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P/M Processing: A Brief Tutorial on Powder Metallurgy and Particulate Materials

Randall M. German
CAVS Chair Professor Center for Advanced Vehicular Systems

ability to conform to the shape of a container.

Overview of the P/M Process:

Mississippi State University german@cavs.msstate.edu copyright82006 R. M. German three justifications for using powders

Introduction
Definitions: Powder Metallurgy a method
of producing components by pressing or shaping metal powders which may be simultaneously or subsequently heated to create a coherent object. It includes powder fabrication, testing, and handling steps. The common abbreviation is P/M.
linkages

between subfields

Industry Structure - shows who works and participates in the field and attends conferences, further showing the flow of materials and information

Powder Technology deals with powder size and shape, powder fabrication, and treating powders prior to consolidation. Powder Processing deals with the conversion of the powder into an engineered shape especially compaction, sintering, and densification steps. Product Characterization
focuses on ensuring proper performance via testing quality, measuring properties, and characterizing the linkages between performance to the powder and process. industry structure

Particulate Materials - small solid particles have fluid-like properties that allow easy forming, leading to unique products often not available via alternative approaches. It is related to powder metallurgy, but includes a broader range of compositions such as ceramics, composites, cermets, and several high-performance products. Particle - a discrete solid with a size less than 1 mm. Particles come in many sizes and shapes, ranging from the size of a virus to a grain of sand. Many engineering particles range from 0.1 m to 200 m in size, with ceramic particles tending toward the smaller sizes and plastic particles tending toward the larger sizes. For reference, human hair is about 100 m wide. Powder solid particles that
collectively exhibit fluid-like attributes, such as flow and an

Powder Characterization
Concerns include the following:
1) particle size distribution 2) particle agglomeration 3) surface area 4) interparticle friction 5) flow and packing 6) internal structure 7) composition, homogeneity.

Why we use powders:

bedsides food additives, paint pigments, catalysts, and inks, there are three clusters based on production cost benefits in large production volumes (ferrous automotive components), unique microstructures in multiple phase materials (self-lubricating bearings), or fabrication of materials difficult to process by other means (oxide dispersion strengthened refractory metals).

Single best tool is the scanning electron microscope (SEM) it gives

three-dimensional size, shape, packing, and agglomeration information.

example SEM of spherical powder

schematic of sieving

mesh wires per inch (larger mesh number is smaller opening size)

terminal velocity balances forces

Stokes law
D = particle diameter V = steady-state settling velocity DM = solid theoretical density DF = fluid density 0 = fluid viscosity D = [18 V 0 / (g (DM - DF))]1/2

agglomerated, small sponge powder in SEM

Primary concern with particle size is determination of a characteristic size. Powders come in a wide range of sizes, shapes, chemistries spheres to sponges: Particle Size Measurements: Microscopy

requires laminar settling of particles, can add centrifugal force for smaller particles.

example of a woven mesh sieve

example meshes openings 60 mesh = 250 m 100 mesh = 150 m 200 mesh = 75 m 270 mesh = 53 m

Light Scattering measure particles dispersed and passing through laser or light detector; Fraunhofer and Mie scattering are captured in single computerized instrument

subsieve smaller than 325 mesh (below 45 m) minus sieve designates powders that passed through that size (ex. -325 mesh < 45 m) plus sieve designates powders collected on that size (ex. +50 mesh > 300 m) mixed designation for
example -200/+325 indicates powders below 75 m yet larger than 45 m disperse particles streaming through light sources provide angle-intensity data for determining particle size most accurate, largest size range, and highly automated instruments, can measure from 20 nm to over 1 mm in single instrument

measure size of images

Screening (Sieve Analysis) measure weight of powder in each screen interval, historical basis for other techniques, but limited accuracy (" 4 to 8% accuracy) and size range (over 45 m).

Sedimentation measure particles based on settling time or velocity in air or water or viscous fluid

3 Light Blocking the dispersion of particles in fluid and passage of particles through detector region Particle Size Distribution: Cumulative Size Distribution shown here as both the
collective population (or number) of particles and weight (or mass) of particles (left axis is percent) smaller than size (on lower axis) when standard deviations are plotted versus log size

Particle Shape: Quantitative Descriptors * aspect ratio (longest over shortest measures) * surface area to size ratio * curve fits to images Qualitative Descriptors usually words based on standard comparative images

dispersed particles cast shadows proportion to size measure shadow size, assume sphere cast the shadow to calculate the size cumulative particle size distribution

key metrics - D10, D50, and D90 Equivalent Spherical Diameter most frequent basis for particle size
based on assumption that the parameter measured was produced from a sphere; usually from particle volume or projected image area or surface area corresponding particle sizes at 10%, 50%, and 90% on the cumulative particle size distribution

words like sponge, sphere, and various fruits and vegetables such as carrot; note special terms such as flake, fiber, and dendritic (fern leaf shaped) and irregular

example for projected image

example particle shape terms cumulative particle size distribution, showing median at 72 m size corresponding to 50% smaller

mean average not used

much

Surface Area: Permeation Approach relies on gas permeation and Darcys law
gas permeation (FSSS = Fisher subsieve size) widely used for smaller (subsieve) powders in refractory metal and cemented carbide fields; usually surface area is converted to equivalent spherical diameter in m

median central size (half larger and half smaller) used very often (same as D50) mode most common size log-normal distribution most common for powders, the histogram looks like a bell curve when the particle size is on a logarithmic scale (normal curve or bell curve or Gaussian distribution); gives linear equation

solutions based on volume, surface area, projected area; give different results so basis of calculation needs to be specified

test set up for measuring powder surface area from air permeation rate

4 Gas Absorption Approach relies on chilled sample (liquid nitrogen) and exposure to gas (nitrogen) that absorbs on surface
external area of powder, measured by amount of gas that sticks or absorbs (BET technique) and surface area is usually given in units of m2/g

tap density powder density

after prolonged vibration

pycnometer density density of the powder if pressed to voidfree condition flow time the time required for 50 g to pass through a 60 funnel; some small powders are not free flowing angle of repose a measure of
the resistance to particle sliding referenced to horizontal evidence of the angle of repose

tests devices

BET technique changes gas pressure to detect when surface is coated with absorbed gas as a means to determine surface area

Compressibility powder is compressed to measure change from apparent density; two forms, press to standard pressure (say 550 MPa and report pressed density or press to standard density and report required pressure Compression Ratio measure of change in density from apparent to pressed = pressed density divided by apparent density Chemical Tests: Standard Tests same as employed in other fields; emission spectroscopy most common Special Tests loss on ignition determine
how much surface contaminant on the powder via heating in hydrogen and measuring mass change

approximate relation between particle size D50 (m) and specific surface area S (m2/g) and material theoretical density D is S = 6/(D D50) assuming the particles are spheres Interparticle Friction: Powder Packing and Flow used to measure how a powder will respond to processing steps density mass per unit volume
(usually g/cm )
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Hall and Scott testers for apparent density (Hall used for free flowing powders, Scott used for powders that do not flow)

Arnold meter fills bushing with powder and slides the powder over a cavity to simulate die pressing, used to determine apparent density

acid insoluble dissolve angle of repose another

measure of interparticle friction, measured as angle from horizontal for loose or vibrated powder powder in acid and measure residue as basis for estimation of ceramic inclusions

apparent density powder in

the loose or poured state, no vibration

Powder Fabrication
Main Approaches: milling, electrolysis, chemical

5 reduction, atomization of melts. Approach selection depends on material, costs, and desired purity. For alloys atomization is usually best. Milling mechanical attrition of powder
performed using tumbling or falling balls; crushers, impact devices, jaw mill or ball mill; intense milling possible with stirred ball mill (termed mechanically alloying or attritor milling)

Electrolytic production of powder from chemical solution by use of direct current

powder produced by electrolysis, good for copper, gold, silver, and similar metals; but not alloys characteristics of electrolytic powders sponge-dendritic, pure elements, some possible contamination from bath chemistry

cubic molybdenum powder formed by hydrogen reduction of an oxide reaction (compounds such as aluminides, carbides); for example the above tungsten powder is mixed with graphite and heated to produce tungsten carbide (WC) vapor decomposition (iron, nickel); for example iron is reacted with carbon monoxide and then catalyzed to nucleate small iron particles

rotating ball or jar mill for mechanical attritioning of powder

grinding rate relates energy input W to particle size output D; W = g [DF-a DI-a] subscript F = final, I = initial, and a = 1 to 2
characteristics of milled powders angular, brittle, contaminated

electrolytic (dendritic) copper powder

Chemical Reaction the production of powders from precursor chemicals such as oxides or compounds or solutions, examples of the chemical reactions to produce a powder are as follows:
reduction (molybdenum, tungsten, iron, copper); example of tungsten trioxide reduced at 1000C by hydrogen to produce tungsten powder and steam: WO3 + 3H2 6 W + 3H2O this process is applied to many easily reduced metals iron, copper, tungsten, and molybdenum are most common products

agglomerated precipitated iron powder from the carbonyl reduction process carbonyl iron

milled, angular powder

growth rings inside carbonyl iron powder reaction techniques include combustion or solid-state routes; for example solid powders are

attritor milling a stirred ball mill, can deliver mechanically alloyed powder

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heated to a reaction temperature to produce a compound: 3Ni + Al 6 Ni3Al air vertical units for intermediate quality (bronze, aluminum, copper)

close-coupled nozzle gas outlet is directly in contact with melt stream

porous chemically reacted or combusted Ni3Al nickel aluminide powder precipitation techniques (changes in solution chemistry) to nucleate and grow very small powders; widely used for pure elements (cobalt, nickel, gold, silver)

example of satellite particles

schematic of vacuum inert gas atomization for production of small, pure high purity spherical powder characteristics of gas atomized powders ligaments and sphere, some splats, some satellites

water atomization melt stream disintegration using high pressure water jets, good for large volume production of lower melting materials (iron, copper, bronze, tin); scale up to large melting batches (like a steel mill)

chemically precipitated palladium sponge powder

Atomization production of powder by the breakup and then solidification of a stream of molten metal, good for alloys and pure metals that melt up to 1700C gas atomization disruption of the melt stream based on high pressure gas can be air, argon, nitrogen, helium
air-horizontal units for low melting temperatures (zinc, tin, solder) inert gas units for high purity vacuum melted alloys (nickel superalloys)

SEM of gas atomized spheres with splats and ligaments

melt pouring into atomizer nozzle

superheat excess heating over melting range of the alloy to ensure no freezing instability the cause of the melt stream disintegration first into ligaments then into spheres (Rayleigh instability) satellite case where small solid
particles stick to larger particles to create agglomerates schematic of water jets being used to atomize a melt stream characteristics of water atomized powders irregular, larger (100 m common), usually highly

laminar flow ability to sweep

particles away from nozzle to avoid satellite formation

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contaminated by water 3000 ppm of oxygen is typical; often can be reduced after atomization by roasting in hydrogen or carbon monoxide

Specialty Atomization Approaches plasma, vacuum melt explosion, spark erosion, niche technologies

small nanoscale metal powder

Example Metal Powders: showing powder, production route, median size, and shape
factors include chemistry (especially purity), material properties (especially chemical stability and melting temperature), application requirements, and costs

SEM of water atomized iron particle

centrifugal atomization
molten material combined with centrifugal force to throw off droplets that solidify into particles

high temperature plasma spray process for atomization

copper, electrolytic, 40 m, dendritic

SEM of plasma atomized tungsten

spinning cup centrifugal atomizer characteristics of centrifugal atomized powders spherical, larger, often bimodal sizes

Nanoscale Powders are generally smaller than 100 nm (0.1 m in size) formed by vapor condensation, chemical reaction, exploding wires or intense milling routes - characterized by high
levels of agglomeration, high surface area, difficult handling

iron, oxide reduction in hydrogen, 50 m, irregular sponge

SEM of centrifugal atomized powder

niobium, milled, 10 m, angular and irregular

8 example costs
water atomized iron = $1/kg carbonyl nickel = $15/kg gas atomized stainless = $15/kg

Atomization Microstructure usually corresponds to how fast heat is extracted

larger particles favor dendritic and only very rapidly cooled particles give amorphous with rapid cooling

Powder Microstructures
Microstructure: the internal arrangement of phases, pores, and grains as seen in a microscope

microstructure measure most common is grain size or secondary dendrite spacing; cooling at a million degrees per second gives about 1 m spacing

tungsten, oxide reduced by hydrogen, 4 m, angular and agglomerated

Commercial Summary in USA metal powder production is a $3 billion industry, and global value is probably just under $10 billion; usually highest cost is associated with lowest use

example structures seen inside powders microstructure feature used for measuring cooling rate

pore and dendrite structure inside gas atomized powder relative cost of metal powders

possible variants include dendritic slower cooling, large

grains with segregation of chemistry evident in microstructure

example particle size effect on microstructure

grain region of same atomic

alignment as crystal

equiaxed mostly crystalline, but

grains are same size and shape due to rapid cooling

grain size measure, like particle size, of crystal dimensions grain boundary region of disrupted bonding at junction of contacting grains, usually about 5 atoms thick nanoscale grain size is small,
generally below 0.1 m, so high

nanoscale crystals below 0.1

relative consumption of metal powders m, so high disorder in atomic structure

amorphous no crystal
structure, no atomic order

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proportion of the atoms are on grain boundaries

production of amorphous materials relies on freezing in random (liquid like) atomic structure

critical cooling rate depends on alloy; defines heat extraction rate to produce amorphous phase:
pure Ni 10,000,000,000 K/s 62Ni-38Nb 2,000 K/s 40Pd-30Cu-10Ni-20P 0.001 K/s production of amorphous materials by atomization favored by high alloy levels, rapid cooling, high droplet velocities, and small particles

melt extraction for rapid cooling circles represent atoms, with high fraction of atoms at grain boundaries in nanoscale materials

example flakes by melt extraction

amorphous metals glassy

fraction of atoms located on interfaces as grain size becomes very small since grain size influences properties, a small grain size opens new properties amorphous state requires rapid cooling possible via cold substrate, small droplets in gas atomization, or intense mechanical alloying metals; lack crystal structure, usually highly alloyed, produced by rapid cooling, atomization can produce if particle size is small

plot showing amorphous phase formation in gas atomization versus particle size and atomization gas (helium extracts heat faster than argon)

Features for Forming Amorphous Metals

1) high alloys (such as Al-Ni-Mn) 2) atoms of differing atomic sizes (such as Pd at 2.74 nm and B at 1.96 nm) 3) atoms of differing crystal structures (such as face-centered cubic and hexagonal close packed) 4) atoms with differing valences (such as Al at +3 and Li at +1) 5) atoms with differing electronegativities (such as Si at 1.8 and Zr at 1.4) 6) compositions near deep eutectics to suppress normal solidification to low temperatures

solidification time depends on particle size / particle velocity and is often in 0.1 to 0.4 s range; dominated by droplet size (smaller is faster) and rate of heat extraction in atomization (turbulent gas is faster) spheroidization time
depends on particle size and viscosity of melt and is often in the 0.1 s range

particle shape sphere if

spheroidization is faster than solidification such as in gas atomization; ligament at intermediate rates of cooling, and irregular if cooling is rapid

basic concept form

composition from atoms that are not similar so solidification into a crystal requires considerable atomic sorting time; example 54Au-26Pd-19Sb, 41Zr-23Be-13Ti13Cu-10Ni, and 40Pd-40Ni-20P

novel properties in the amorphous alloys strength and hardness corrosion resistance elastic modulus magnetic response wear resistance

amorphous structure where the atoms (circles) have no repetitive pattern but are in random positions

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relative volume fraction in a feedstock (around 60 vol.% solid)

agglomeration process for joining powders into clusters, used to make small particles that feed and flow easily deagglomeration or dispersion the breaking apart
of agglomerated powders to attain discrete particles comparison of strength and elastic modulus, showing special character of amorphous alloys

Dry Mixing - mixing involves shear, diffusion, and convection

fundamental mixing processes diffusion, convection, and shear

dusting tendency of powder to

spill fines during discharge or flow

example of Hall-Petch effect for steel (strength depends on

inverse square root of grain size): 30 m gives strength of 290 MPa 5 m gives strength of 430 MPa 1 m gives strength of 700 MPa

saturation all of the pores are

filled with liquid

aggregate a hard cluster of particles that is not easily dispersed or broken into discrete particles packing the use of mixtures or blends of powders to improve apparent density, bimodal compositions lubricant polymer mixed with a powder to minimize tool wear in the forming step (common examples are zinc stearate, stearic acid, and lithium stearate) binder polymer mixed with a powder to provide strength and transport such as in extrusion (common examples are paraffin wax, polyethylene, or mixtures of various oils and polymers) Justifications: several reasons for mixing and blending:
eliminate inhomgeneities offset separation during shipping add lubricant or binder minimized dusting form new alloys or composites to remove lot-lot variations mixture homogeneity is measured by the uniformity of the ingredients throughout the powder lot

Tailoring Powders
Activities: these occur after powder fabrication targeted to matching powder to production process attributes, but care is required to avoid hazards, explosions, worker health issues, or fires Definitions: pyrophoric a powder that
tends to burn in air

double cone mixer for batch dry blending and mixing powders

mixing combination of powders

of different chemistries (such as iron, copper, and graphite are mixed to give a sintered steel)

Mixing Rate end of mixing when segregation and mixing reach balance rate of mixing equals rate of segregation
mixing rate measured by the mixture homogeneity (standard deviation in composition over repeated small samples): M = Mo + exp(K t + C) where M is the homogeneity, Mo is the initial mixture homogeneity, t is the mixing time, and K and C

blending combination of
powders of same chemistry, but different sizes, shapes, or production lots

feedstock a mixture ready for shaping or compaction solids loading the

combination of powder as a

Mixing Variants: dry versus wet powder batch versus continuous

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depend on the mixer design, mixer operation, and powder

fluid bed powder in chamber with forces gas lifting the particles against gravity as a polymersolvent spray is added to the moving particles granulation powder, polymer and solvent are tumbled as solvent evaporates to give agglomerates

Wet Mixing: used to form slurries, pastes, and thermoplastic feedstock for injection molding and extrusion Examples: some polymersolvent combinations used for agglomeration:
paraffin wax-heptane cellulose- acetone polyethylene glycol-water

apparent density increases with mixing time, but is degraded by higher lubricant contents

variants include simple mixtures, intentional coatings or surface bonds, and further diffusion bonds

Mixture Density theoretical density of powder-lubricant and powder-power mixtures follows inverse rule of mixtures:
1/DM = X1/D1 + X2/D2

agglomerated spherical particles granulated into a large cluster

spouted bed similar to fluid

bed with particles traveling in a circular path to ensure all particles are equally coated (superior to fluid bed for powders)

DM = theoretical mixture density

X1 = weight fraction of component 1 D1 = theoretical density of component 1 X2 = weight fraction of component 2 D2 = theoretical density of component 2

Agglomeration: intentional bonding of small particles to appear large

spouted bed to coating polymer onto powders such as for agglomeration

examples of mixed, agglomerated, and diffusion bonded powders

Bonding Forces van der Waals (very weak), pendular (drops of liquid at contacts), and funicular (liquid nearly fills voids between particles so pores are spherical)
at saturation (all pores filled with liquid) there is no bonding strength

large agglomerates formed by spray drying

spray drying powder-solventpolymer mixture is sprayed into hot chamber, solvent evaporates, producing large agglomerated balls of small particles

decrease in dusting with polymer coating

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this model says infinite viscosity at the critical solids loading

continuous twin screw mixer

Particle Packing: Types of Packings ordered such as the stacking of bricks and random such as how balls fill a container

pendular bond state with wetting liquid at particle contacts pendular bonds provide agglomerate strength; estimated pendular bonding force F F=3(D change in powder-polymer density with composition

( = liquid-vapor surface energy

D = particle size

critical solids loading corresponds to peak in density in powder-polymer mixtures; same as maximum in mixture viscosity ordered packing of spheres

viscosity resistance to shear;

diffusion bond case; electron micrograph and X-ray element map of diffusion bonded Ni on Fe particle thick paint is hard to stir since the high particle content makes it more viscous

coordination number
number of touching spheres or particles example ordered packings simple cubic, coordination of 6 and density of 0.52 face-centered cubic, coordination of 12 and density 0.74

Wet Mixing: Batch Mixing double cone twin shell double planetary various tumbling containers high intensity blades
plot showing how relative powderbinder mixture viscosity changes with solids content

Random Packing most typical of powder processing dense random corresponds

to the tap density, highest density possible without pressure; for spheres coordination number near 6, packing density near 0.60

loose random corresponds to

apparent density, density on filling a container without pressure or vibration; for spheres coordination number near 7, packing density near 0.74

viscosity versus composition

0M = viscosity of powder-polymer mixture 0B = viscosity of pure binder N = solids loading (vol. %) NC = critical solids loading (vol. %) batch mixer double planetary 0M/0B = (1 - N/NC )-2

Improved Packing to improve packing density fill container with larger powder first

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1) fill holes in packing using smaller powder (with vibration) 2) holes require smaller powder is about 15% size of larger powder 3) optimal ratio is often 70% large and 30% small 4) spheres pack best density of packing is given by density of large powder plus density of small powder times porosity in large powder bimodal packing behavior packing density versus composition packing; example, make one powder conductive and other powder nonconductive, then percolation corresponds to conditions where the mixture is conductive

bimodal two modes in the particle size distribution multimodal multiple sizes, so
particle size distribution will show many peaks bimodal packing at optimal composition

schematic showing difference in percolation (left) and isolation (right) giving differences in conduction

contiguity measure of the

same particle-particle contact area per particle as a percentage of the particle surface area or perimeter

polydisperse broad size range

Optimized Packing the peak bimodal density f*

f* = fL + fS (1 fL) were fL and fS are large and small particle packing densities composition of peak XL* in terms of fraction of large particles XL* = fL / f*

example of particle shape on packing

Furnas Relation first models for optimized packing, relied on wide particle size distributions

packing density of cylinders based on length to diameter ratio example of a high packing density broad particle size distribution

upper drawing is no percolation version, showing no contiguity, while lower version is connected to be percolated

Percolation: Percolation long range connections between particles of the same species in a mixture; particles are in long
contacting strings within the

percolation limit composition where first continuous string forms (how much conductor is added to insulator to cause the insulator to become conductive)