better than NaCl because no sodium is introduced. You are adding the H+ ion but, that is good. The reason you add sulfuric to the distillation is for the H+ ions it provides. If you notice the chemical symbols for acids, they always start with H. When you dissolve the silver/copper you rid the nitric of H+ ion and need to provide more. The Cl problem using HCl is the same as with using salt. Muriatic acid is a less pure form of hydrochloric acid. It usually contains a little iron (3) The only way to not add anything new is to cement the silver out of the spent nitric with solid copper. You simply put the copper into the solution and all the silver plates out on it, in a lumpy cement-like form. The purest forms of scrap copper are those used to carry electricity - copper wire or copper buss bar. Wire doesn't work as well because the cemented silver hangs up among the strands of wire and is much harder to rinse out. The buss bar should be clean, not plated, with no solder or connectors. Cut the buss bar so it sticks an inch or two out of the container, so you can remove it easily. The more pieces of buss bar, the faster the silver will cement out. Another advantage in using copper to drop out the silver is that the silver doesn't end up as silver chloride, which requires a fairly difficult process to convert it to silver metal. The cement silver is fairly pure silver metal. If you rinse it well, it can be 99% pure. When using copper to drop the silver, you don't add anything new. You do add a little more copper to the solution from the buss bar, about 1/3 oz for every ounce of silver cemented out. Also, if you didn't use up all the nitric, when dissolving the silver, the extra nitric will dissolve some copper.

Cementing
Really nothing will interfere with the copper method. It's very selective. The only things it will drop is silver, gold, and the platinum group. Everything else stays in solution. I think copper will also drop mercury but, it's never or rarely present At one place I worked, we dissolved large volumes of stuff with aqua regia maybe 15 drums per month. There was gold, platinum, palladium, and a lot of

159 base metals in the solution. We added urea and dropped the gold. Then we used buss bar to drop the Pt and Pd. Worked great. Be careful when melting stuff with zinc in it. When you do, if you see white cobwebs floating around, get away from it. It's very bad to breathe.

Tin
I agree with Steve. It sure sounds like tin. Sounds like you're doing silver solder. Actually, the slimy tin compound that's produced is called metastannic acid (acid tin oxide). If you had silver solder, you probably didn't need to shot it. The silver solder I've worked was in thin strips. You probably had more surface are before you shotted. Just cut it in pieces. I never paid much attention but, I've read a few times that, when there is free nitric in the copper solution, the solution is blue. When there is no free acid, the color is green. To me, the green color indicates there is no nitric left in the solution and, therefore, there is probably some undissolved silver in the slime. I would dilute the main silver solution 1 to 1 with distilled water, filter, and drop the silver with copper buss bar. The filtering is easier if you let it settle then pour, dip, or siphon off the top clear solution and filter it first. When it's finished, filter the bottoms. You shouldn't have put any gold in with the silver. Now you have to pay the piper. Now it's mixed up with the metastannic acid and, it sounds like, some undissolved silver. Metastannic acid won't dissolve in any acid so, you'll have to dissolve the silver and gold, instead. There's a possibility it will dissolve in hot sodium hydroxide but, it's a waste of time since you'll still have to go though the procedures below in order to separate the silver and gold. Here's how I would do it. (1) Silver. After filtering the slime, put it into a very small amount of 50/50 nitric, diluted with distilled water. Heat it until no more reaction. Add a little more if you need it. This dissolves the silver. Try to filter and rinse it as well as you can. Add the solution and rinses to the main silver solution. (2) Gold. a) Put the filtered slime, filter paper and all, into a heatable glass container. The paper will pulp up and will help in filtering (you can buy paper pulp filtering aids).

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b) Barely cover with hydrochloric or muriatic acid (both are HCl) and heat until it is a little steamy. c) Add the nitric acid, dropwise, until there is no more fizzing with an addition. Add the nitric in spurts, a few drops at a time, and allow each spurt to quit reacting before adding the next spurt. Stir before adding the next spurt. d) Add a shot of HCl. If there is no reaction, you are finished. e) If there is fizzing, do the nitric again. f) Repeat until there is no fizzing with either acid. Sometimes, the acid additions will have to heat up a few seconds before the fizzing starts. g) Dilute 3 times with tap water, filter and rinse well, and drop the gold with sodium metabisulfite. If you did steps (c) thru (f) right, and kept out excess nitric, you won't need any urea. Note on Glassware. Just because something is Pyrex, it doesn't mean that you can use direct heat on it. I notice you are using a vacuum filtering flask on the hot plate. These are made too thick and uneven (wall thickness) for direct heating. They will exhibit thermal shock and break. It might not break today but it's going to break sometime. You need Pyrex (or, Kimax) containers designed for direct heating. These are coffee pots, beakers, erlenmeyer flasks, and other lab containers. Don't use Pyrex things like measuring cups, vacuum filtering flasks, or battery jars to heat with. You can also use Corning Ware containers to dissolve in with a lot of direct heat. You can use either the white, flat-bottomed type or the amber, see-through ones.

Silver plated items

A traditional silver cell is only used to process solid silver that is at least 90% (sterling silver, e.g.) pure to 99.99%. Like aqua regia is for gold, a silver cell is the final purification step for most silver recovery operations, no matter what items are started with. Most all silver plated materials have copper or copper alloys underneath the silver. I know of no common cell that will selectively remove silver plate from

161 copper based items, except the strong sulfuric cell that you are presently using. However, what do you do next, economically? Silver stripping was included in the original sulfuric patent but, I've never played with it. The patent holder was a plater and stripping faulty plating was the original intention of the patent I once developed a cell using cyanide plus a large amount of sodium hydroxide that didn't eat the copper and worked quite well but, you had to keep the parts moving in a tumbler. The silver (or, gold) that stripped automatically plated out on the cathode. The coinage metals, gold, silver, and copper, are found together in nature and have many chemical properties in common. All can be dissolved in cyanide, for example. The high sodium hydroxide in my cell slowed greatly the attack on the copper. This system is, obviously, beyond your scope. In the books, about the only method given is the super nasty, super dangerous hot concentrated sulfuric plus a little nitric - I think they say 5% for the nitric. No electrolytic cell. All you have to do is immerse the parts. For thin plating, heating isn't necessary. Here again, this process doesn't work economically. It's designed to strip faulty plating off so the parts can be replated. Most refiners don't want silver plated items. Basically, silver plated copper is considered as contaminated copper. Most silver plated copper only runs 1% silver. Some silverware is higher. Don't buy it unless you pay a lot less than copper price. If you do have a bunch of it, look for a refiner that burns boards, melts all the resulting metals into ingots that run about 65% copper, and then ships the ingots for further refining. He might, just might, pay you a small price over copper market. He always needs cheap copper and can add the stuff to the melt. He often needs extra copper to lower the melting point of hi-temp melting items containing lots of iron and nickel. The big smelter he ships to will pay him for the silver.

Dental amalgam
The age old question, "What do you do with dental amalgam?" Not as bad as, "What do you do with silver plated copper wire?" Amalgam is composed of silver, tin, and mercury. The mercury is a little over half of the total weight. You first have to either retort off the mercury or, pay someone else to do it. Maybe you can find somebody more local than you think. After the mercury is gone, the silver/tin alloy runs about 69/31, if I remember right. This alloy is not easy to refine. You can't use nitric acid because the nitric acid dissolves the tin and converts it to metastannic acid, a slimy mess that can nearly stop the action and shut you down. The only good way I've seen the silver/tin alloy separated is in a silver cell. And, that's tricky.

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--You could sell it as is. Dental refiners will buy it. The silver runs 33% - $62 per pound -as is. Shop around and find the best price. --You could have it refined. The minimum lot charge may be around $250. Your 35 pounds of amalgam is worth, intrinsically, about $2170, in silver, less charges. Only God and the refiner knows how much money you'll end up with. --You could find a buyer that would buy the Ag/Sn alloy, for probably more money, after the mercury is removed. You better make damned sure all the mercury is gone, however. You don't want the buyer to melt it and get mercury poisoning. -- You could get a silver cell and separate the silver from the tin, after the mercury is gone. Then, sell the pure silver.

More on silver plate

With only a few pounds of silver plated material, you'll be lucky if there's an ounce of silver, total. Unfortunately, especially for the amateur, I can think of no way to make a profit in working this type material. Also, no refiner that I know of, wants this material. Basically, you have a low grade copper alloy contaminated with silver.

Dissolving silver in sulfuric acid

An old method that is still used for dissolving silver from hi-silver, lo-gold dore' bars was to use boiling concentrated sulfuric acid, with nothing else added. I think they used fine-grained white cast iron vessels. The process is very, very dangerous. It is detailed in T.K. Rose's, "Metallurgy of Gold".

Silver coins
Quote: I have 2.169 of pre 1947 silver coins so a 50% silver content If i sell them on ebay ill probably get 200 pounds for the 2.169 kg Or i could refine myself into around 99% pure 10 oz bullions ? How much

163 would a silver buyer pay ? or Should i simply keep the coins as an investment??? i dont mind what i do 200 pounds isnt going to make alot of difference to my life so i can afford not to sell them. What would you do ??

One neat thing about coins is that you know exactly what the PM content is. Don't destroy this by melting or dissolving them. Keep them as coins You have about 35 oz of silver. You can get about 80%, ballpark, by selling on Ebay. 50% silver alloys are costly to refine, maybe 10 times more so than 90% silver. The cost is due to the fact that a silver cell doesn't work on silver below about 85%.Therefore, the 50% Ag has to go through a costly pretreatment. Buyers and refiners don't really like this stuff and you will take a beating when selling it. Were I buying it, I might give you 60%. It would take several 1000 dollars to set up to properly refine 50% silver. Investment? Maybe, or maybe not. Your guess is as good as mine. If you can get 80% on Ebay, then do it. I think money should be "turned."

Steel wool canisters for photo fixer

Steel wool canisters are usually used to remove final traces of silver from waste fixer solutions, after the bulk of the silver has been removed electrolytically. The steel wool canisters are not easy to melt, even with a crucible furnace. I think you will have zero success with a torch. More than likely, much of the steel wool remains unreacted and the steel wool mass is partially intact. This results in very difficult melting and a low silver content. The best scenario is when all of the steel wool is gone and only a black sludge remains. The black sludge contains silver and is always very high in sulfur, from the breakdown of the hypo. The sulfur must be eliminated. This is usually done in a crucible furnace by the use of rebar. The rebar is cut in about 2 or 3 foot lengths and is allowed to soak, with some stirring, in the melt. The iron from the

164 rebar combines with the sulfur to form an iron sulfide, which slags out and separates from the silver metal, when poured into an oiled or carbon coated cast iron cone mold. The pieces of rebar must be long enough so they protrude well out of the crucible and the furnace vent hole and then they are totally removed, by hand, when the reaction is complete. Borax and soda ash are used for a flux. The slag will generally be thick and will retain many silver BBs. I don't consider this a process for the amateur. It is quite difficult to get all the silver. Also, there are a lot of potentially dangerous sulfur fumes emitted. You must be set up to do this and, from my experience (I have run, literally, tons of this stuff), a well ventilated gas crucible furnace is a must. #10 If it's marked "Sterling", it most probably is Sterling. If it isn't marked "Sterling", it is probably silver plate on copper. There are exceptions but they are rare. It takes about 1.4 mL of nitric plus 1.4 mL of distilled water to dissolve 1 gram of sterling silver. Here's the way I do it. 1 - Weigh the sterling, figure out how much nitric and water you need, and measure out these quantities. 2 - Put the silver in a Pyrex or plastic container. The container should be about 5 times larger than the total amount of liquid needed. I prefer a plastic bucket. 3 - Add all the required water to the container. 4 - Put the container under a fume hood. 5 - Don't add all the nitric at once - it could create a foam-over. Add only about 1/5 of the required amount of nitric. It will soon start fizzing, heating up, and producing toxic red-brown fumes. When the reaction nearly stops, very slowly give it a stir. 6 - Repeat step 5 until all the nitric is in. When the reaction has slowed down, stir it completely, remove the stirrer, cover the container, and let it work and settle overnight. If blue crystals have formed, add a little hot distilled water to dissolve them. 7 - After settling, siphon off the top solution. If there is any undissolved silver on the bottom, dissolve it in a minimum of 50/50, nitric/distilled water.

165 8 - Combine all the solutions and filter. Put the filtered solution into a clean bucket. 9 - Put several bare copper buss bars upright in the solution. They should be long enough to stick several inches out of the solution. The silver will start cementing onto the copper, as a grey sludge. Stir occasionally. 10 - The next morning, test to see if any silver remains in the solution. Put a drop of HCl or salt water into the solution. If a white cloud appears, silver remains. Keep cementing until there is no white cloud. 11 - Filter and rinse well, with hot distilled water, until all the copper solution has been removed from the silver. Traces of copper can be seen better by collecting some rinse water from the tip of the filter funnel and adding enough ammonia to make it basic. Traces of copper will show blue. 12 - Dry, and, if you want pure silver, melt the silver powder and run it through a silver cell. Otherwise, you may as well sell the original sterling, as is.

SULFURIC STRIPPER
Sulfuric stripper part 1
In another thread, someone asked if the sulfuric could be reused. The answer is no in the present system. The reason is because of the water dilution that is used to gather the black sludge. And, of course, if you try to strip with the diluted sulfuric, it would be worthless since, you will dissolve everything - copper, nickel, etc. It has been suggested that the water could be removed through a boiling and distillation process. I feel that this would be expensive, dangerous, and unnecessary. There is a simple way to avoid the dilution and use the concentrated sulfuric over and over again. In the early '70's, I used this same system on a grand scale. I had a 50 gal tank and used the same solution over and over for several years. I used a mild steel tank and made the tank the cathode. I was stripping gold IC's on plating type racks (see the diagrams in the original patent - #2185858 - go to Google patents - Google/more/patents). We ran about 300 gold IC's every 20 minutes. Every few weeks, when the solution became saturated with gold, we allowed the gold to settle and then pumped the solution off the top into a second stripping tank. We then harvested the sludge in the first tank and commenced our stripping in the second tank. We could tell when the solution was saturated by observing the

166 amperage. Normally, when the parts are finished stripping, the amperage goes to zero. When saturated, the amperage doesn't go to zero because the large amount of gold creates conductivity between anode and cathode. Here's how I would modify your setup: (1) When you're ready to harvest, carefully stir up the solution with a stir rod. One of the straight parts of a plastic clothes hanger works well. Use the rod to knock down the gold clinging to the sides of the container. Put something (a piece of 1" wood?) under one end of the container to tilt it. Allow the gold to settle overnight. Since the container is tilted, most of the gold will settle at the opposite end. (2) Instead of pouring the solution into water, carefully pour the solution off of the sludge into a clean, dry container. This could be any suitable container but, it would be best to use a second stripping container. This way, you only have to pour the sulfuric once and you don't lose any stripping time. Be careful not to pour off any sludge. But, even if a little sludge gets transferred, don't fret; you'll get it next time. If the sludge gets stirred up, tilt the container again even more, let it settle, and pour it off again. The idea is to pour off as much sulfuric as possible without pouring off any sludge. (3) Treat the sludge as normal, by putting it into water. (4) You will lose a little strong sulfuric in the process. Top it off with a little fresh sulfuric and start stripping. (5) If you dissolve a lot of nickel in the solution, it will, eventually, make the solution stop stripping. There is almost always nickel plating under the gold plating. To avoid dissolving the nickel (it dissolves very slowly), make sure you remove the parts as soon as the gold has finished stripping. (6) SAFETY. Pouring strong sulfuric can be a very dangerous proposition. Pour slow and steady. If you're shaky, you shouldn't be doing this work. Don't get cocky. If you have a hangover, wait until tomorrow. Make sure your gloves and the outside of the container are dry. Wet gloves will slip. Don't allow strong sulfuric to remain on the gloves, as it will eventually attack them. When pouring, it is best to put the receiving container in a cheap plastic tray (WalMart). If fact, it would be best to get a fairly large tray, about 6" deep and perform all operations in the tray. It makes dribbles a lot easier to clean up. When pouring, pour away from you. Protect your eyes and face with, at least, a full face shield. If a splattered spec of sulfuric gets on your arm, you will immediately feel it start burning. Don't panic and drop the container. Grit your teeth and put it down carefully before running to the faucet or dipping your arm in a bucket of fresh water. Always have a lot of fresh water handy. Don't wear cotton clothing or any nice clothing. Although ugly, polyester clothing stands up the best. Think smart and look before you leap.

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Although I learned every one of these safety tips the hard way, I have never been hurt, even though I operated systems as large as 200 gallons. I have no scars and I still have my sight. I have ruined a lot of Levis. Listen to me.

Sulfuric stripper part 2

I used to run a lot of gold plated IC lids with Gold/Tin braze on them using this stripper (not exactly - see below). When you try to strip a bunch of small parts, like these lids or pins, in a pile, in a basket, only the surface of the pile strips. The pins in the center don't receive current and remain unstripped unless you stir them up quite often. This problem was solved by using a "plating barrel". Here's a good shot of a plating barrel: http://www.singletoncorp.com/portable_barrels.html This will give you an idea of prices: http://www.luster-on.com/home......et=d8.html Notice the black cable going inside the barrel. There's one on each side. On the ends of these cables, there's a lead slug that flops around on the inside of the barrel, as it rotates, making eventual contact with every part. The lead slug is called a dangler. It's hard to see in the photo but, the barrel is finely perforated to allow the passage of solution and current. The speed is variable but is best run about 3 rpm. In short order, everything is stripped. They are expensive and come in various sizes. Our barrel was about 8" in dia. and 12" in length. Also, they are made of various materials. The mfgr. can suggest the best material that will stand up to conc. sulfuric. You could probably made a barrel out of finely perforated steel or, steel with large holes lined with a spot welded heavy screen, using solid teflon bearings. The holes would have to be small enough to prevent the pins from falling out. I must warn you that the standard solution formula won't work on gold alloys, such as Gold/Tin. I doubt that it will work on most karat golds. It took me a year to come up with modifications to the solution to make it eat alloy. I've been tempted to give you the info but, I can't do it. It's too valuable. I formed two very profitable businesses using the process. I made enough to live on the beach in Malibu for 5 years. My son's best friend in high school was Charlie Sheen. It's still viable. The parts are still there and I'm the only one that can process them. No BS. Your present system works great on plated gold, like pins, however. The volt/amp relationship is tricky. You can't use a battery charger, like yours, on larger batches. You need a power supply that can be adjusted. If you tried

168 running a much larger batch using your uncontrolled power supply, at a constant 6 or 12 volts, you would peg the meter, blow the fuse and, if there is no fuse, you could blow the power supply. It's hard to see, only running a pin or two, what really happens. Here's the way it works, assuming a larger batch: When you first turn it on, at 6V, the amps go sky high. As the gold strips, the amps go down and the volts go up. When the gold is gone, there is zero amps. It tells you when it is finished. I used a 12V, 200A rectifier for the 50 gallon tank. Here's the way I ran it. I started with the volts at zero. I slowly turned up the voltage and watched the amperage. At first, it may only take 2 or 3 volts to get, say, 175 amps. As the gold strips, the amps steadily go down and you can steadily increase the volts to maintain the 175 amps. At some point, you will have 6 volts and 175 amps. At this point, you stop adjusting. The amps go down and the voltage climbs. Soon, the amps will be zero and the volts will probably be max. If you think about it, any adjustment gives constant power - volts times amps, even if they are both changing. Also, if you think about it, any size power supply would work, no matter how large the batch. The time it took to strip the gold would depend on the available power output. A very small power supply would strip all of the gold but, it would take more time. You could control your power supply by plugging it in to a Variac, a variable transformer. Variacs work on most devices. I think they will work fine on a battery charger. On the left in the photo. http://variac.com/

Sulfuric stripper Get a free plating book

Bill, The barrel was plastic. Polypropylene, I think. The danglers were, therefore, the anode. Sue, The barrel I was using was scrounged but, it was like new. It came with the lead danglers. If I remember right, the lead was harder than normal so, it probably was an alloy. To be honest, it always worked great so, I didn't pay much attention to the danglers. They never seemed to change. I don't remember any fluctuations in anything. Recently, on the Web, I noticed that a lot of the danglers were steel balls. There are other types of contacts. Center bar contacts are just that, a center bar at the axle position. There are also button contacts, which are rows of metal buttons, about 1" in dia., mounted and wired, somehow, on the insides of

169 the barrel. They also sell a self contained barrel. It looks like a cement mixer pointed up at a slight angle. You put the solution and the parts together in the tumbler. I've only seen it in photos so, I don't how the contacts work. To all, I would like to suggest a book. It is called the, "Metal Finishing Guidebook and Directory" and is about 900 pages. You can't buy it. It's a trade book. You only get it with a subscription to Metal Finishing Magazine, which is free to plating people. It is upgraded each year and is sent, in the spring, as the mags 12th issue. If you've just barely missed the date, you'll have to wait a year to get it. To get a subscription, on the online form, you'll have to type in the right things to convince them that you're in the plating business. I doubt if they check on you. http://www.metalfinishing.com/magazine/index.html Of the many books I own, I have used this book the most, even more than Hoke. Plating and refining are very closely knit, especially electrolytic refining. I spent about 10 years in the gold plating business and I still have a 1968 issue, my first one. Here are some handy chapters with refining applications, all in good detail: Ultrasonics; Barrel Plating; Gold, Silver, Platinum, Palladium, Rhodium, Ruthenium Plating (separate chapters); Stripping Metallic Coatings; Chemical Analysis; Thickness Testing; Identification of Deposits; DC Power Supplies; Rack Design; Pumps; Mixing; Industrial Ventilation; Wastewater Treatment.

Sulfuric stripper part 3

In this case, it's reversed. The mild steel suffered no attack over several years except for very slight etching at the top of the solution where the sulfuric, iron, and oxygen, from the air, all contact each other. The welds weren't affected either. Use welding rod that contains no nickel. Nickel is the one bad actor in this whole system. Although slow, the sulfuric will attack nickel or nickel alloys. Also, much nickel will make the solution stop stripping. I have thought, over the years, that a small addition of chromic acid or potassium dichromate would prevent nickel attack but, I haven't tried it. There is no problem with stray currents. If I remember right, the tank sat on the concrete floor. It was made of 1/4" steel, since 50 gallons of sulfuric weighs about 800#. When I first experimented with this solution, I was using a standard, thin, 4 liter stainless lab beaker. In a few days, the solution ate a hole in the beaker. The stainless was magnetic. Probably 400 series with no nickel. But, 300 series, with nickel, would probably have been eaten sooner. Maybe, the chromium, in both SS series, is attacked also. There's one thing I should mention. Strong sulfuric is a desiccant. In other words, it absorbs moisture out of the air and gets weaker. People in high humidity areas

170 may notice this. Probably not, though, since the absorption slows down considerably as it gets weaker. Good to know, though. When I ran the 50 gallon system, I used bare brass racks to hold the parts. Here again, I got no attack except for slight etching where the top of the solution, the brass, and the air all met. Also, due to water absorption, the solution was probably weaker at the surface. And, weak electrolytic sulfuric will attack most base metals.

Sulfuric stripper part 4

At this full strength, the stripper may not work as well as it would if you were to dilute it a little. If you do dilute it, follow these instructions. If you're sure about the strength, I would dilute it to start with. Even if it isn't that strong, the dilution probably won't hurt DON'T POUR THE WATER INTO THE SULFURIC!!! If you do you could create instant steam and splatter the acid all over. Instead: (1) Calculate how much water you'll need for a 5% (1/19 th water) dilution, by volume. This depends on how much acid you need for the cell. For example: For 19 fluid ounces of acid, use 1 fluid ounce of water. The ratio doesn't have to be perfect, just close. (2) Measure the required water. Add the water to the empty cell. (3) Put on your gloves and face shield. Carefully, add the required sulfuric to the water. It will get hot at first but, will cool off when most of the sulfuric has been added. Don't be startled if it fizzes a bit when you start adding the sulfuric. (4) When the sulfuric is in, carefully stir it until blended. Try not to slop it over the sides.

Silver in the sulfuric stripper

I'm having a little problem following you but, it seems that what you are doing could be very dangerous. I have never seen the 95H2SO4/5HNO3 combo used electrolytically and see no reason for doing so. This is an immersion method. It works slowly at room temp. You can speed it up with heat but, hot concentrated sulfuric is very dangerous to work with, especially when you've added nitric to it.

171 There is a very good possibility that the conc. sulfuric will eat the glaze off of the crockpot. If this happens, the ceramic will soak up the sulfuric like a sponge and will break when heated. Talk about dangerous. I've been there and done that. Getting the silver out of the conc. sulfuric is a big problem. You can't add the salt to the conc. sulfuric. If you do, the chloride from the salt, instead of dropping silver chloride, will immediately be converted to dangerous chlorine gas. In order to drop the AgCl, you will first have to dilute the cooled sulfuric with about 9 volumes of water. ALWAYS ADD THE ACID TO THE WATER!!! NEVER ADD THE WATER TO THE ACID!!! The problem here is that the silver is only slightly soluble in dilute sulfuric. When you dilute, a lot of the silver drops as silver sulfate. Then, when you add the salt, you will end up with a mixture of silver sulfate and silver chloride. This mixture won't completely work with the Karo syrup method. I no longer have a Hoke book. I do remember that, towards the back of the book, she mentions some INDUSTRIAL processes that are used. I think the dissolving of silver by hot conc. sulfuric acid fell into that category. This was commonly used for hi-silver, silver/gold dore' bars. If I remember right, it was done very hot in a cast iron vessel. Very dangerous method if you're not set up properly to do it. Lots of SO2 fumes, also. I know that the wide availability of silver plated copper base scrap is like a carrot dangling in front of your nose. I've gone through this myself and can guarantee that the way you're approaching it is no good. The only method I've found that works economically and fairly safely, on some materials, is electrolytic cyanide containing a lot of sodium hydroxide. Most silver plated copper scrap runs in the ballpark of 1% silver, about $2 per pound. It's not worth the injuries you could sustain by the method you have outlined. You still have to dilute it first to cement it. With cementation, you'll end up with a mix of silver sulfate and silver metal. Cementation with strong sulfuric won't work because copper is only slightly soluble in strong sulfuric. In order for silver to cement, copper has to dissolve but, the strong sulfuric won't allow it to dissolve. Strong sulfuric and weak sulfuric are like 2 totally different acids. Once above about 85%, sulfuric starts doing some unique things.

Sulfuric stripper part 5

Please explain what stalling or stopping means.

172 If you have too much gold in the solution, the amps won't go to zero when all the gold has stripped. It's been so long that I don't remember how the saturation of gold affected the stripping rate. Does your ammeter go to zero. Try cleaning all of your connections. They corrode quite easily and lose contact. The anode is the gold plated parts you are stripping. It is connected to the positive (+) lead. The other electrode, the screen I assume, is the cathode and is connected to the negative (-) lead. Is this how they are hooked up? Both are called electrodes. Harold, Please forgive me but I found out, in practice, that the system will strip no matter what voltage you use (almost). I always started the voltage at zero and slowly cranked it up. I was processing large loads and my 200 amp rectifier might nearly peg, at the start, with only 1 or 2 volts. Within maybe 30 seconds, the amps started decreasing and I would slowly crank up the volts to maintain maximum amps. After a few minutes, the voltage was about 6 or 8 and I could walk away safely without worrying about the amps banging the peg and blowing a fuse. I was stripping thick gold braze and, after about 15 minutes, the amps were at zero and the volts were pegged, at 12 volts. All gold was stripped. After running this thing for years, I have come to the conclusion that if, you have a controllable power supply, it makes no difference how large it is. The only difference is that a smaller power supply will be proportionally slower. Instead of 15 minutes for a 200 amp supply, a 20 amp supply might take 150 minutes. They are both 3000 amp-minutes. I don't think that Mason, who wrote the patent, had a very good feel for how this system works. He probably found something that worked for his narrow application, and Western Electric forced him into a quick patent. Since I've been on the forum, I've always been against the use of these fixed power supplies. You are so limited by using them because, if you overload them, the power supply could burn out, if there's no fuse. Steve, correct me if I'm wrong about this. If you had a control, you could load the cell with as much stuff as you could squeeze into it. I know that controllable power supplies are much more expensive. On one thread, I suggested that you could plug these into a Variac. But, they're also expensive. On this same thread, Steve suggested another way.

Sulfuric stripper part 6

173 The anode (+) is always the one that dissolves. The cathode (-) is the one that plates. To plate, you must have a metal dissolved in the solution. In this strong sulfuric system, since there is essentially nothing dissolved in the solution, nothing will plate onto the cathode. The gold dissolves from the anode but, it immediately precipitates and forms a powder and, therefore, it is not dissolved and doesn't plate out. If your sulfuric is too weak, there is a much better chance of dissolving copper and nickel, and both of these can plate out on the cathode. You could probably use about anything that's conductive for the cathode as long as it's something that doesn't fall apart, like carbon.

Using sulfuric drain cleaner

Like Steve said, don't dilute the sulfuric. Sulfuric, when very strong, will dissolve only traces of copper and other base metals. As you dilute it with water, more and more base metals will dissolve. Thus, the blue green color of your solution. The amps aren't going to zero because you're dissolving copper and nickel. Were I you, I would start over. It does, however, improve the stripping to have a little water in the solution. If I were using the 94% "liquid lightning" product, I would add 5% water, by volume. Always add the acid to the water. However, _____ has been using this product at full strength with great success. Steve is using a sulfuric drain cleaner product that is slightly weaker and would never need additional water. I think he has also mentioned a greenish solution. _______. Please don't take offense. You seem to be a very experimental type person, and thats great, but you often seem to not look before you leap. I don't want you to get hurt. There's tons of info on this forum to keep you safe and, yet, get maximum capabilities out of these chemicals. If you want to experiment, I would suggest asking us what we think about your idea, before you do it. When you gain experience, you'll know better about what you can or cannot do.

Sulfuric stripper part 7

When I ran this stripper, for many years, I never melted the black gold sludge. I just rinsed it well and put it right into aqua regia, filter paper and all. It dissolves almost immediately, with much foaming. I first covered with HCl and heated it slightly. I then fed in the nitric in very small increments to prevent it from foaming over. If any silver is present, you'll collect it in the aqua regia filter. Nothing is lost.

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Sulfuric stripper part 8

Please forgive me but I found out, in practice, that the system will strip no matter what voltage you use (almost). I always started the voltage at zero and slowly cranked it up. I was processing large loads and my 200 amp rectifier might nearly peg, at the start, with only 1 or 2 volts. Within maybe 30 seconds, the amps started decreasing and I would slowly crank up the volts to maintain maximum amps. After a few minutes, the voltage was about 6 or 8 and I could walk away safely without worrying about the amps banging the peg and blowing a fuse. I was stripping thick gold braze and, after about 15 minutes, the amps were at zero and the volts were pegged, at 12 volts. All gold was stripped. After running this thing for years, I have come to the conclusion that if, you have a controllable power supply, it makes no difference how large it is. The only difference is that a smaller power supply will be proportionally slower. Instead of 15 minutes for a 200 amp supply, a 20 amp supply might take 150 minutes. They are both 3000 amp-minutes. I don't think that Mason, who wrote the patent, had a very good feel for how this system works. He probably found something that worked for his narrow application, and Western Electric forced him into a quick patent. Since I've been on the forum, I've always been against the use of these fixed power supplies. You are so limited by using them because, if you overload them, the power supply could burn out, if there's no fuse. Steve, correct me if I'm wrong about this. If you had a control, you could load the cell with as much stuff as you could squeeze into it. I know that controllable power supplies are much more expensive. On one thread, I suggested that you could plug these into a Variac. But, they're also expensive. On this same thread, Steve suggested another way.

Sulfuric stripper part 9

I have never used glycerin in the sulfuric cell. In fact, I've never gotten a good explanation of why it is used. I have also never used the sulfuric cell for stripping silver. The hassle of getting it out of the solution has always outweighed the benefits. The patent was used to reclaim and eventually replate parts that had faulty plating on them. I don't think that the reclaiming of small amounts of $1.29/tr.oz. silver ever entered their minds. Trust me, there is no economical way to recover silver from silver plated copper alloys, except for maybe the cyanide/hydroxide electrolytic method that I mentioned earlier. This is a shame since there are zillions of tons of this material

175 out there. It is basically contaminated copper. If anyone ever figures out how to do it, they could become wealthy. Good luck.

Sulfuric stripper part 10

I've noticed a trend, on this forum, to shy away from the sulfuric cell as a method of running pins. In my opinion, the stationary copper mesh basket isn't the best way to go about this. Also. I feel that the sulfuric cell is far superior to any copper dissolving method, if it were engineered right. I think if someone were to come up with a rotating basket, all would be well. I've been thinking of maybe using a slow turning BBQ rotisserie setup for this. A plastic container, with holes in it, could be mounted (centered) on the axle. The container would be filled a little over half full with pins. The container would only be about 1/3 submerged and the axle would be kept out of the solution. Most rotisserie axles are square and this would make it easy to turn the container, if the plastic were thick enough. One section of the axle, near one end. would be ground round and a springy metal anode contact could be used to constantly apply current to the axle. Something like a brush on a slip ring. I see the rotisserie being mounted on a board under the tank. The tank would have two cathodes connected together, one on each side of the basket container. As the container turned, pins would touch the axle and provide current to the whole mass of pins.

Sulfuric stripper part 11

I've noticed a trend, on this forum, to shy away from the sulfuric cell as a method of running pins. In my opinion, the stationary copper mesh basket isn't the best way to go about this. Also. I feel that the sulfuric cell is far superior to any copper dissolving method, if it were engineered right. I think if someone were to come up with a rotating basket, all would be well. I've been thinking of maybe using a slow turning BBQ rotisserie setup for this. A plastic container, with holes in it, could be mounted (centered) on the axle. The container would be filled a little over half full with pins. The container would only be about 1/3 submerged and the axle would be kept out of the solution. Most rotisserie axles are square and this would make it easy to turn the container, if the plastic were thick enough. One section of the axle, near one end. would be ground round and a springy metal anode contact could be used to constantly apply current to the axle. Something like a brush on a slip ring. I see the rotisserie being mounted on a board under the tank. The tank would have two cathodes connected together, one on each side of the basket container. As the

176 container turned, pins would touch the axle and provide current to the whole mass of pins.

Sulfuric stripper part 12

I can't see how it would make much difference, especially when only running a few parts at a time. The 12V setting will do it faster. It will also provide more amps. If I were doing a large batch in a basket or a tumbler, I would probably start it at 6V and, when the amps fall, I would raise it to 12V at the finish. However, I always used a completely variable PS for this purpose. I sure Steve could give you best way to do it with a battery charger.

Sulfuric stripper part 13

I think you're making a mistake by using weak sulfuric. As I understand it, you're using 4 Molar, which is only 20-25% sulfuric. This is why you're having problems with the copper dissolving and plating out. The stronger the sulfuric, the less copper (or, anything else) will dissolve. I always used concentrated (~96%, by weight) technical grade sulfuric with about 5% to 10% water, by volume, added (add the acid to the water!!). You need a little water to perk up the speed. A 10% water addition, by volume, is equivalent to about a 5% addition, by weight, since the sulfuric is almost twice as heavy as water. Conc. sulfuric can be used without the water but, a little water will speed it up. If you're in a humid climate, only use 5% water as the sulfuric will absorb water from the air. I daily stripped the gold and gold braze from reject, sealed, side-braze CPU packages in this system, at the rate of about 50,000 to 100,000 of them per week. This was a commercial venture. I mounted them on bare brass or copper racks, using piano wire spring contacts to hold the parts. There was little or no attack on any part of the rack, tank, or other portions of the packages, when using the strong sulfuric (it was slightly modified - my invention - in order to strip the brazes). I then re-plated the packages and returned them to the customer for re-use - Intel, AMD, and AMI were my biggest customers. We basically recycled their reject parts, for re-use, and charged them half the cost of a new package. Since most of the gold value was in the brazes used on the chip and the sealing lid, we removed much more gold than we put back on. The extra gold recovered essentially paid for the process. I used a 50 gallon welded mild steel tank and made the tank the cathode. After using it daily, at room temp, for about 2 years, there was hardly any visible attack

177 on the tank, except a little at the solution surface, where the acid, the steel, and the oxygen in the air all met. Don't use stainless - it will be slowly eroded, due to the presence of the Cr and Ni. Nickel (and probably cobalt) is the bad actor in this system. If too much is dissolved, it will stop the action. I have thought about adding a little potassium dichromate to the sulfuric to inhibit the attack on the nickel, but I've never actually tried it. Your use of a glass fish tank is scary. I sure wouldn't want 4 gallons of sulfuric in my lap. If you go to the strong sulfuric that I suggest, you must go to a steel tank because it will likely attack the cement that holds the glass tank together. Search around a scrap yard and you will find some sort of mild steel container that is just the right size and shape for what you need - cheap. I would try to find a container that is at least 1/8" thick. When using the stronger sulfuric, you will get far less fizzing than you will with a weaker solution. The trick is to start the rectifier at zero and slowly crank it up. At first, the amps are high and the volts are low. After about a minute, the amps will drop, somewhat, and the voltage will increase. As you slowly crank up the voltage, the amps will first increase and then will decrease. At some point, when the gold is completely stripped, the volts will be at about 9 (or, higher, if desired) and the amps will be zero. At this point, all of the gold is stripped. This won't work with a more dilute sulfuric because it will continue to attack the base metals and will therefore continue to draw current. With the stronger sulfuric, nothing deposits on the cathode (the mild steel tank). The gold forms as a powder and settles to the bottom. The solution is then drained off and the gold is easily recovered and then refined in aqua regia. I might mention, eagle2, that there's a hell of a lot of difference in concentrated sulfuric (96%+) and battery acid (about 40%) in this system. The battery acid will dissolve almost everything. Conc. sulfuric, with a little water, will only essentially dissolve and precipitate the gold. There will only be very minor amounts of base metals in the gold sludge. When using the conc. sulfuric with only 5-10% water, by volume, regular gold plating will completely be removed in a minute or two. Sure beats 30-40 hours. With my modification to the solution, the gold brazes took about 15-20 minutes. I've only dented the surface of this subject. I have maybe 20 years experience of working daily with this solution on a grand scale. I'm game, if you want to go deeper into this.

TERMS: My definitions. There are variations but these give the general idea.

178 Electrowinning. The electrodeposition of metals that have already been put into solution before the solution is put into the electrowinning tank. Uses an inert anode. Pure metal deposits on cathode. Impurities remain in the solution. Electrorefining. Electrolytically dissolves an impure anode and simultaneously deposits pure metal at the cathode. Those impurities that dissolve remain in the solution. Those that don't dissolve are usually collected in an anode bag. Electrostripping. Selectively removing a metallic coating, electrolytically. The dissolved metal either plates onto the cathode or immediately precipitates out, as in the gold/sulfuric system, above.

Sulfuric stripper part 14

Quote: I have read electro stripping articles that describe the stripping action on gold plate or bullion. The gold never goes into solution in sulfuric. The underlying base metal is attacked through microscopic imperfections in the gold plate. These metals oxidize and go into solution. This loosens and breaks up the gold plate into fine bits. You can see the yellow glitter falling or floating.

Hey, Al, I would suggest you read the original patent on this: #2185858. http://www.google.com/patents?.....dq=2185858 According to this, the gold momentarily dissolves due to the presence of persulfuric acid. It then immediately precipitates. I have read elsewhere that this is due to the presence of small amounts of sulfurous acid, which is basically a sulfite. Also, there is no such thing as the existence of gold sulfate in the strong sulfuric. It has nothing to do with the acid penetrating though the porosity of the gold plate and attacking the underlying base metals. In fact, the underlying base metals are hardly attacked at all. According to the patent, this is due to the formation of an oxide coating on the base metals. In practice, there will be very, very minor amounts of base metals co-mingled with the precipitated gold. This assumes that the concentration of the sulfuric is above a threshold strength. The patent says this threshold is 60%, but I really don't like it that weak - I would keep it much higher. Also, the patent suggests using nickel sulfate as an accelerator. I think this would be a big mistake, since too much nickel will completely stop the stripping of gold. If this happens, the solution is dead and you'll have to start with fresh solution.

179 I should also mention that there's no glycerin in the original patent. Down the line, some yo-yo added glycerin for some reason and this myth has perpetuated itself. Reminds me of the lady who always cut the end off on a big ham before putting it in the oven. She said she did this because her Mother had always done it. Come to find out, her Mother's oven was too small to hold a big ham. The Merck Index assumes that the metals are just soaking in the acid. This is much different than when a voltage is applied. The voltage maintains this oxide film on the base metals. To prove this to yourself, make up a small amount of the conc. sulfuric with 10% water and run a piece of clean copper in it, at about 6V for, say, 30 minutes. After mixing the sulfuric, let it cool down first. Weigh the copper before and after. I would also suggest first to attach the lead and apply some voltage, before putting the copper into the solution. In other words, go in live. Someone said that this is an art and not a science. I don't believe this at all. An art becomes a science when you can always predict the outcome. In this case, using the strong sulfuric, with a little experience, the outcome is 100% predictable. I never worried about the build up of heat in the solution. Probably, this was due to my using a 50 gal tank. With your 3 gal tank, you probably won't have problems with heat if you use the strong sulfuric. With weak sulfuric, the current is always high and the solution will continue to heat up. With the strong sulfuric, the current goes to zero, when the gold is stripped. This should also give you a clue that the base metals aren't dissolving. I still hate the use of large glass containers, especially when heat is involved. In the early days, we used 5, 7.5, and 10 gallon Pyrex battery jars for aqua regia. Every so often, one would break - all by itself, it seemed at the time. It wasn't a pretty sight. The use of a steel container and making the container the cathode is much, much better. What if you accidentally dropped the steel cathode into the glass container, e.g.? Shatter city, with 3 gallons of sulfuric in your lap. According to this link (about 2/5 down the page), 100 deg F, 88% H2SO4, will attack mild steel at the rate of .03" per year. Certainly not enough to worry about. http://www.resistoflex.com/sulfuric_graphs.htm Forget the Merck Index and do your own experiments in small beaker sized quantities. Collect your own data. The Merck Index and the data in the CRC Chemistry/Physics Handbook are based on pure, simple, isolated systems. Quite often, when the system is more complex, as this one is, the results can be totally different, especially in electrolytic systems. I think you're making this thing a lot more complicated than it really is. Just try the strong sulfuric. No more dissolving of base metals. No more large amounts of base metals sludge. No more cleaning of the solution itself - just use it over and

180 over, as is. And, as a bonus, the amps go to zero when the gold is all stripped - it tells you when it is finished! When the gold sludge gets so high that it creates a partial short between the electrodes (you can tell when - the amps won't go to zero), let it settle, syphon or decant, and remove the gold. The solution is then reused, as is, without any treatment required. If there's a little gold sludge left combined with the solution, don't worry about it. You'll get it next time. The magnetic pins are most likely Kovar - 54% iron, 29% nickel, and 17% cobalt. The nickel and cobalt don't dissolve much in the strong sulfuric. Probably due to the high iron content. The only base metals I've had problems with are the high Ni or Co superalloys - inconel, hastelloy, waspalloy, rene, stellite, etc.

Sulfuric stripper part 15

If the gold is very thick, it can take a while to strip. The only times I've seen silver used under the gold, the gold was very thick. The black solution is a good indication that the gold is stripping. Let the cell work until the amps fall to near zero. Let this, not time, be your guide. A little water can speed things up, considerably, if the sulfuric is quite strong to start with. Do you know the original strength? With 95+% acid, I would suggest trying an addition of about 5% water, by volume. For safety sake, add the acid to the water. After dilution, let it cool.

Sulfuric stripper part 16

As Lou said, cyanide would be the best. We received gold backed silicon wafers by the drum full and tumbled them in cyanide. Unfortunately, you don't have cyanide. The sulfuric cell should strip them quickly and cleanly. I envision making a small steel rack that would allow you to separate them (maybe an inch apart) and run a number of them in a row at one time. They shouldn't need clamping - contact with the rack should suffice. It may need an occasional jiggle. Most likely, you will have to separate them. If you run them in bulk, they will stick together and prevent gold dissolution.

Sulfuric stripper part 17

181 I would try using the standard concentrated sulfuric cell. I've had good luck with H2SO4 stripping gold from aluminum, with no attack on the Al. Probably could strip the Au in seconds. I would guess similar success with Ti.

Sulfuric stripper part 18

Quote: You can also use white elmers glue. Just a small bit dissolved in the sulfuric. Works the same as Glycerin.

No offense intended, but how does glycerin work in this system? What does it do that you can detect? How can you tell that Elmer's glue works the same? Quote: The process works fine with out glycerin.

I agree with this statement. Glycerin isn't in the original patent. Someone, later on, decided to use it and, when the word got out, everyone started using it. To me, using glycerin in the H2SO4 stripper is kind of like buying a gadget to keep tigers away from your door. No tigers come to your door, so it must work. I never have heard a straight answer on what it does, if anything. I ran this system for many years (started in 1970), on a very large professional scale, without glycerin, with zero problems. Would someone tell what is the practical purpose of using it? I'm waiting with baited breath.

Sulfuric stripper part 19

Somewhere, early in the forum, this tumbler idea was discussed in detail. For many years, I used a small (8" dia.) commercial plating barrel in the H2SO4 stripper. They are expensive, however. On a small scale, I can visualize a small perforated, closeable plastic container with a rotisserie rod running down the center. Only the bottom portion of the container would be in the solution. I would fill the container about half full of parts. Anode contact to the rod would be made with a spring contact on a rounded portion of the rod. As it turned, the parts would make contact with the rod. Traditionally, it is assumed that only 1/3 of the parts make contact in a plating

182 barrel, at any given time. It would, therefore, take 3 times longer to strip than it would with a direct contact. There are other ways to do this. Maybe one could use metal danglers to make contact inside a plastic tumbler. If I remember right, in the early discussion, lazersteve had another idea that sounded pretty good. Can't remember what it was. Search.

TELEPHONE SCRAP
Palladium points
I've run a lot of old telephone wire relays that have pure palladium points. They look like they're made with very short lengths of thin wire, with flattened surfaces. Every pure Pd point I've seen looks like this. It sounds like your points are similar. We selectively dissolved the copper with hot concentrated sulfuric acid plus chromic acid and thought that only pure palladium remained. We tried nitric first, both hot and cold, but it always dissolved a little palladium. The first time we sold them, about 100 ounces, the buyer dumped them out on the table to look at them. He saw a small metal staple in the pile and grabbed a magnet to remove it. When he removed the magnet, it picked up a huge clump of points. An unpleasant surprise. We looked through a microscope and discovered that there was a thin magnetic nickel backing on the points, although you couldn't see it with the naked eye. We removed the nickel with hot concentrated HCl. Check them with a magnet. From my experience, I would bet that you dissolved some Pd in the nitric, especially if you totally dissolved all the copper. Due to their relative positions in the electromotive series, copper will tend to dissolve before palladium. However, when the copper is almost gone, the palladium will start dissolving. After all, the standard solvent for palladium is nitric acid. Use stannous chloride to test for palladium in a drop or two of the solution. If palladium is present, it will produce a brown-yellow color. Anytime you have pure solid palladium (or any other pure solid platinum group metal), you should avoid dissolving it, since it will be very, very difficult to get it pure again. Try to select a solvent(s) that will dissolve everything but the palladium.

183

One time, we ran a 50,000 pound (including the plastic relay cases) batch of these telephone wire relays. They ended up being worth about a dollar per pound, since palladium was worth only about $60 per ounce at the time. Today, they would be worth about $6 per pound.

TORCH MELTING
Cleaning gold in the melt
You should be proud of what you've done. It looks better than 998, unless there was any discoloration (usually reddish) on it? The crystal and the pipe look pretty good. Pure gold is hard to photograph. Also, the good crystal and pipe can sometimes be reduced, or obliterated, in a torch melt button, as opposed to a crucible melt. I like to cast my gold instead of making buttons. I also keep the flame off of the bar, after pouring. I would say that, in a torch melt, discoloration (usually reddish) is the most reliable indicator of all. It's either there or it isn't. If it's there, your gold is offpurity. For 999.5, or better, gold, you have to get rid of the metals that are causing the discoloration. Many dilute acids will dissolve the discoloration, but this treatment is only cosmetic. The garbage is still there. Here's the way I do a torch melt: If dirty, I first try to clean the gold, when molten, by alternating very small pinches of niter and borax (preferably anhydrous). I add 2 or 3 beads of niter and watch. You will see the oxides of the metals rise to the top, in the form of a whitish film on the surface of the gold. This is collected to the sides of the melt with a pinch of borax. I don't cover the gold with flux. I use small amounts so that the flux runs off the convex gold meniscus and collects on the side. This small ring of flux also makes it easier to pour the gold and leave the flux behind. If the gold is most likely pure, the surface will will bright, shiny, reflective, and still, with no white stuff forming or collecting. If you can't achieve this, after 4 or 5 chemical applications, you may have to shot and redissolve the gold and rerefine it. This will go faster the second time. However, If the whitish film is getting less and less with each chemical cycle, the chances are good that you can ultimately clean it. Watch carefully and play it by ear. Although it is rare, it is possible to get crystal and a pipe and still get discoloration. Discoloration and 999.5, and better, gold don't seem to co-exist. If, after cooling, there is a fern-like crystal pattern on the surface, the gold is probably contaminated with platinum. This material will have to be re-refined.

184 Also, it doesn't take much Pt to create a dirty grayish look to the gold powder, especially when dry. You'll have a better chance of not re-precipitating Pt in your gold if you use Ferrous Sulfate for your 2nd drop. However, the FeSO4 requires excellent rinsing - see Hoke for the best procedures for using FeSO4. When re-working gold (whether Pt is present, or not), the best books suggest (1) Using a different precipitant when re-working the gold, and, (2) Melting and shotting the gold before re-dissolving. In other words, they don't dissolve the powder until after it is melted.

Removing slag from the bar

Get about a 1/4" steel rod, about 6" long, and lightly tap the slag that's on the gold. I prefer doing this under running water. With practice, it should shatter the slag without marring the gold. The slag powder will rinse off. If the slag is in a hole, you sometimes have to carefully dig it out. If you just use pinches of flux, in the proper order, and learn to pour the gold off without any flux coming along for the ride, you won't have that problem. Practice.

Melting dishes
I totally agree with Harold. Jeweler's Melting Dishes are the absolute best way to go for torch melts. There are 2 types: the less expensive round sided type and the heavier ones with flat sides. The heavier one looks almost exactly like a big cupel. I would suggest using the heavier one and buy (cheap) the handle for it, also. There are 2 types of the heavier ones - get the flat type without the shield about an inch thick by about 3" wide. I once saw a jeweler get 25 oz of pure gold in one of these dishes. I only do 10 ozs at a time. I like to use a small rat-tail file to form a shallow spout on the edge of the dish. I would buy at least one extra dish. Use one for very pure gold and the other for things like karat gold. If you're doing silver, get another one. I like another one for inquarting. And then there's platinum. The less cross-contamination, the better off you'll be. The dishes aren't cheap, but, with care, they'll last for many, many melts. I don't worry much about BB's left in the dishes. I'll get them next time. If you insist on using cupels, don't use bone ash. They have a tendency to fall apart. Try the cheaper Composite cupels, with Portland cement in them, or the Marbor type. However, some of the cupel will likely be stuck to the bottom of the button. I only use cupels in a pinch.

185 A better substitute for a melting dish, than a cupel, is a standard clay assay crucible, which many of you have, I think. I've seen them sold on Ebay as melting crucibles. I use the 30 gram size - maybe, $1.50 to $2 each - maybe more. On the inside, they have a rounded bottom and work well as melting dishes. Lay the crucible on it's side on a hard surface and carefully break off the top section of the crucible with a hammer. You can nibble them down with the hammer, or you may find that pliers work well. End up with the crucible about 1-1/2" to 2" tall jagged edges are OK. Treat it as you would a melting dish. If you want to reuse it, pour the metal into a mold or into shot, instead of letting the button freeze in the crucible. It's hard to get the buttons out without screwing up the crucible.

WASTE DISPOSAL
Waste disposal part 1
In my early years, I used sodium hydroxide (NaOH) a lot, for cleaning up solutions, but stopped when I realized it wasn't buying me anything. The metal hydroxides (MeOH) are very voluminous and took up about as much space as the solution I started with. They retain water (I seem to remember as much as 75%-90%) even though they feel dry. Filtering them is a real challenge. Each metal, as a hydroxide, forms at a specific pH. Starting on the acid side, and adding NaOH, the MeOH's drop out in a definite order, starting at about pH 5.56.0. On paper, it would seem that you could get a clean separation of the various MeOH's, by adjusting the pH. In practice, this is very hard to do, as there is much cross contamination. I have tried this on several occasions, with some of my money making schemes. The EPA tests solids for the presence of heavy metals by very slightly acidifying them to about a pH of 3 or 4 and then by analyzing the solution for the various heavy metals. Metals in metallic form will generally pass the test, since they don't dissolve. The MeOH's won't pass the test since they dissolve at that pH. In other words, MeOH's are toxic heavy metal wastes. Nothing has been gained by separating them from the solution, unless there's not much of them. The iron or aluminum method of removing metals from solution is another story. The metal drops as metal, which usually isn't toxic waste, if you can rinse all of the chemicals out of it. The solution remaining is an iron or aluminum solution which is a very low level waste solution. I think this should be the way to go. Harold and Steve have made excellent posts covering this method which, I have a hard time finding. Maybe, they can outline a step by step.

186 This legal cleaning up of solutions might be the most important topic on this forum. We should all put our heads together. The info on this forum is really getting spread out. One thread might have 5 topics on it. Nobody's fault - it just worked out that way. What would really be neat on this forum would be an index that is upgradeable. Dream on.

Waste disposal part 2

This used to be a common way to get the metals out of the acid and neutralize it at the same time. The problem is that the resulting metal hydroxides or metal carbonates are considered, by the EPA, just as hazardous as the solution was. Also, they are very voluminous. If you have a lot of metals in the solution, the volume of hydroxides or carbonates could equal the solution volume you started with. Nickel hydroxide will feel dry, crumble in your hand, and still contain 75% water. I did invent a filter that compressed the hydroxides pretty well but I still don't use this method. It doesn't gain you anything. I would use aluminum or, maybe, iron to drop the metals, depending on what metals you are dealing with. After filtering and/or pouring off, you THEN neutralize the acid. Look for posts by Harold or Lazersteve on the subject. In this method, you end up with metal powders. If you filter, rinse, and dry them well enough, I can't see how they would be considered hazardous. They're metal. I think Harold wrote about accumulating this metal powder scrap.

Waste disposal part 3

This is true but, if there were any base metals (copper, nickel, etc.) in the original solution, they would precipitate, as hydroxides, when adding the caustic soda (sodium hydroxide). These metal hydroxides are very voluminous and, if you have enough of them, they would occupy as much space as the original solution did. These metal hydroxides are also considered very toxic by government agencies. If any metals are in the solution, you are better off dropping the metals, as metal powder using the aluminum (or, steel) method as covered by Harold somewhere on this forum. Metal is much less toxic than metal hydroxides,

Waste disposal - part 4

187 The standard methods of refining are generally polluting and people spend tons of money in equipment to handle the pollution. I've always felt the best way would be to develop new non-polluting methods. For example, there are companies, especially in California, that are using purely mechanical methods with no chemicals. The recovery technology in Europe is light years ahead of that in the US.

Waste disposal - part 5

There is a misunderstanding that occasionally crops up on the forum about base metals that are dissolved in acids. Many people think that the reason for dropping out these metals, with iron or aluminum, is to recover them so that they can be sold, as is, or after melting. Not so. No one will want to buy the powder and melting the powder is most probably cost prohibitive for most all of you. You'll never get the stuff melted with a torch. So, what is the reason for dropping out the base metals? It is to convert highly toxic heavy metal solutions to much less toxic iron or aluminum solutions. The copper, nickel, etc., solutions are definitely considered by the EPA to be highly hazardous waste. I don't exactly know they classify the Fe and Al solutions, but surely they must be ranked a peg lower. As far as solids are concerned, I know basically how the EPA tests them. They mix up enough acid (and water) to make a solution with a pH of about 4 (I think), add the solid to this solution, and then they analyze this solution for heavy metals. In the 2 photos of copper powder that Steve posted on the link below, the pink copper metal in the 1st photo wouldn't dissolve and would, therefore, be legal, as I understand it. In the 2nd photo, the green copper compound would dissolve in the pH 4 acid solution and, therefore, it would not be legal. http://goldrefiningforum.com/p.....php?t=1066 The old way to make solutions legal to dump was to drop out the base metals with an alkali, such as sodium hydroxide, sodium carbonate, or lime. The base metals start dropping as hydroxides, carbonates, etc., at a pH of 5.5, depending on the metal(s) involved. The problem is that these hydroxides, etc. will redissolve at a pH of 4 and will fail the EPA test. You're just trading one form of hazardous waste for another. Another problem is that these metal hydroxides are very voluminous. I have dropped the metals out of a drum of acid solution and ended up with a drum full of metal hydroxides. I haven't kept up with the EPA rules. When I owned refineries, I always had my own wastes hauled off legally and, every place I have worked for (at least in the

188 last 25 years) either had their wastes hauled or had legal treatment facilities. However, I have had a few garage operations, although not for quite a few years. I have been where you are. I know. Some one here should find, study, and interpret the latest laws and post them under this "Legal Things" category. Legal stuff bores me to tears. I will, however, help work on the technical aspects of how to comply. If we work on it, I'm sure we can come up with a cheap way to handle these wastes. The best technology and knowledge for handling wastes comes from the electroplating industry. Their wastes are almost identical to ours. At one time, this industry was notorious for dumping toxic wastes illegally. When the EPA and OSHA clamped down, they made an example of these people. The plating shops had to comply or, they had to shut down. Probably 80% of them went out of business. Lots of great new waste control technology has resulted. The thing that would bring you people and this forum down is if you all dumped these solutions illegally. This is a taboo subject that no one likes to discuss. It's a big elephant in the room that everyone ignores. If we would openly talk about it, we could come up with viable solutions (no pun intended). Be good citizens. Don't ruin this for everybody else.

Waste disposal part 6

When you neutralize an acid solution that contains heavy metals, you end up with metal hydroxides or metal carbonates. In the EPA's eyes, these solids are still hazardous waste, based on their method used to test them. Also, these are difficult to handle. They are very voluminous and are hard to filter and dry. They can feel dry in your hand and still contain 75% water. I would suggest first, before neutralizing, that you cement the metals, AS METALS, using another metal that is higher on the electromotive scale, such as iron or aluminum. The results would be metal powder and a solution containing Al or Fe. Then, after removing the powders (rinse them well and prevent oxidation), you could neutralize the solution. You end up with Al or Fe carbonates or hydroxides, which are considered much less hazardous. They will, unfortunately, also be difficult to handle.

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