64 Soybean, Blood, and Casein Glues 64 ues 64-1 Wood Glues» Blends 64.2 Blood Glues. 44 Formulation 643. Casein Glues 647 ‘Alan Lambuth Preparation * Formulation Bosse Cascade References. 64-10 64.1 Soybean Glues'-* 64.1.1 Preparation Of all the available agricultural “seed meals,” only soybean meal has ever developed any significant use rial for wood glues. The principal reason is that its protein content, the active constituent for adhesives, is the highest available among commercial seeds and legumes, The protein assay of oil fe soybean meal ranges from about 35 to 55% on a dry basis and averages 44 to 5090 in commercially blended soybean meals and flours. The remaining dry meal content consists of about 30% carbohydrates, 39%6 fiber, and 696 ash, In addition to protein, soybeans contain a very high percentage of triglyceride oil, which is sel in ‘many ways. Asa result ofthis unusually high content of both edible protein and unsaturated oil, soybeans. have been a very important agricultural crop to mankind for about 5000 years. In view of this long history as a foodstuff, the use of soybeans in adhesives for wood is a very recent development, dating only from about 1920, In practice, the oil is removed from coarse-ground soybean meal by high pressure extrusion or solvent extraction. The two products are then sold separately into their respective markets. The extracted soy- bbeans,as meal or flour, are widely used for human nutrition around the world, For these food applications, soybean meal is deliberately heated of “toasted” during processing at temperatures above 160°F to enhance the digestibility of its proteins and carbohydrates. When soybean meal is intended for adhesive uses, the processing temperature is carefully maintained below 160°F, to preserve the alkaline solubility of its protein content. To further prepate it for adhesive applications, oil-free soybean meal is ground to an extremely find flour, mostly through a 325-mesh screen. At this fineness, measurements for process control must be made by a standard test of fine powders for specific surface, calibrated in square centimeters per gram. The normal range of specific surface for “adhesive grade” soybean flous is 3000 0 6000 em'/g 641642 Coatings Technology Handbook, Third Edition TABLE 64.1 Typical High Alkali Formulation for Soybean Glue Component Pass by Weight Water a 60-70°F 15 Adhesve-rade soybean flour 7 Pine ol or diesel ol defoamer y ‘Mix 3 min o until smooth iter a 60-70°F us ‘Mix 2 min or until smooth Fresh hydrated lime (a5 suey ia) 2 Water a 60-70°F 4 Mix min 5085 sodium hydroxide solution “ Mix tm Sodiutn scat slution 2 Mix t min rthophenyt phenol 5 ‘Mix 10 min ‘Normally blended with the soybean four for dust conto 3.9080 Na,0, 28.79% SiO, 41” Baume 64. ‘To become an adhesive for wood or paper, soybean flour must first be wetted with plain water and then reacted with a strong alkali such as sodium hydroxide or trisodium phosphate. (The alkali should not be present during initial wetting, or permanent lumps of dry flour will form.) The chemical action of the alkali on wetted soybean flour particles is to unlold or “disperse” their complex protein structure, ‘making all functional sites available for reaction with wood functional groups. The carbohydrate content of soybean flour becomes similarly dispersed. While this alkaline dispersion step is essential for converting, soybean proteins into useful adhesives, it also starts a slow process by which the same proteins gradually lose viscosity and adhesive efficiency through hydrolytic destruction. As a result, soybean ghies have a definite working life, usually 6 to 8 h at inside temperatures. Fortunately, the acids in wood neutralize most of the dispersing alkali shortly after glue application, so the dry adhesive bonds of soybean glues to wood surfaces are preserved indefinitely. ‘As the strong alkali in soybean glue reacts with wood, it causes a distinctive brown discoloration called alkali stain, This prominent glue line discoloration has limited the use of soybean adhesives in fine furniture and paper products, for example. As a result, soybean adhesives have found their widest application in structural and paint-grade wood products such as plywood, millwork, lush doors, and. prefabricated assemblies. I is possible to prepare nonstaining soybean glues for wood and paper by using ‘much milder alkaline dispersing agents such as calcium or ammonium hydroxide. However, the full adhesive potential of soybean protein is not developed by these moderate alkaline treatments. The resulting glues yield significantly lower bond strengths, adequate for paper and chipboard but not really satisfactory for structural wood joints ‘Typical high and low alkali adhesive formulations are given in Table 64.1 and Table 64.2. The high alkali glue mix was used successfully from about 1930 to 1960 to bond interior-grade soft-wood structural plywood. ‘The addition of hydrated lime and sodium silicate in the high alkali formulation accomplishes two purposes: it helps maintain a level glue viscosity for a longer working life, and it improves the water resistance of the cured adhesive bond by forming water-soluble proteinates, Orthophenyl phenol imparts long-term mold and bacteria resistance to soybean adhesive bonds when glued wood products areintended for use in highly humid locations. It is currently approved by the U.S. government for this purpose. Since the alkaline pH of calcium hydroxide isso moderate ime and soybean flour can also be blended into a single dry package, requiring only the addition of water (in two steps) to prepare the adhesive 2 Wood GluesSoybean, Blood, and Casein Glues 643 ‘TABLE 64.2 Typical Low Alkali Formulation for Soybean Gl ‘Component Parts by Weigh Water a 0-70°F 2s Adhesve-rade soybean flour 7 Pine oi or diesel ol defoamer » Mic until smooth Water a 60-70°F 150 Mic until smooth Fresh hydrated lime (as a suey ia) Py Water at 60-70°F 30 Mic 5 *"Nocmally blended with the soybean Mou for dust contol ‘This formulation has been used extensively as a briquetting binder for charcoal and other powdered. ‘materials and for paper laminating to wood, ‘One of the big advantages of soybean glues over many synthetic resin adhesives is their capability to be cured either hot or cold. Hot curing is accomplished in a conventional steam or oil-heat press at temperatures between 230 and about 270°E, For plywood, a pressure of 175 psi is generally employed. Curing time is about 1.5 min per quarter inch of panel thickness, the higher press temperatures being, used for the thicker panels. On dry wood, the cold curing of soybean gluesis accomplished in an unheated press at about 150 to 175 psi in 15 min, During this clamping cycle the soybean glue film develops a sufficient gel strength by dehydration into dry wood to hold the plies tightly in contact when pressure is removed. Complete adhesive cure develops at room temperature over the next several days, but ‘machining can begin in about 6 h. This widely used and patented procedure was called the Noclamp Process. Ibis unique to soybean-based adhesives and certain low soluble blood glues. 64.1.3 Blends Another unique feature of soybean proteins as adhesivesis their compatibility with other protein adhesive ‘materials to yield “blend glues” of enhanced performance properties. The two most widely used combi nations have been with dried soluble animal blood and with milk casein. In each case, the somewhat granular dispersed consistency of the soybean glue adds useful working and curing properties to those of the two animal-derived proteins. The normal combining limits are between about 20:80 and 80:20 soybean to animal protein, depending on the performance properties desired. Examples of these blended. protein adhesives may be found in Sections 64.2 and 64.3 For applications requiring extremely smooth and fluid soybean glues, mote in the nature of size coatings, soybean proteins are available as extracted and dried powders at somewhat higher cost. Typical uses would be as paper overlay adhesives, boxboard adhesives, water-based paint binders, and paper sizes. Tor structural wood bonding, they are not as cost effective as soybean flour adhesives and they also tend. to flow excessively in wood joints under pressure, Table 64.3 describes atypical paper overlay glue. ‘This glue is extremely smooth and stable. Its formulation illustrates the use of a formaldehyde donor, in this case, hexamethylenetetramine, to partially cross-link the dispersed protein for longer working life and improved water resistance. Other formaldehyde sources and additional compounds have been widely used with soybean glues for these purposes. The additions are always small, about 196, and are usually made at the end of the mix. For sizes and coatings, other moderately alkaline salts are frequently used to disperse fine soybean flour or extracted soybean protein, These include the sodium or potassium carbonates, phosphates, and borates, as well as ammonium hydroxide. The borates offer some advantage with soybean flour, as they also complex the carbohydrate constituents to yield increased viscosity and improved tack. None of these compositions can be considered to be adhesives in the structural wood bonding sense, however. ©2009 Tyr Ar Gap.644 Coatings Technology Handbook, Third Edition TABLE 613 Extracted Soybean Protein ation Component Paste by Weight Water a 75°F 3A Extracted soybean protein 100" Chins cay 100" Powdered sodium site » Pine olor diesel ol defoamer » Mix 15 min ‘5085 Sodium hydroxide soltion 6 Mi 5 Hexamethylnetetvamine i 6 Water a 65-75°F ‘ Mix 64.2 Blood Glues* 64.2.1 Preparation Animal blood has a very long history of use as an adhesive in lime mortars, cements, and wood glues. From the Far East to the Baltic to the early Americas, there have been legends and reports of indepen- dently discovered adhesives applications from blood. In all cases, the raw material was fresh whole blood, which was subject to rapid spoilage. This undoubtedly limited broader historical uses for blood. protein glues. Blood adhesive technology as we know it today began in about 1900 with the development of a commercial method for drying fresh whole blood without causing it to lose water solubility. Onee this had been accomplished, blood proteins could be dried and stored indefinitely for use on demand. The only preparatory step needed was the removal from freshly collected animal blood of the clotting substance fibrin, to make the blood stable for processing ‘The most commonly available dried animal bloods are beef and hog, with a lesser quantity from sheep. On a worldwide basis, their primary uses at this time are as protein-rich feed supplements and edible binders for domestic animal and pet foods. In certain cultures these bloods ate used extensively for human nutrition, Poultry blood, which has a very high lysine content (and too low an intrinsic viscosity for adhesives), is used exclusively as a feed supplement, For most food applications, whole blood is quickly coagulated to total insolubility with dry heat or steam. For adhesive applications, it is very catefully dried in vacuum pan ovens or spray dryers to yield controllable levels of cold water solubility. Dried bloods in the range of 80 to about 93% solubility (marketed as high soluble bloods) dissolve almost completely in cold tap water. On the addition of alkali to the water, they become extremely smooth, livery gels. Dried blood particles in the range of 25 to 40% solubility (low soluble bloods) are really wetted only in cold water. They require the addition of a fairly strong alkali to the water to become completely dissolved and dispersed into useful adhesive form. Theit dispersed consistency is always quite grainy, a characteristic that is particularly useful for certain types of adhesive, described late. Dried bloods in the 40 to 70% solubility range have intermediate dispersed. consistencies, tending toward smoothness asthe solubility level rises, 64.2.2. Formulation ‘The adhesive constituents of dried animal blood indude serum albumin and globulin and also red cell hemoglobin, Collectively, they provide nearly 100% adhesive-functional proteins in dried blood solids. Due to differences in composition and proportions of these proteins inthe blood from various animals, there is wide variation in alkaline dispersed viscosity levels among soluble bloods, hog yielding the lowestSoybean, Blood, and Casein Glues 645 ‘TABLE 644 ‘Typical Commercial Formulation for Blood Glue Component Pars by Weight ‘0% soluble dried animal blood 100 Water a 60-70°F 40 ‘Mix 3 min of until smooth Water a 60-70°F 0-120 ‘Mix nti smooth Ammonium hydroxide, specie gravity 0.90, 6 ‘Mix 3 min Powdered paraformaldehyde (sift in slowly while mixing) 15 ‘Allow to stand 30 ain ‘Mix briely until ue ld and smooth > Variable for viscosity contro and beef the highest. There are also significant viscosity variations within blood samples from a single species due to differences in age, activity, and nutrition. As result, commercial lots of dried blood for adhesive uses are always blended in large quantities to help maintain uniformity of glue performance, In formulating adhesives from soluble animal bloods, the dry powder must be initially wetted and redissolved in plain water. The wetted blood is then subjected to one or more alkaline dispersing steps tounfold the protein molecules and render them fully adhesive. (Ifthe initial water is alkaline, permanent lumps will form.) Unlike the vegetable proteins in legumes such as soybeans, high soluble bloods can be adequately dispersed with moderately alkaline compounds including hydrated lime and ammonia to become useful wood adhesives, Simple dispersions of this kind represented the earliest class of blood- based adhesives discovered and used around the world. Much later it was learned that the addition to simple blood dispersions of chemical crosslinkers such as aldehydes greatly increased their water resis- tance. Glues ofthis type were successfully used during and after World War I to bond aircrat propeller laminations and other structural components. In this form, blood glues represented the most water- resistant wood bonding adhesives available until the advent of phenol-formaldehyde resins about 1932. ‘Table 64.4 gives a commercial example, ‘Ammonium hydroxide yields sufficient dispersion at moderate alkalinity to expose most of the adhe- sivesfunctional polar groups on the protein structure. The paraformaldehyde actually gels the blood. protein briefly, but it thins out again to yield a workable adhesive viscosity. The useful life is about 8 h. ‘This glue delivers adequate bonds when cold pressed, but it provides the most water-resistant bonds if hot pressed to a minimum attained temperature of 160°F. During World War II and for 20 years thereafter, blood protein glues were used extensively in the snufacture of interior and intermediate grades of structural plywood (water-resistant but not water- proof). By ths time it was found that the highly alkaline multistep dispersion techniques employed with. soybean glues yielded excellent consistency and adhesion when applied to dried animal bloods in the lower range of solubility. The resulting glues were used in large quantities to bond structural plywood until about 1960. (See Table 64.5.) ‘Since prior heat treatment of the blood itself has already reacted or “denatured” a significant portion of its protein content toward insolubility, glues ofthis type bond strongly and develop significant water resistance when cured without heat. In addition, the lime and silicate dispersion steps yield protein derivatives, which further insolubilize these blood glues upon cold curing. For optimum bond strength and weather resistance, however, hot pressing to a minimum glue line temperature of 160°F is still recommended. Whether cured hot of cold, blood glues of this type normally meet the published mold, resistance requirements for plywood without the addition of preservatives Another form of blood glue employed extensively from World War II until about 1960 (and again during the petrochemical shortage of the 1970s) involves blends of high soluble blood with “adhesive- grade” soybean flour. In this combination, blood protein provides the water-resistant bonds and rapid hot cure, while the soybean flour provides the desired granular consistency for machine application and. ©2009 Tyr Ar Gap.646 Coatings Technology Handbook, Third Edition ‘TABLE 64.5 ‘Typical Commercial Formulation for High Alkaline Blood Glues Component Parts by Weight Water a 60-707F 00 20% Soluble dried animal blood % 200-Mesh wood four By Diesel il (defoamer) » ‘Mix 3 min o unl smooth Water a 60-70°F 0 ‘Mix? min or uni smooth eesh hydrated lime (a suey ia) 0 Water a 60-70°F 2» ‘Mix min 0% Sodium hydroxide solution i ‘Mix 10 min Sodiutn sicate solution 3s ‘Mix § min * Nonmally dey blended wit the dved blood for easier handling and dust cont. 90% NiO, 287096 SO, 1° Bau. ‘TABLE 64.6 ‘Typical Commercial Formulation of Blood-Soybean “end Glue Component Parts by Weight Water a 60-707F 0) Adhesive grade soybean four e 9% Soluble died animal blood 3 200-Mesh wood flour o> Pine olor diesel ol defoamer > ‘Mix 3 min or uni smooth Water at 60-70°F 260 ‘Mix? min or uni smooth eh hydrated lime (as suey ia) * Water a 60-70°F 6 ‘Mix min Sodium slicatesaluton® rn ‘Mix 1 min 5085 sodium hydroxide solution wo Mix $ min rthopheny! phenol 5 ‘Mix § min Notmally blended with the soybean flour and died ‘Mood for dust contra. 189M Na.O, 2.7086 SiO, 4° Baume assembly time tolerance and, in addition, reduced cost. A commercial example of these so-called blend. eles is given in Table 64.6. Unlike straight, low soluble blood adhesives, soybean-blood blend glues must be hot pressed to ensure adequate water resistance and must also contain a preservative. As an alternative to orthophenyl phenol, final additions of alkaline phenol-formaldehyde liquid resins (resoles) have proved effective for imparting, ‘mold resistance to these blend glues. About 15 Ib of a 43% solids phenolic plywood adhesive resin would. serve wel in the formulation of Table 64.6. Up to this point, the adhesives discussed have relied on alkaline dispersed animal or vegetable proteins as the active ingredients. Another type of protein-containing wood glue is commercially significant, namely, alkaline phenol-formaldehyde (PF) resin adhesives fortified with soluble dried blood. In this, ©2009 Tyr Ar Gap.