POWDER METAlLURGY

SCIENcr

Tallie 1.1. Example Applications for Metal Powders. ;lPDlication

abrasives

example uses metal polishing wheels, grinding-media seed coatings. lawn und garden equipment jet engines. heat shields, rocket nozzles valve inserts. bushings. gears, connecting rods colorants, filters, catalysts paint. hard facings, thermal spray barriers asphalt roofing. r.aulking contacts, wire clamps, brazes, connectors heat sinks. inks, microelectronic packages locks. wrenches, cutting tools furnaces. thermocouples. conveyor trays sound adsorption, cutting tools, diamond bonds solders. electrodes, weld filler greases. abrudable seals relays, magnets, cores dies, tools, bearing'. hurdfucing hip implants. amalgams, forceps metal recovery, alloying shielding. filters. reflectors copiers. cams, gears. photocopy process carrier fuses. ammunition, penetrarors vitamins, cosmetics. soaps. ballpoint pens catalysts, drilling bits ' tools, dies. fillers. cements. wear surfaces inks. coatings, laminates explosives. flares, fuel. colorants.

:( 'Chapter One
Introduction to Powder Metallurgy
Frame of Reference
Among the various metalworking techno logics. powder metallurgy is the most diverse manufacturing approach. One attraction of powder metallurgy (P/M) is Ihc ability to fabricatc high quality, complex parts to close tolerances in an economical manner. In essence. P/M takes a metal powderwith specific attributes of size. ~hape_ and packing, then converts it into a strong. precise. high performance shape. Key steps Include tllc . shapingor compaction of the powdcr and the subse uent thermal bondi I of the articles by sintering. e pr cess effectively uses automated operations with low relative energy consumption, high material utilization. and low capital costs. These characteristics make P/M well aligned with current concerns about productivity. energy. and raw materials. Consequently, the field is experiencing growth and replacing traditional rnetalforming operations. Further. powder metallurgy is a flexible manufacturing process capable of delivering a wide range of new materials. microstructures. and properties. That creates several unique niche applications for P/M such as wear resistant composites. This book provides an introduction to the scientific principles behind powder metallurgy. One primary audience is the student becoming acquainted with P/Mas a processing science. Additionally, the engineer involved in powder metallurgy cap also benefit from this text. Frequently. empirical observations go unexplained and processes remain inefficient because of an inadequate understanding. This book provides a logical presentation of underlying basics without dwelling on the technological specifics covered in detail elsewhere. '. The P/M process relies on a different philosophical approach to component fubrica, . tion than is encountered in traditional metalworking. Specifically. the versatility of P/M gives an expanded latitude to the processing-of-materials: Material chemistry, heat treatment, and microstructure are variable, and the distribution of phasesand microconstituents (including porosity and.reinforcing phases) is controllable. . Theapplications of P/M are quite extensive. 'Several examples will be developed. throughout this text; however, as an introductory illustration of the diversity,consider the u~~ of metal powders in the fabrication of tungsten lamp filaments. dental restorations. od-Iess' beilrings, automotive transmission gears, armor piercing projectiles, electrical Contacts, nuclear power fuel elements. orthopedic implants. business machine parts. high-temperature fi hers, aircraft brake pads. rechargeable batteries. 'Intl jet engine COIll-

;'gril:ulture ;1\:roSp;IC~ automotive chemicals coatings construction electrical electronic

hardware

heat treating industrial joining

lubrication

m..gnctic
manufacturing

medical/dental

rnctullurgical
nuclear

office equipment ordnance personal petrochemical

plastics

printing ~yrotcchnics

ponents. Funhcrruorc. metal powders find uses in such products us puint pigments, primcd circuit boards, enriched [lour, explosives., welding electrodes. rocket fuels, printing inks. brazing compounds. ;!nd catalysts. Table 1.1 provides a collection of some common uses for metal powders in tep]'s of the industries. Although thi; diversity aids growth. it also makes the study of powder metallurgy as a technology difficult. Consequently, this text emphasizes the basic principies without dwelling on the specific applications.

Pefinitions
A few terms must he understood before beginning a discussion of powder metallurgy. First. a powder is defined as a finely divided solid, smaller than 1 mm in its maximum dimension. In most cases, the powders will be metallic, lilt ough in many instances they

POWDER

METALLURGY

SCIENCE

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arc combined with other phases such as ceramics or lymcrs. An important charactcrislie of a powde.r i~ its relatively high surface area to volume ratio. The particles exhibit behavior t~at IS intermediate between that of a 011 and a liq I Powders will flow under gravity to fil~ con~ainers or die cavities. so in t IS sense they behave like liquids. They ar~ com~resslble like.a gas. But the compression of a metal powder is csxcntiilly Irreversible. like the plastic deformation of a metal. Thus. a metal powder is casilv shaped. with the desirable behavior of a solid after processing. . . P?wder metall~rgy. is the study of the processing of metal powders. including the labneutron. charactenzat.,on. and conversion of metal powders rnto useful engineering components. The .processmg sequence involves the application of basic laws of heat. work. and defonnallon to the powder. It is the processing which changes the shape. properties and structure of a powder into a final product. An extended list of definitions relating to powder metallurgy is given in Appendix A. The three main steps in the scheme of powder metallurgy are illustrated in Figure 1.1.

powders

chemistry

'.

Powder Metallurgy Processing

microstructure chemistry packing size shape fabrication
Figure 1.2. A tetrahedron illustrating the interdependence between several aspects 01 P/M. including the alloy chemistry. powder characteristics. processing variables. and linal product performance.

sinter forge hot press

density ductility magnetic

strength conductivity microstructure

Agu~e 1.1. Th~ conceptual flow for powder metallurgy from the powder through the processing to the final product. Example concerns are given foreach of the three main steps.
18

, First is the general area labeled "powder tccluiology" which is concerned with the nature of powders. Emphasis is given to ihc Iabric.uion. classification. characterization. and handling of powders. Secondary concerns arc with the sampling. safety. packu!;ing. and transportation. Examination of a powder for <ize and shape arc common and imponant activiti~s in the field of powder technology. Traditional powder consolidation activities include compaction and sintering. The concerns :It this stage are with the forming and densification of the powders. Finally, the conceptual now turns to an emphasis on the final properties. with concomitant uucruion to product microstructure. Students cannot separate the three activities. Decisions concerning the powder type and its fabrication influence the case ul' compaction and sinicring. Likewise. the type of consolidation sequence applied to a powder will affect the final compact properties and . i: specific property goals require attention to the powder, processing. and chemistry. In Figure 1.2. a tetrahedron is used to represent the interdepeence of the chemistry. pow- " der, processing. and properties. Conceptually. this book follows the flow chart in Figure 1.1. Emphasis is given to describing the effects of the many process variables. including the relations between powder characteristics. ease of consolidation. and final compact propert ies.
1'1

POWDER METAlLlJRC,y

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Brief History
The very early uses of metal powders have been traced to several parts of the world. : \ .: For example. gold powder was fired 0010 jewelry by the Incas. and Egyptian uses of iron powder date back to 3000 Be. Another early example isthe Delhi column in India which dates from about 300 AD. This column is made from approximately 6.5 tons of reduced iron powder. During the 1800's the use of powder metallurgy techniques began in earnest: The need for platinum laboratory apparatus led to the development of chemically precipitated powder and new consolidation routes which avoided high tempe:atures. Such activities occurred in both Russia and England where precipitated powders were hot-worked to overcome the inability to obtain the high temperatures needed for casting platinum. About this same time. coins were fabricated from pressed and sintcrcd copper. silver. and lead powders. The modern era of powder metallurgy is traced to Coolidge who used' tungsten powder to develop a durable lamp filament forEdison. Subsequently. cemented carbides, porous bronze bearings, and copper-grnpbue electrical Contacts were developed in the 1930s. By the 1940s. P/M was involved in the fabrication of new tungsten alloys, ferrous structural alloys, and refractory metals.

The initial interest in powder metallurgy grew from an expanding materials base, forming the common elements like copper and,iron by a new. lower cost t~hnology. Sir.ce the 1940s. several less common materials have been processed fro!" powders. incluJing the refractory metals and their alloys (Nb, W. Mo. Zr. TI. and Re). Additionally. the structural metals have come through a _major growth during the.~e time period. The majority of the structural powder-produced parts ~re.ba5ed on I~~':\.:.... Hcwevcr, several compositions tailored for nuclear, aerospace, eicctn.clli. and magnetl~ .. ' . applications arc processed by P/M techniques, ., .. . . '. .' Equally exciting has been the evolution in applications. The spint 10 DpplylO~ PIM. has undergone a recent change. Initially. powder-based components were selected Simply for .heir low costs. More recently, the basis for selecting D powder metallurgy route has been associated with improved quality, homogeneity. or properties. coupled with,an -: . attractive cost and productivity. The high temperature nickel-balled lIu~ralloys: high specific stiffness aluminum aircraft alloys. and. cOOlroll~d thermal expansron alumlO~m-,. matrix composites offer gnod examples of this evolution. Not only, can they be mad.e, i . with h:ller material economy hy powder approaches. but new and Improved cornponrions arc being developed to take advaruagc of the chemistry an~ microst~cture con~rol. The expansion or P/M prll\:e~sillg into areas requiring high quality materiuls and uruque properties will creat~ even more opportunities in the future.

Edison demonstrated his basic incandescent filament bulb system for lighting in 1879. For the technology to grow he required an inexpensive and durable filament material resistant to repeated heating cycles. His early choice was carbonized natural fiber. These efforts built on earlier work in England that used platinum filaments in evacuated glass containers. But by the late 1800's the efforts to find a durable lamp filament 'had largely focused on carbon filaments with various treatments to increase the optical output. By 1905. Whitney had optimized metallized carbon filaments with outputs of 4 lumens per watt. At this time the investigation turned to the refractory metals. first tantalum and then tungsten. The first tungsten ' lilal~ent was produced from powder mixed with an organic binder that allowed s~apmg by binder-assisted extrusion. The binder.-wns.burned off and the particles smtered to make a fragiie filament. The output was 8 lumens per wall. twice that of. the carbon filaments. In 1910. Coolidge developed ductile tungsten filaments u~mg tungs(en powder and controlled deformation processing. Tungsten allowed a ~Igher operatin~ temperature and gave more light in contrast to the other options. n 1937. the coiled filament was developed andin 1959 halogen W;JSadded to regenerate the coil during operation. Today. I kg of tungsten powder produces 150.000 filaments for 40 W bulbs, each giving approximately 1000 h of life with an outPUt approaching 13 lumens per watt. However. the life of the tungsten filament may be ending: New clcctrodeless lamps that operate at 13.56 MHz using quartz arcs have de . . monstrated efficiencies of 135 lumens per watt.

Reasons for Using Powder Metallurgy

Many auributcs contribute III the succe~s of P/M. Three overlapping categ?ries dom!~, narc '1I1U nrovide an introductory concept lor the use of powder metallurgy. Figure 1.3 1\ a venn d'iag '1111 showing how the upplications for .P/M can be c~tegoriztd. First are the . many applications which rely on the economical production of ~omplex part~. . Components Ior the automotive industry represent good exa~ple!i of this area .and their production is a large rIM activity. Within the area o.f economical parts. ~roductlon come cr nccrns with productivity. tolerances. and aurornauon. Both th~ precls~on and cOlit.nre very anracrive , while with cuxung there are problems associated with .se~regallon, machining. and maimaining final tolerances. Prealloyed powders allow fabflcat.'on bcl~w the melting temperature. Thiv eliminates segregation and other defects associated With

casting. '. if . As Figure 1.3 shows. there arc also unique property or micr~structu~ Just~ Icall~ns Ior using P/M approaches. Some examples include porous metals. OXide d.'spemon strengthened alloys. ccrrncts (ceramic-metal composites). and c~mented carbl~es.9'he inability [0 fabricate these unique microstructures by other techOlque.s has contributed ~ large pan to thegrowth of riM. The final cir~le sho~n on the ~enn.dlagram corresponds to captive applications. These arc the materials which are quue difficult to .process.by other techniques. Ideal examples arc the react~ and refractory metals for which meLl1ng , , is not practical. Another emerging group of materials is amorphous or glassy met~ls. 10 many cases. it is desirable to form a powder and develop low temperature processmg to , .~ avoid the microstructural damage accompanying elevated temperatures. Powder metal-

70

I'OWOLU METAlLU/~(jY

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I UIIGY

Economic cost precision productivity (example: automobile gears)

.. ,
iron and steel aluminum copper

CapUve refractory reactive (example:

Unique alloys microstructures composites (example: stainless steel filters)

nickel tungsten stainless steel tin

Ideal Applications (example: porous tantalum capacitors)

relative production
Agure 1.3. The three main reasons for using powder metallurgy are shown in the form of a VeM diagram. The Intersection of the circles represents anideal area for applying powder metallurgy In the future. Figure 1.4. A comparison of the relative production for some common metal powders. Note the logarithmic scaling and dominant role of iron and steel. fonn microstructures, 4) Economical consolid.uion of specialty alloys. typically composites containing mixed phases; these will often be fabricated by enhanced dCllsificat.ioll processes. 5) Synthesis of nonequilibrium materials such as a~lOrphous. microcrystalline. or metastable alloys. 6) Processing of complex paris with unique ingredients or UIlCOIll, man shapes.

lurgy techniques are attractive since all of the processing can be performed in the solid state. . Usually elements from all three categories exist in most P/M applications. Indeed. the major growth and expansion will most likely come from further combinations of economic, captive, and unique aspects in.forming unique.low-cost. high quality products.

The Future of POWder Metallurgy

The past successes of P/M have come from the economic benefits. evident in nclysis of the volume of powder used for several material systems. A relative comparison of powder production qua~tities is given in Figure 1.4.This normalized plot shows that common e~gineering systems constitute the largest use segment. relying on the lowest cost matenals. More recently, the unique and difficult-to-process materials have contriOO.tedto the .expansion in the tech~ol~gical base. The same attributes are expected to continue merging to form new appltcattons for powder metallurgy. Six areashold .he nece.ssary ingredients for continued growth: I) High volume production of precise. high quality structural.parts from felTOUS alloys. 2) Consolidation of high performance rnateri"als. where full density and reliability are primary concerns. 3) Fabrication ofdifficult-toprocess materials. wbere fully dense high perfonnance alloys can be fabricated with uni22

There are many industrial and consumer materials that arc available <IS powders. They include minerals. cereals. coffee, and metal powders. On a tonnage basis. metal powders are a relatively small activity when compared to common powders such as sand andccrcnl=Tbc worldwide consumption of met~1 po.wders amounts to approximately 109 kg/ye<lr. Industrial minerals .con~umptlon IS times larger. and even coffee. tea. and tobacco consumption tS at least 10 kg/year. Of the metal powders. thc majority are iron r~nd stee.1.As illustrated in Figure 1.4 on logarithmic scaling. those amount to nearly 10 times thc consumption of aluminum powder. which is. approximately twice that of copper powder, which in turn is approximately twice that of nickel powder. and so on .

l?8_.

POWDER METAllURGY SCIENCE

Powder metallurgy is in a prolonged, if not steady. growth phase. The use of metal powders continues to expand and the field is growing faster than other metalworking technologies. Moreover, the need for trained personnel is growing even more rapidly because of the diverse and difficult applications being developed for PIM processing. . The feedback from design engineers indicates that as knowledge about PIM expands there will be 'many more applications. The majority of the current uses relies on economical net-shape processing. The future promises more challenges with the combination of cost savings and factors such as reliability, quality. strength, dimensional control. and unique shaping capabilities. Widespread appreciation of these advantages will provide both economic and technological growth opportunities. Research using metal powders offers hope for even more diverse applications, including rapidly solidified magnetic , alloys. new aircraft alloys. improved metal matrix composites, and ultra-high strength structures involving very small scale microstructures.

wing structures. Contrast the expected powder requirements

(or these two nelda.

1.2. ?owder metallurgy contributes to a range of automcdveeompceeau, Identify one such component and give the chief performance requlrements (check Table and 1.1 Chapter Eleven for ideas).

1.3. Consider the alternatives to powder metallurgy for the tabricalion from tungsten. Why are fusion techniques not applied to Ihis product?
IA. Powder metallurgy was once known as "metal ceramic processing does this name suggest?

of lamp filaments:" :' " with ' '

ceramics."

What similarities

1.5. What are some of the key differences between ceramic and metal powders and how might these differences influence processing? 1.6. One of the challenges of PIM processing is to minimize tooling costs,especially din- , ing product development efforts. The need is to reduce errors in the construction of production tooling to ensure final dimensions and properties meet specifications. What steps might help to minimize pre-production tool costs?
1.7. In spite of a low melting temperature (232C). Identify some possible applications for tin powders. '

Suggested References
K. J. Anderson, "Materials for Incandescent MRS Bulletin, 1990, vol. IS, no. I, pp. 52-53. Lighting: 110 Years for the Light Bulb." Metallurgy, Rowrnan Publishers. edition. and

tin is widely

used as powder. a this defini-

,F. Clark, Advanced Experimental Techniques Littlefield. New York, NY. 1963, pp.I60-163.

in Powder

C. G. Goetzel, Tre~iise On Powder M~fall~i'~~~"f~ur '~~'I~;"es. Interscience New York, NY. 1949. H.H. Hausner and M. K. Mal, Handbook of Powder Chemical Publishing Co., New York, NY, 1982. and J. Y. Wood (eds.), Powder Metallurgy: Metals. London, UK. 1991. London, UK. 1960.
W. D. Jones, fundamental L Jenkins

1.8. Give <I short definition tion in engineering terms.

of powder metallurgy

in lay terms andembellish

Mmllurgy,

second

1.9. Metal powders exhibit fluid-like behavior. Identify a common object or product that relies on this attribute.
1.10. Metal matrix composites. such as aluminum reinforced with silicon carbide whiskers. are a new application area for PIM. Identify and explain some of the concerns . associated with' the fabrication of such materials.

An Overview. The Institute of Edward Amold Publishers.

,.:

Principles of Powder Metallurgy,

~.

,1

E. ~Iar (ed.), fowder Metallyrgy: Applications. Society for Metals. Metals Park. OH, 1983. F. Y. Lenel, fowder Metallyrgy Federation, Princeton, NJ, 1980. K. H. Roll, "History pp. 14-20. of Powder

Advantages, and Limitations, ,

American

Principles and Applications, '

Metal PowderIndustries

vol. 7, ninth edition of Metals Handbook

Metallurgy," Powder Metallurgy. E.Klar (ed.), ASM International Materials Park OH 1984 '" , .

r ~\ .

StUdy' QUestions
"

.,. ,

,,, 1.1. The Uses for met I d th diff a POWers range from the very sophisticated to mundane. Consider e I erent properties sought for aluminum powder for use in rocket fuels andircraft a
24
25

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Chapter
Concepts

!".!~_ _ ,.

Powder Characterization
All powder processing starts with a powder; therefor~; one must understand the nature of powder to understand the process. A particle is defined as the smallest unit of a powder that can not be subdivided. Generally. powder metallurgy deals with particles that arc larger than smoke (0.0 I to 1 urn), but smaller than sand (0.1 to 3 mm). Many metal powders are similar in size 10 the diameter of a human hair (25 to 200 urn). The scanning electron microscope (SEM) is one of the best tools available for observing the discrete characteristics of metal powders. An array of SEM micrographs for several different powders is shown in Figure 2.1. In this series of micrographs. variations in shape from flake to spherical and in particle size from the submicron toI mm illustrate the wide range of possible characteristics. Concerns beyond particle appearance require quantitative data. including the following: I) particle size and distribution. 2) particle shape and its variation with particle size.' 3) surface area. 4) interparticle friction. s) now and packing. 6) the internal particle structure. and 7) composition. homogeneity. and 'Contamination . . T~ fully specify the ,nature of a powder it is also necessary .to qualitatively describe h?w It was. fabricated. When dealing with powders. not only the properties of both indiThee, partl~les but also the collective (bulk) properties of a powderlot must be studied. ; ~ropertles of a single particle include size. shape. chemistry. microstructure. density. an ~ness. For abulk lot of powder, characterization implies measurement of those Pro~nl~s, and packing, now, and surface attributes. Both quantitative and qualitative d escnpllons are av '1 bl C' .... . d'bed al a e. onsider the particle Image 111 Figure 2.2. The Image can be escn as a rou d db' I value I ~ e ut irregu ar shape. However, such information is of limited of th~ n c~~~.t, dimensioning the particle is quite difficult because of the shape. Some min tpoSSI e size. measurements are shown with the image. Widely differing size detera Ions are POSSIble d dl , difficult epen mg on the Size parameter used and the shape. Shape is a sary to t~ m~asure. Usually a simplifying assumption for the shape is necese Size II1formation to a single parameter.

-I

"

: t,,

r~~:;:;

FIgure 2.1: S<;~e examples of the diverse 6~ a~ Iizes of metal powde'* u seen In the scanning eiectron microscope. These exMIpiea Illustrate. variety of materials, fabrl cation methods, and particle shapes: a) tellurium, milled, acicular, b) Iron alloy, argon atomized. spherical with aggtomerated fines, c) tungsten, gas reduced, polygonal aggrega!es, d) tin. air atomized. rounded and IIgamental, e) Iron alloy, centrifugally atomized.
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,

(COfIt1nuftd)

28

POWDER

MI IN..LURGY SCllNCl :

1'( 'WI '1 I . 11\1,\, 111.'11/\111 IN

possible size measures A ~ projected area S = surface area V = volume I:i = projected height W = projected width M = maximum cord length

equivalent spherical diameters: 0A= (4A/7t)112 0s= (S /7t)112 0v= (6V /7t)1f3

Figure 2.2. The projected image of a rounded but irregular particle. Six possible measures of the particle size are shown. three of which are based on projected dimensions and three of which are based on equivalenl spherical diameters. .

This chapter introduces a hroad spectrum IIr tests as an armamentarium for asscssing a powder. Such characterization of a powder is an important aspect of powder production. research. product. development. process control. and property optimization. As a rule. tests should be applied selectively to measure the critical powder features.

Powder Sampling and Dispersion

Collecting a representative sample of powder tor analysis can be difficult. Consider the scope of the problem. A typical production lot may be several tons in size: a sample of that lot will probably he on the order IIf ;1 k ilogr.un. Many modem analytical insuu- . mcnts require sample sizes or a gram or k". Assuming a spherical shape. the particle population in one gram depends on the ,i/e .md material density (rhcorcucal density). Table 2.1 gives examples or the large number of panicles involved in I g samples or small particle sizes. Only at the laq;e silL" doc the number of particles injust om: grarn fall below the nonnal standards forstati\ticrl siguificance in a measurement. Hence, concern is not with errors introduced by small \al11ple sizes: it is how well the sample represents the entire powder lot. Sampling errors can be avoided using xomc simple rules. Powder samples should be
Table 2.1. Number of Particles Aluminum, Iron, and Tungsten in
Olll\.,'c;

ram .Sarnple of Munosized Powders of

spherical, f) tin, splat quenched, flake, g) stainless steel, water atomized. rounded and Irregular, h) palladium, eIecttoIytIc, sponge, I) nickel. carbonyl decomposition, porous and cubic, D 'Iron-bued metallic glass, CN5hed ribbon, angular plates. k) titanium. sodium reduced and milled, lrreguIar,and I) niobium hydride, milled, angular (photograptu courtesy of P. Hugo, D. KubIah. T. S. WeI, R.iaeecea, and J. Murray). 30

particle diameter. um
0.01 1.0 1000

material (theoretical
AI (2.70) 7.0.1017 7.0.1011 7.0 10~

density glcm ') Fe (7.86)

2.4. 1017

_.
<

vt(19.3) 9.910Ih 9.910'fl 9.9 101

2~~. 10"
2.4 10~

POWDER METALlURGY SCIENCE

~.-.
powders, especially those below lOO..,n, will ~ibit suffICient capillary rorc:cso.lpan-. t raneously agglomerate with water contenu of t~ by. volume (as liule as O.l~ by': weight). The capillary forcf actually increases as the meinure content decreases. Consequently, polar molecules are used u dis~rsant(with smaller powders.. These polar. mo'ecules typically <Irecarbon chains with charged anwn'icor cationic terminal gtoups. scch as hydroxyl (OH). sulfonate (SO)'). sulfate (O~O):). andl1:Jllmonia (NH/). Shear: ' forces are effective in conjunction with the disPersant indeagglomenuing fine powders.. . The shear can be delivered using ultrasonic agitation ~ intensive mixina. The internal energy of a material is temperature' dependent, but ~tially ilis independent of the surface area. However, ,!,he interfacial coeri)' ~CI with the size of a particle. Consider the size scale where ihc i~terflClal enctJ)' eqUJ:ls.thC '.internal energy for a particle. For gold, the interfacial enc:raY is ~ product or the specific surface area times the surface energy .r. At room temperature, the internal r energy of gold is approximately 600 MJ/m and the surface energy is approxi~ ' mately 1.4 11m2. Equation 2.2 can be solved for the' particle size where the internal' and surface energies are equal. giving

taken from a moving stream, not from stagnant lots. A major problem arises if the sampleis taken after shipping or after experiencing other forms of vibration. In such cases, it is important to blend the lot before sampling so that settling effects are minimized. The sample should be taken from maay points. Lowest sampling errors occur through the use of a rotary riffler, which divides a flowing powder into rotating containers. If a static . sampling procedure is necessary, then many small samples taken from random locations avoids bias. No matter what approach istaken, it is necessary to critique the possible sampling errors and their effect on skewing the measurement of powder characteristics. Dividers or thieves that take multiple random samples aid that task.Sample quality is highest when it is a blend of several small specimens taken from a moving powder stream, such asa conveyor belt. Most metal particles are cohesive because of their small sizes. Thus, they are not easily dispersed. Although van der Waals forces are small, adsorbed moisture causes particle agglomeration. (Adsorbed surface films are loosely bound to a surface, in contrast with absorbed films that are chemically attached and are difficult to remove - water forms an adsorbed film on stainless steel, but chromium oxide is an absorbed film.) An agglornerate is defined as a cluster of particles held together by weak forcesthat can be overcome by a stress much below the intrinsic material strength. An example ofan agglomerate is dried mud, which can be crumbled by low stresses. In contrast, an aggregate can not be dispersed easily since it is a cluster of crystals or particles held together by strong bonds. such as cementing agents. The concern here is with dispersion of agglomerated particles. A particle represents both internal energy (that scales with theparticle volume) and surface energy (that scales with the particle surface area). Let Er represent the total energy, V represent the particle volume, and A represent the particle surface area. Then the total energy is a linear sum,

..

~ = 6 r! D.
The solution gives a particle size of 14 nrn, which corresponds to approximately' 150,000 gold atoms. At this size. approximately O.3%.of the atoms I1tC on the particle surface, but the disrupted bonds as~atcd withlhose atoms contribute SO% cf the particle energy. In a nanoscale powder, it is~t1mated that the first five Jay, ers of atoms exhibit disrupted bonding. which corresponds to about'2~ of the atoms for the 14 nm gold particle.

e; = YA

+ ~V

(2.1 1

.:

where is the surface energy (J/m2) and ~ is the internal energy (JIm"). Assuming a sphere, the area will scale with the square of the particle diameter D and the volume will scale with the cube of the diameter. Thus, the energy per unit volume is effectively a measure of the cohesive potential per.particle, expressed as, EIV

Particle Size
.

= ~+ 6 rID

[2.21

~ecause the energy per particle scales inversely with.the size of the particle, the driving ~~ for agglomeration becomes larger as the particle size decreases. That creates a sig: ~cant problem in powder characterization because an agglomerated small powder will s' Improperly assigned a larger particle size than is representative of the actual powder. ince ~any processing attributes depend on particle size, improper characterization can create,dlffiCulties. To characterize a powder for size or other attributes requires that it be prot.perly dispe~, which becomes more difficult as the particle sizedecreases. Surface . ac rve agents can great I' in f1uence power co hesi or di d . . to y esion ispersion. Th th e us, nrst step IS pa~~ove adsorbed moisture or other agents thatcause particle agglomeration. For large . IC es that may be sufficient for dispersion and accurate characterization. Smaller

Particle size is a determination of the dimensions of a particle. The size of a particle. depends on the measurement technique. specific parameter being measured, and particle: shape. Particle size analysis can be achieved by ~y or several instruments which USUAlly do nOI gl~e eq~ivalenl determinations due t~di(ferences in the measured ~fllSlef5;; Most particle Size analyzers use one geometncpararneter and make the assumpllo~ of a, spherical particle shape. The basis for analysis ca{l be any of the obvious geometric: val~: . ues, such as surface area, projected area, maximum dimension, minimum cross-sectionalarea, or volume; Particle size is probably Orlc.p! the n:lost important characteristics to the : er metallurgist. Size data are most use(ul when presented within the context of the irernent basis and the assumed particle shape. e example size parameters are diagrammed in Figure 2.3. For a spherical particle, ~ s the is a single parameter. the diameter. However. as the particle shape becomes more
33.

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1'()wt)~ll MEIN.LUI~u'( ~LI~Nll

I't 1\v11I1,',11!\1.:J\llllilLl\lIUN

singlesize parameter is obvious, Consider a plateor flake-shaped panicle (Figure 2.3b):. at least two parameters are needed to fully describe the size: Diameter and width. As the shape becomes less regular. the number of possible size parameters increases. For the rounded shape in Figure 2.3c. thesize can be described in terms or the projected height (random). maximum Icngth.horizontal width. equivalent spherical volume, diameter of a sphere with an equivalent surface area. and so on. For the irregular shaped particle shown in Figure 2.3d. there is reat difficulty in g defining a single panicle size. Since the size depends on the attribute measured. it is common to find disagreement between the particle size distributions obtained by many different instruments. Usually a spherical particle shape is assumed and the size is given in terms or a single parameter, the diameter. The use'of scanning electron microscopy provides a mechanism for demonstrating how well this assumed shape relates to the actual particle character. It is important to use a particle dimension characteristic of the powder.The particle in Figure 2.2 illustrates the approach. The size may be given in several ways.Equivalent spherical diameters are generated from values such cis the projected cross-sectional area or particle volume. Table 2.2 lists the results of various measurement tech1iques for comparison. The maximum horizontal width W is termed Ferer's diameter.'~ similar parameter is Mvtin's diameter. which is the particle width me~sured on the orizontal ~ bisector. The muimum cord length M and height H are. equally -viable measurements of particle size. For nonspherical powders, these measurements aredependent on the panicle orientation. ' " The equivalent spherical 'diameter can be determined from surface area. volume. projected area or settling rate_measurements. For example. the panicle in Figure 2.2 has a , projected area A. The equivalent spherical projected diameter DAis calculated by setting the projected area equal to the equivalent area of a circle, , A = rtD/14
(2.31

complex, the difficulty in defininga

Table 2.2. Comparison figure 2.2 Measurement

linear measures

of Particle

Size Determinations Value

for the Particle Shown in

projected height projected width maximum cord length

equivalent spherical diameters

IV I'vI

"

1.00 0.72 1.03 0.76

1.45

projected area surface arca ' volume thus. DA =

(4

0.95

At

tu'"
;1

11.41
measured volume \ ', the equivalent spherical volume diameter D, is

Alternatively ..for given as, '

D" = (6 V I

iu'"
Ihcl1, the

11.51
equivalent spherical surface diameter 12.61 such mcasurcmcurs
10

If the external surface area S is measured. D, is simply. D~ =

(5/n)ll.'

It is possible to combine and size.,

form ratios as new coefficients

for shape

\--

~I

(0
~~
W

For a cubic panicle with a size of I um as measured on each edge the projected area A. surface area S. and volume V give the equivalent spherical diameters, A = I 11m x I 11m = I (urn)?
5 = 6 r\ = 6 (um)?

V = 1

urn x

prn x

I urn = I

(urn)!

Thus, the equivalent spherical panicle sizes are calculated as follows: D/o, = (4 A / n)ln == 1.13 urn D~= (5/ n)lf2 = I .38 urn Dv = (6 V / n)lf3 = 1.44 pm c) rounded, Irregular d) Irregular particle size. The number of possi. .r"

a) sphere

b) flake.

Rgure 2.3. Atllllostratlon of the diffICUlty In measuring

Depending on the choice of measurement technique, this equiaxed panicle can give up to a 22% variation in the apparent size. Clearly. an indication of the parameter measured is important to convey accurate size information.

ble size meuurea Increases sa the particle shape becomes more complex. .
34

POWDER

METALlURGY SCIENCE

... ~ -

----:--

.
:,

Measurement Techniques
Microscopy A widely applied technique for particle sizing uses the ability of the eye to rapidly size dispersed particles in a microscope. Many procedures relevant to testing metal p()\~. dcrs are identified in Appendix B. Although microscopy is rcasonubly accurate, thc tcdiurn of sizing statistically significant quantities of particles has led to use of automatic imagc analyzcrs. The image for analysis is ~el~eratcdby optic.al (either rdlectc.d or transmilled light). scanning electron or trans~lssion electron microscopes. The instrument choice depends on the panicle size: however. thelarger depth of field in the SEM is a distinct advantage. especially since it shows surface topography and can provide x.ra~s for compositional analysis. By microscopic counting of diameter. length. height or area. a frequency distribution can be generated. The distribution will record the relative Irequcncy of the selected particle dimension.

.,

Figure 2.4. Agglomerated tungsten powder. showing a common' difficulty"In separatlno. .. particles for size analysis by microscopy techniques: a) is a scanning electron micrograph" . and b) is a transmission electron micrograph 01 the same powder.' .

A wetting liquid causes agglomeration of small panicles because of the strong capillary force at the panicle contact. For example. the capillary force between a panicle and a flat substrate depends on the wetting angle and quantity of liquid. but approximately equals. .

F" = 5 Dy where F" is the capillary force.' D is the panicle diameter (assumed spherical). and y is the surface energy of the liquid. Consider the panicle size where that force will equal the gravitational force on the particle. The panicle would adhere to the top of a container. The gravitational force on a panicle is given as the mass times acceleration:
F = re DJ ~ P 16
.1:. III

where g is the gravitational acceleration. D is the particle diameter. and P", is the particle density. Combining the above two equations and solving for the particle size gives the critical condition where the capillary force equals thegravitational force.
D = [30 yl (re g Pm)JII1

guish the actual particle size and shape. One technique (or dhpersing II microscopic sam-, pie is to mix the powderwith a 40% naphthalene and 69% camphor eutectic composition. This mixture melts at 32"C and can be easily mixed with powder (or dispersion onII mounting slide. Subsequently. the eutectic is removed by vacuum sublimation. leaving the panicles dispersed for observation. . Intelligent discrimination between single and multiple panicles is a common problem in particle size analysis. Counting two or more small panicles as II large panicle will, skew the distribution toward the coarse sizes. This. is significan: since processing response and final properties arc sensitive topanicle size. Improper size measurements will give false indicuticns. There are problems with measurements dependent on pOlnfde orientation. Generally it is preferable to rely on parameters which lire orientation independent. The equivalent spherical projected diameter D~.OlS shown in Figure 2.2. is particularly useful for such measurement. Screening Screening is a common technique forrapidly anulyiing panicle si,le. A square grid of evenly spaced wirescreates a mesh. The mesh size is deterrnined by' the number of wires per unit length, The opening ~ii'.e varies inversely :~ith the mesh size: large mesh sizes" imply ~Illall ~pening sil.e~ and vice v~rsa. Th~ most common convention (o~spe.ci(~ipg mesh size relies .a." .{he number of Wires per inch. For example, 200 mesh implies ~OO wires per inch. or '1'27 urn between wire centers. For thllt mesh. the wires are 52 11min diameter. thus. the remaining opening size is 75 prn, Mesh sizes cannot go to v~ry small opening sizes. Consequently. the screening t~~lique is usually applied on.ly to panicles larger than 38 urn. There arc electroformed meshes available downto 5 urn, but agglomeration and particle adhesion to the mesh generally make the smaller electroformed screens of lillie practical use. The opening sizes for the standard series ofscreens appears in Table 2.3. That screen series has openings nominally spaced at a ratio of the fourth]7

If the fluid is water and the solid has a density of 10 g/cm\' then the surface energy is 0.07 11m2 and the critical panicle diameter is 1850 prn, indicating a large panicle. The calculation demonstrates the difficulty in dispersing metal powders when they have adsorbed moisture films.

Obtaini~g a dispersed sample for image analysis is a major problem. Frequently. agglomeration or coincidence OCcursas shown in Figure 2.4. making it difficult to distin36

I'O\IJ!JER MEIAlLUI~Liy ~(Il Nli.

I'OWl )11:I I \i'I:AlIlIIILI\II0N

Tllble 2.3. Standard Sieve Sizes

mesh size 18 20 25 30 35 40 45 50 60 70 80 opening. 11m
c

mesh size 100 120 140 170 200 .230 270 325 400 450 500 600

opening. 11m 150 125 106 90 75 .03 53 45 38 3? 25 20

1000 850 710 600 500 425

.. 355
.300 Z50 .,211 180

...

root of two (in the ratio 1.19). Screen analysis begins with 11 !>IaCIc screens with decreasing mesh openings. As of illustrated in Figure 2.5. the smallest opening size is at the bottom. The powder is loaded onto the top screen arid -thescreen staclc is agitated for a period of 15 minutes. For panicle size analysis sample size of 100 gis usually sufficient when using 20 em diameter screens. After vibration. the amount of powder in each size interval is weighed and the

interval pcrccnt calcul.ucd I'm each \1/,' 11;1,lillll.1\ fully automatic cycle is possible. The powder passing through a mesh isdesignated by a - sign and that retained on a mesh is designated by a + sign. For example. -100/+200 mesh powder would have passed through a toO mesh screen but nOI a 2nn mesh screen and would be between I SO and 75 pill in size. By convention. powder h<.:lllw.JS um (-325 mesh) is termed subxicve powder. Although screening is the most widely used size analysis technique. il is not without its problems. Screens will have from .Vir, 10 7'/()'pcnni$sible variation in average opening size as a manufacturing tolerance. Further. individual openings can be up to 50% larger than the prescribed mesh size. That creates a softcut point rather than a sharp division. A common problem is overloading. especially with the smaller screen openings. Overloading blocks the mesh openings. thereby inhibiting powder from reaching the limiting screen size. Hence, the size dal;1 arc skewed toward the cOflrser panicle-sizes. The' problem increases with the arnouru of powder per unit screen. area, content of fine particles." and SID'Il\cr screen openings. Another difficulty results. from the differences in screens and techniques. In general. with any powder an R% error can be expected in a screen analysis if the screens and techniques are not fully specified. The difference between results can be. reduced 10 approximately 4%. if the.screens are the same. Differencesas.small as 1.% can be achieved if full control is e.xercised over the analysis. Thus. it is pointless to ascribe better than I % accuracy to a sieve analysis. Defects in screens will allow oversized panicles In pass. Also. too long a screening dural ion may result in the panicles breaking into finer pieces. Too short.a screening duration will give insufficient time for fines to pass all the way through the screen stack. Because of those difficulties. itis important to use standardized lest methodologies. The following test results were obtained using sieve analysis with two sieve sets and 100 g samples from the x.unc powder 101.

InItial . (1009)

f'.:~

final

. ...... ...-

---.-.

......lI~-_
Increasing mesh, decreasing particle size

mesh size +20 -20/+30 -30/+40 -40/+50 -50/+70 -70/+100 -100

set I 0.5. 2.\.2 17,6 26.5

.. t, . . ,

ill1

0.4
16.1

1 X.4' ..

7.5 6.3

24.7 26.2 18.5 7.7 6.4

pan-

*
38

motion

Figure 2.5. Sieve an8.tysis relies on use of a stack of mesh screens of progressively smaller opening sizes (~r mesh numbers) for capture of particles based on the projected cross sectional siz.e . "

Note that the samples may not be totally random. However. here the cumulative particle size distributions (obtained by adding the retained weightsjare very similar except at the -20/+30 and -30/+40 mesh points. That indicates the ossibility p that the 30 mesh screens were significantly differerU!~An appropriate next step would be to inspect both 30 mesh screens for damage (rips oroversize openings) and to repeat the analysis with a calibrated 30 mesh screen,

l?

POWDER

METAllURGY

SCIENCE

Screening is also useful in obtaining sized powders. This procedure is termed classilication and is used to tailor size distributions. In several applications the ability to process a powder is dependent on controlling the particle size. Consequently. screening provides a means for removing specific size, fractions. Sedimentation Particle size analysis by sedimentation is most applicable to the smaller sizes. Particles settling in a fluid (liquid or gas) reach a terminal velocity dependent on both the particle size and the fluid viscosity. On that basis. particle size can be estimated from the settling velocity. Depending on the particle density and shape. sedimentation techniques are nominally applicable to particles in the 0.02 to I00 urn range. The extension of sedimentation to the lower particle sizes depends on the use of centrifugal forces. High fluid viscosities are needed for analysis of larger particle sizes. Particle size analysis by sedimentation uses apredetermined settling height and places a dispersed powder at the top of a tube. Usually the test is performed in a fluid such as water. but air can be used for smaller particles. Measurements of the amount of powder settling at the bottom. of the tube (weight or volume) versus settling time then allow calculation of the particle size distribution. Obviously. the fastest settling particles are the largest while the smallest can take considerable time tosettle. Automatic instrumentation for performing sedimentation analyses use light blocking. x-ray attenuation, weight or settled cake height to determine the size distribution. Centrifugal forces can be added to .accelerate the test for smaller particles. Assuming a spherical particle shape. settling at the terminal velocity in aviscous medium is represented by abalance of forces. The buoyancy and viscous drag forces act to retard particle settling as diagrammed in Figure 2.6. Alternatively. the gravitational force (or the centrifugal force if applicable) acts to cause particle sculing because of the higher panicle density. At the terminal velocity. the forces are balanced. The gravitational settling force equals mass times acceleration.
I

buoyancy force

t
fluid

"

'.'

~ FV
~ vls.cous drag force

kF1=O
,'.

at terminal velocity

FG
gravitational force
'.

FIgm. 2.6. The force balance leading to a constant settling velocity for a spherical partie c1e ill a viscous fluid. nient to work with a known -culing height H while measuring the time {or settling such cases. the particle size can be calculated from the settling time as fellows:
0= {/8 H TJt
I.

In

i: t (PH' - P,J/J":

(2.111

tion. It is suspected

Fc=KP.,1t0<f6

(2.71

where 0 is the particle diameter. K is the acceleration (gravity). and Pm is the particle density, The buoyancy force is determined by the volume of fluiddisplac::d by the panicle. Fn=gPI1tD'<f6 where PI is the density of the fluid. Finally. the viscous drag force FI' is given as.
Fv=.31tOVTJ 12:91 (2.81

nickel powder is to be analyzed {or particle size using sedimentathat the particle size is near 8 urn. If the powder is dispersed in water at the top of a settling column 100 mm high. then what is the expected settling lime? From Stokes law.
V = HIt = g D1 (P - PI) f (/8 TJ)

A spherical

where h is the teml'lnal . vc I'ocuy an d TJIS t h e flUIid vi V n i . For a se dirmentauon expcn-. . VISCOSity. rneru, t e velocity is calculated from the height and time. Combining equations gives.
V

where H = height = 0.1 m g = gravitational constant = 9.8 m/s1 D = particle size = 8. 10-6m P",;: nickel density = R.9.1()l kg/ml PI= water den. ity = 10l kg/rn! 7] = water viscosity = 10l kg/m/s

.'
.

=g0

t; - PI)

f (I (J 7])
IS

12.101 known as Stokes law. It is experimentally

40

for the terminal v I' '. e ocuy, which

This gives the velocity as 2.8. 10" m/s/nnd for a O.i m settling height the corresponding time is about 360 s or 6 min. Tne Reynold number is 2.2. 10') which is within the range assumed {or Stokes law.

most convc-

~I

PO\.VDER METAlliJRGY SCIENCE

1'( )WI '11.'

"'\",'''

III,VAIIC

IN

A~ with all panicle sizing techniques, size analysis by sedimentation is nut without it~ error sources, First, the basic approach is limited to a narrow size range with some flexibility possible through adjustment of the acceleration and fluid viscosity. However. for particles below I pm slow settling and turbulence (thermal gradients) can make it unrcliable. The upplicuiion of centrifugal forces in thcrmalty ivol.ucd cluunbcr-, ha" been uvcd with success in some laboratories. That has allowed extension or sedimentation techniques to panicles a.~ small as 0.01 ~111. Certain particle characteristics can be qui.c troublesome. Intemal porosity in the powder decreases the mass. thereby causing slowc.: particle settling. For irregular panicles. thesize parameter is somewhat difficult to visualize -slnce settling depends on the hydraulic diameter. Furthermore, an irregular shaped panicle may not take a ,tmight trajectory: hence its nonconstant velocity and uncertain path length hinder accurate sizing. Foreknowledge is necessary (appr?x,irrate particle size and panicle density) before setting up such a test. In those cases of an unknown powder. mixed powders of 4iffering densities (for example copper and tungsten), or newly synthesized powders, those parameters may not be known. There are mathematical limits to Stokes law.The derivation assumes that viscosity controls settling. but this breaks down when thc Reynolds number RN increases over approximately 0.2. In term~ of the settling parameters. the Reynolds number is given as. {2.12\ Also. the panicles are assumed to reach terminal velocity rapidly. These factors usualIy limit the technique to particle sizes below approximately 60 prn. For exarnpic, the maximum"'panicle size for aluminum (density 2.7 g/cm.l) settling in air is about _'\5urn, while for tungsten (19.3 g!cm'). settling in air it is about 17 prn, The container walls should not interact with the particles during settling. The particle-panicle in.eruction must be zero: consequently; concentrations should be kept below one volume percent with no agglomeration. Finally. the fluid and powder can not react chemically. so combinations such as iron powder in water are not advised. In spite of these several ditficulties, sedimentation techniques are in use for several powder systems. suchas th~ refractory metals. ' Elutriation applies to sedimentation techniques where the fluid flow is in the opposite direction to gravity. This variation of the sedimentation technique provides a means of generating panicle size distribution information. as well as separating a powder lot into sized fractions. The greater the fluid flow rate. the larger the particle size carried away by the flow. Another variation of the sedimentation technique is air classification. Air classification achieves a separation of powders into selected size fractions using a cyclone or a spiMing disle.(up to 12.000 RPM) and a cross-current air now as shown in Figure 2.7. Tfle centrifugal forte provides a constant panicle velocity, while theair flow achieves . size separation by Stokes law effects. Figure 2.8 sketches how the particle trajectory is aligned intermediate between the fluid flow and drag force vectors. Differences in the deceleration of panicles exiting from the disk are based on the particle diameter and 42

To demonstrate the limiting sizcIor sedimentation analysis in air for tungsten powder is 17 urn. combine Stokes law with the assumed maximum allowed Reynolds number or 0.2. Solving I1clIl1 Stokc-, law and the Reynolds number equations for velocity and then cqu.uinj; the IWI! velocities gives.
f) 11141\

=118RNll-'I(~p

to -r))/" I
III

where D " is the maximum particle size, N,\, is the Reynolds number (assume the lower limit of 0.1). 1) is the fluid viscosity (I,R \O'~ kg/m/s).!: is the gravitational constant (9.8-m/s1). p, is the fluid density (1.2 kg/m'), and POll is the metal density (19.3 I O~ kg/m'). Solving the above equation with these values gives D of'17 prn. If water is selected instead (viscosity or 10'" kg/m/s and density of I03'kg/m"). then the upper particle size increases toapproximately 27 prn.

powder feed rotating disk

air __ . flow

1 ,
f

II I ::::
~ ~
.,,.. . ~~

[[[[

.> ~

ifj

- ...

e..J

1' ....

....

disk

""

:::: ::::

II..
"It

I ~"'" 't fine .

-;--1t ..

~ ~ flow

air

A\
r>.

coarse

dll/fder Figure 2.7. Particle size separation based on air classification of a powder using a rotating disk and constant air flow. The smaller particle sizes are separated from the larger sizes based on the centrifugal terce and air velocity.

powrXR

ME1Al LlJJ.:tiY \ClLNC I

".

"0'

~ ~I~W ~

J:

particle

--Q-~ drag force

ce~~;~~gal

powder feed

. ..
:

.~','
\ ~'

..

"

t~put!rp
~.
"

.. ' . ,',

trajectory

.....~

,':. '

Figure 2.8. The particle trajectory in air classification depends o~ h~w the particle responds to the combination of centrif~Qal an~ visco-us drag forces. which In turn depends on t~e particle size and mass. . . ." ~1 '." . '. mass. Consequently. lighter or smaller particles are deflected by th\! air flow and separated from the larger particles. Control of the disk rotational speed ana air flow velocity. provides the means of altering the particle size separation. Air classifiers are generally applicable to the size range from I to 150 prn, although the actual behavior varies with the inverse square-root of the material density. Light Scattering In streaming techniques for size analysis. particles are dispersed in a moving fluid. Size determination ..is based on a discontinuity in the fluid strearridue to the presence of the particles. With careful instrument calibration, the discontinuity size can be related to particle size. Most devices are highly automated. so particle size analysis by streaming is popular, but expensive. Streaming methods provide a large dynamic ratio; the ratio of the largest to smallest particles that can be measured simultaneously. In modem instruments relying on multiple detectors. the dynamic ratio can be as large as8000. There is. however, a minimum particle size that can be detected. A versatile streaming technique available for analysis of particle size is based on light scattering. Low angle Fraunhofer light scattering using monochromatic (laser) light and dispersed particles is widely used for automatic size analysis. Particle size affects both the intensity and ungular extent of scattering. A fluid stream with dispersed particles is passed in front of a detector system, such as diagrammed in Figure 2.9. The data rclati.tg t~ panicle size are collected using a photodiode detector array. With coherent (laser) h~ht the angle of scattering varies inversely with the particle diameter. asllustrated in i Figure 2.10. The intensity of the scattered signal varies with t~e square of the particle diamete-, Computer analysis of the intensity versus angle data will determine the particle SI2.edistribution. Depending on instrument design, the dynamic ratio can range from 30 ~o 5~. far in excess of most other automatic instruments. Fraunhofer forward scattering IS typically applied to the I to 200 urn size range. The smallest particles should be at leas~ twi~e the wavelength of the laser light for detection. As with other approaches to particle Size analysis, the particle shape is assumed to be spherical. Detecting agglornera. sample cell
,',.

',

Figure 2.9. The principte of particle siie analysis using. forward laser light scattering~'Th~:~: /., powder is dispersed and fed into the sample cell wherescatte,ring takes place, The defec.:;<,. tor system measures the angular'intensity tor subsequent computer calculation 01 !hElper-. . ticle size distribution. . . . . '.:. . .'
.~ .'
')'

incident laser beam

large particle

"Iens
..".,:. -----; .' .,...
_

'detector array

----- -.

-~-:small" particle

--.

------.........

Figure 2.1oj Small particles provide a wider scattering angle than large particles, giving a basis for particle size analysis based on laser light scattering.
*(. '. .

tion is difficult, but can be: mi~imi2.ed by proper dispersion and ultrasonic deagglomeration. The technique is in widespread use because data 'collection is easy: Mie scattering is applicable to particles generally below 3 11m and overlaps with Fraunhofer techniques. Here. the detector is located at 90" with respect to an incident
4~ .

------------,--.:..-_---_._.
44

POWDER ME1N.LURGY SClENCl

,'( )WI)II:,It"I:", II I;I/A/I(IN

light beam. Consequently, both detectors can be incorporated into one instrument to expand the dynamic ratio during. an analysis. Another light scattering technique uses the Doppler frequency shift. associated with moving particles. For huge particles. the sample is dispersed in air' and accelerated through u nozzle into a partial vacuum, initially propelling the panicles at nearly sonic velocities. As the particles slow. two-laser Doppler shift readings are made to extract the time of flight and estimate the particle size.The approach can size panicles between 0,5 .and 200 JIm at count rates of I()~per second. For smaller particles, the thermally induced random motion. known as rownian B motion, provides sufficient velocity for sizing the particles. The Stokes-Einstein equation gives the relation between the particle diameter D and, the translational diffusivity DT as follows: ' 12,13\ where k is Boltzmann's constant, T is the absolute temperature. and 1] is the fluid viscosi,ty. In a size lUUIly~istechnique termed photocorrclationspcctroscopy. laser light is used to detect the Doppler frequency shift of particles in a fluid. Theapproach uses an internal beam splitter for calibration as sketched in Figure 2,1'1. Over the panicle size range from approximatety 0.00510 ~.prn, the reflections from the particles 'give frequency ,hif:s (rom 1000 to I Hz, depending on the inverse of the panicle 'size. TIle,' intensity versus ire.quency information is collected over a period of minutes. The outputis analyzed to deconvolute the particle slze distribution from thesignals. To use that approach one must : know the optical properties of the fluid and panicles, fluid viscosity, and temperature. ... The advantage is it's applicability to verysmall panicles with few assumptions about the inherent particle size distribution.
I

Modern laser light scancring inxtnuncrus combine 'various light sources and detection techniques to give dynamic ratios of 7000 (0.1 to 700 urn) or more. Consider this range in terms of the number or particles, The mass of one spherical panicle at 700 um equals the m;I~' or 3.4 . 10s particles at 0,1 !lm.'ln terms or familiar size scales. a ratio or 7()()() Icngth, to I is the same as i4 ntm out of I km or <} inches out or r mile. The nonual ruler has an accurate dynamic ratio of 300 . that is I nun increments in a total length or JOO nun.

Electrical Zone Sensing The electrical conductivity or ;1 fluid p;I""1g through ;1 small aperture in all iusul.uor provides a method of measuring the number alld size or part ides suspended in the fluid. Conductivity mcasurcmcut is achieved I", 111;lkillgthe fluid conductive and applying ;1 small voltage across the opening. A COIlIIIlOIlechnique for measuring blood cells. it call t he applied to sizing powders, The main katllrl'~ or the d~vicc arc shown in Figure ~,12,

to pump

scatterIng r--+---sampl~ partIcle electrode fluid cell

~ !.----. ~./

. '; '-"-"e.
. ::::0f" ~ aperture

tttt '

.,

.:

electrode

~ ~
photo detector

particle

..............,

partial reflection

'-"-" electrolyte

'-"--'
,

FIgure 2.11. Very ~ particles undergo Brownian motionin a fluId, the velocity c'! the motion provides Infonnatlon on particle size as measured by the Doppler shift of .:I laser

OO~.
46

Figure 2.12. The principle of partictesize analysis using electrical conductivily changes in a small aperture zone due to the streaming 01 particles dispersed in an electrolyte flowing through the insulating aperture.
47

POWL>ER MEiAlLURGY

SCIENCE

lIuld flow

higher dcusity materials xuch ~IS iron and tungsten. For tungsten powder. the technique is limited to particles below 6 urn. Another difficulty is maintaining 11 low powder coneentrtion to avoid coincidence (multiple particles) in the aperture. Experience has shown the instruments are susceptible' to electrical noise and aperiure 'plugging by agglomerates ~. or large particles. Generally. better results are obtained.fer low density materials (such u.~ ceramics and polymers). Light Blocking .; .. Particle size analysis based on light blocking iOimilJir toelectrical conductivity and'. is another variation of streaming analysis, A light beam is' interrupted by a now or dispersed particles a~ shown in Figure 2.14. As a particle passes in front or the window. it .. partially blocks the light reaching the photocell. Assuming a spherical particle shape. the amount of-light blockage is equated to an equivalent circular cross-sectional area. The dynamic ratio for the technique is 45. The lower particle size is determined by the optical resolution. with I urn being typical. Particle dlspersion in the fluid is important to avoid- . inf coincidence. Measurements are similar to those obtained using electrical zone sensing techniques in terms of both problems and Iimitations. XRay Techniques .. . Two x-ray techniques call be applied 10 size analysis of very small particles. .' Diffraction line broadening for crystalline materials. has several causes, including. strain . and small crystal size. The destructive interference from the crystal is not complete at, angles slightly off the Bragg condition. .1

current (expanded scale)

time

current

time

Figure 2.13. An expanded view of the aperture from Figure 2.12. The streaming fluid carries a particle through the aperture. During passage, the particle reduces Ihe current in proportion to its volume and provides a basis for counting and sizing. A narrow aperture in a nonconductive glass tube carries a flow of electrolyte (I % sail water) under a small pressure differential. An electrical current is'maintained between the electrodes inside and outside of the tube. As shown in Figure 2.13. dispersed particles in the electrolyte are carried by the fluid flow into the apertureanq cause a decrease in conductivity. The decrease in the aperture conductivity is proportional to the. particle volume and thereby generates pulses related to particle size.Through calibration procedures a~d selection of the appropriate aperture diameter (about 1.6 times the largest particle Size) the technique can be applied to several size ranges. The dynamic ratio is approximately 30 with a lower particle size capability of 0.5 urn. . . The wide range of applicable particle sizes is an advantage of the technique. Approp~iate aperture selection avoids plugging problems while ensuring goad resolution of the distribution. Particle settling in the outer chamber during analysis causes the data to be .skewed to the finer particle sizes. As an empirical rule, the electrical zone sensing techOlque is only valid when, . . .. D
(p~ .

..
light source

II ~------------II
("

wlndows
.~(j

P,Y'} < 500 .

r , 12.141 time
. J.,

~~:~ D is ih.e particl~ diam~ter in }l~, P., is the theo~etical d~nsity of the.powder in .: .and P,IS the fluid density, also In g/cnr'. The particle settling problem IS acute for

FigL're 2.14. Particle size analysis based on.light blocking, where the Interrupted light beam is used to size and count particles based on their proJected area,

--------~'i>OVmrr. ......--~.,..-.------------.-ll ~ lUI~t', Y \( IL Nt I

.. -

1"'\\,1111.,

'I I"l

1111."\111"

12.1.'i 1 'where ,t is the x-ray wavelength, cI.il is the interplanar spacing. and () is the diffraction angle. The width of the diffraction peak increases as the thickness of the diffracting crys1:11 decreases. The most useflil approach to particle size analysis using x-rays relic: 011 the peak width a! half of the maximum intensity us diugrummed ill Figure 2.15. Peak hro.ulyning ut thai intensity depends. in pUf!;on the number of diffraclillg planes ill the ny~tul. :.;J11e Scherrer formula gives (he crystal size D in terms of the broadening B. diffraction r angle 9. and x-ray wQveleng(h ).~s foJ.lows:'

IIll' hroa!it-lIill!! due 10 I'arlil'k ~i/l', a ,1;11111:11.1 :1 dilll'l'l'l1t with the lest powder. Ily lIsil1!! a slal1d:lld \\'1111;1 uruch lar!!er hroadcning :JI a similar diffraction angle call be measured. hroadening. then the particle size broadcninp /I i~ calculated fl'rem:e 01" the squarc,
III

dillrarti(ll1 p.nrcrn is 111i~l'd rryxta] size Inver I )1111) thl' If B.,. is the 101a1 measured from the total using the dif-

lJ: = B,.-' - H/

12.'171

~
'.

' ~.

..'

,.
..

.D = 0.9 ).J(8 cos(O})

,,' , , ' , "',, , ' " ; I

12,101
.

<,

Jt is easier to measure the crystal size at large diffraction unglcs (high index planes) and with larger incident wavelengths, The wider the diffraction peak. (he smaller the panicle 'size. For accurate size analysis by peak broadening. the effect of strain mus: be subtracted. That can be accomplished' by analyzing for the amount of broadening versus the diffrac, tion angle. Additionally. broadening due to machine sources. beam diverucncc and sum, pie size must be subtracted. Typically. the peak broadening is best applied 10 annealed or briitle materials where strain,'is not aconcern. Milled metal powders will usually exhibit rion-unifpnn strains and CDn ,not be analyzed accurately by x-ray broadening. To .solatc

where B.\ is the IX:ak broadening for the ~lal1dard. Thetechnique is best applied 10 partiFk~ in the 50 lillj size range. Under careful cxpcrimcntul conditions, x-ray peak broadening can be used for panicles up 10 0.2 pill eOO nm) in size. However, the technique gives only a mean crystal (panicle) size with 110 disuiluuion or shape information. Thc second x-ray technique is sm;dl :ll1gk ~catlerill!!, which can determine the size distribution if tilt:' particle share is known. The inl~n;'il)' of x-ruys scattered by a small panicle varies with the particle volume. Small ;l11gh: x-ray scuncring is most useful for particles below $0 run in size. The technique a"lImes the particles to be dispersed without iutcrparticlc interference. The x-ruy illlL'n,ity versus angle is measured within the () to .'. range III estimate either the panicle ~ilL'di~lrihlllioll l1I' the particle sh:'1ie. Comparison ,!Jf Particle Size Analysis Techniques Analysis otpanictc size depends upon ml';I~uring,lilc response of a particle10 some physical icst.vlngcncral. a spherical partirit' ,Ilape is' assumed: difficulties often can be traced directly 10 Ihal assumption. Because (If the differing physical attributes tested hy each technique and the assumption of a~phl'ril'al particle.shape. the various size analysis techniques will yield very different rc-ulr-, Oil '<line powders. Table 2.4 and Figure 2.10 provide comparisons of the several technique available for panicle size analysis and give the approximate size range of upplicabilitv. dynamic ratio. approximate sample size, approximate analysis lime. and basis for the distribution (population or weight). The figure and table generally reflect the best posxihle measurement range obtainable for metal powders. Often . larger panicle size ranges or dynamic ratios are claimed. bUI nOI demonstrutcd with the denser metallic panicles and the courser panicle sizes. With respect 10 relative cost, automated instruments arc expensive. In the simplest sense, an accurate panicle size analysis is possible uxing simple instrumentation and basic physical principles (for example with a watch and water filled graduated cylinder). The selection of a technique depends on several factors including availability and approximate particle size range.

x-ray Intensity

= broadening

Imax

Particle Size Data

dlHraction angle, 29 Figure 2.15. X-Ray peak,broadening Is measured in terms of the width 8 at an intsnsltv one half of the maximum. ' .
"

Once particle size data are collected, concern turns 10 an analysis of the distribution, The distribution is given in terms of a histogram or frequency plot showing the amount of powder in each size increment. On such plots, the m6'de is the peak particle size. Consider the sieving data in Table 2.5, which ~ivc the weight of powder retained on each screen after sieving. The firs: task ill Ihe analysis is 10 convert the data into incremental
'>1

..

so

.' .,: ..
;

POINDER MF.TAlLURGYSOENCr

.. Table 2.4. Comparison technique microscopy optical electron sieving (wet and dry) wire mesh electroform sedimentation gravity centrifugal light scattering Fraunhofer or Particle Size Analysis Approaches size range.
jim

e.,

dynamic ratio

sample size. g
<I <I

relative speed 'S S I

basis"
P

0.1l and up 0.001-400

30 30
20

~ntages by dividing each increment by "ilie: .toti.I.~ple weight. The histogram (or these data is generated b.y plotting the incremental percenta~ venus the screen opening size. Sucha plot ;s given in Figure 2.17 for the- data frdm 'Table 2.5. Notice (or chis plot' the particle size is converted to a log scale. thereby. miXing the increment widths equal. In most instances. metal powders are found to ~xhibit a bell shaped curve (Gausshln or' .. Table 2.5. Example Particle ~ile Dlstrlbutlon mesh size opening Data interval percent cumulative percent

38 and up
5'- 120 0.2 100 0.02-10 1-800 0.1 - 3 0.5 - 200 0.005 - 5 0.4 - 1000 1-600 0.0 I - 0.2 0.00 I - 0.05

20
50 50 <200

100 >5 5
I

w w w
w
P P

~m
212

weight' '. retained. g 0-, . 0'

s
F

70
80 100
120

180
I~O

Mie .
velocity Brownian electrical zone sensing light blocking x-ray broadening small angle

<5
I

30
400 1000

w w
p

125
J06 9{)

I
<I

30
45

5 3 I' S S

140 170 200 230 270

75
63

1.1 3.0' 8.7 13.2 16.5 20.8 18.0

16.9

':'~'
\~

..

53
45

325
400
500

13.6
10.8 0.0

P P or less)

38
25.

0.0 0.9 '. . 2.5, 7.1 10.8 13.5 17.0 14.7 '.1'3.8 11.1 8:8 0.0

0.0 0.9 3.3 10.4 . 21.2 34.7 . 51.7

~,

66.4:

80.2 91.3. , 100.0. -. 100.0

e: ,.

S slow (I hour or more). I intermediate (-1/2 hour). F P = population basis. W = weight basis ___ ----------~xray

= fast (:t/4 hour

total weight = 122.6 g weight percent

Il:=j

0.001 0.01

' 0.11 1

small. angle xray broadening light blocking electrical zone lensing Brownian light scattering velocity ilgh! scattering II1Mle light scattering Fraunhofer light scattering __ -I centrifugal sedimentation r--_-Igravlty sedlmantatlon electrofcrm sieves wire mesH sieves electron. microscopy optical microscopy
1000

20
15 10 5

..
.I

'''-

~modeslze 75to90~m

,..

.
I-

screen analysl1

rh
100 particle 8Ize,~m

1000

10

:i'fO ""'''100

particle size, um Figure 2.16 A co . ful size ranges for each. Ive pot of particle size.anatysls techniques and the nominal use- . . mpara!' I '.

.,..

Figure 2.17. A histogram plot of the screening data from.TabIe 2.5 with the particleSIze axis en a logarithmic basis. The most populous size Is termed the mode, her& ItIs between 75 and 90 urn,
t 53

52

PowoER

METmURGY

SCIENCE

_____

...:.-

.__

_JW_''_" r,. '_ 1

II,W,\,

_'_"_"_/A_'_'I_IN

size intervals),

Finally, the standard deviation a is calculated

from thc arithmetic

mean as

cumulative

percent finer.

follows:

100r----------.~wt~~~
75 50 2S
.0.L--_......c::J1:::.-..L-...l....J -t- . ,

a=

II /IN)!:

n,: \.,. l) ..... I"! :

12.201'

10

1000

Basis lur Plots An analysis determined by micr\l~(lIp) techniques giws the pupulution of p.miclc-, versus their size. However. an analysis taken by sieving techniques provides a weight distribution. It is important to state the hasis for plotting particle size information. Consider the difficulties ill comparing tW(I ~ets of data on differing bases. The weight distrihution is skewed to the coarser particle sizes in comparison to the population based . distribution. The particle size data from Figure 2.1 X have been replotted in Figure 2.19 along with i1i~' population bused distribution for the same powder. The obvious differcncc in placement of the two distr!I)\I~~o'.l~ he seen in comparison of the median sizes c;.~,.l (72 IIIll VcTSUS' -12 um). For any partil'ic Sill'. ';I~suming a spherical shape allows calcula-, tion of the number (If particles 1/ kunwin;; till' weight \I' and thcuretic,tlllletallit:llsity I~",:'

Figure 2.18. The cumulative particle size distribution plot lor the data in Table 2.5. The arrows Indicate the standard deviations lorthe distr;ibution.

1/

(I

\II I (P .. ,

IT

IJ')

12.211

-normal distribution) when plotted on a log size scale. termed log-normal. A cumulaiivc . particle size distribution is generated by adding the interval percentages and plotting the result versus the lower incremental panicle size. An analogous distribution could te gen. crated by plotting the cumulative percent larger than a given size. The raw data trcrtrncnt . is outlined in Table 2.5 while the resulting plot is shown in Figure 2.1 X. The information . given in a screening analysis is with respect to the weight of powder larger than the specific screen sizes. In Figure 2.18. a smooth curve h~s been used to connect the known points. On the smooth cumulative. particle size distribution. the median size corresponds to the 50% value, The mode. particle size corresponds to the most frequent particle size. which ill the highest peak on the histogram distribution. The standard deviation and mean size can both be calculated by usual procedures. The standard deviation sizes (+ or one standard deviation) correspond to the particle sizes at roughly 84% and 16% (more precisely 84.13% and 15.87%). , For histogram data; the ari.lhmet'ic mean size D ",., and the geometric mean size D x'" arc . calculated as follows: . . ,. I~.IX} log (D,..I

where D is tll'e diameter. Direct comparison llf weight ,II1dpopulation based particle size distributions is invalid.

cumulative 100

finer
-1
/

I I

population,'
75
I
I I I I

50

I
I

25
I
I I I I

I I I I I
I

0 10

'"

100 particle size,

IlITI

1000

= (lINlEy/log

(01)

12.191

where D/ is the midpoint size for each interval. y/ is the frequency of occurrence in the size interval. and N is the total number of occurrences (N is the sum of ., v.over all
S4

'" Figure 2.19.A comparison 01 the cumulative particle size distributions as determined 011 the basis of weight (e.g. screening) and population (e.g. microscopy). The population drstribution is,displaced toward the liner particle sizes.
55

POWDER

METALLURGY SCIENCE
. -;.

" IW! JI,.;IIINW

II J.V J\IIOl'f

. Common Distributions It is useful 10 review some of the shapes of panicle size distributions encountered in P/M. TIle typical bell curve' which occurs when 'the interval panicle si,.e data are ploucd on a log basis is shown in Figu'ie2.17. In contrast, the plots in Figure 2.20 show variations including broad and narrow distributions as well as a bimodal distribution (two peaks). Normal powder fabrication practices can not form a single sized powder

(rilonn<iispcrse). The t"ypi\'al pnxluc: is polydispcrsc, ~iih II wide rall~~:uf:Jlartich: lIii'.cs. -. Vr;ry special efforts a(\' lll'l'Ik'd tll achieve amonesizcd powder. rllh~.lluently. II median or mean size and the dispersion in particle srze.arene<i:e$S~:tyinform;lIio!l. The disPeisioq-, is effectively the standard deviation. A common pr3c~ice'in P/Mh iodistillthepart;icle .. si:.e distribution information into three points c!esi~~'icci /)vii D.I!;: and DIU' corres- . pOmling III the pari ides sizes at the 90. SO. ~and' 10 petceru, paints on the cumulative distribution. . ' ".' , , : / , .',' . , ... . ', ::..
.:

frequency GaussIan (log-normal)

cumulative frequency

Log-Normal

SizeDistributions

',' .,

;.

..' '~'.

':.

100
%

Most powders follow the log-normal form in th~ir.nril.ur.&I.unscreened state. A log! ' ' normal size distribution gives a bell curve whendie fr~quen~y is plotted on a linear scale-, . against the log of the panicle size. This distribution !=ant>edeseribedmathematically .by, .' a modified form of the Gaussian probability function,;Let P(x) be the probabilit~ of observing a part iclc size described by .r=!I/(si:r ),~iving " , ' .. ':.' "'.

o~~-....,....:--log size poiydisperse (broad) log size

12.211
when' U is the natural 'Io\!:,rithlll of the mean particle size and CT.. is the standard devia- .. ' ':. . tion of the distribution (on a logarithmic scale).
.'

100
%

12.231 -.
Figure 2.21 gives a xchcm.u ic comparison
al lJa:c:s. The linear scaling shows a skewed

o .... ~--.....,..;...-log size monodlsperse log size

of a panicle size distribution ploued on S/:ver: , particle size distribution while the log seal.:, ' ing gives the expected bell curve. The cumulative particle size distribution Fix) c!n be expressed in tenus of the iutcgr.rl or P(.I'} over the. interval (rom 0 tor,
: Ft.r)=

ill

t: Ptxtdx

\2.241

log size blmodlai '.

'11' ~ "" .~

o '-----'-~---100

log size

;---

OL-~-----log size log slze ~~~~:: ;"~-hA comparison of Ihe common types of particle size distr~butions. showing the I the frequency and cumulative plots.

which i~ uw:III}' given on :, pcrccnrage basis. Consider a plot of standard deviations instead of percentage . Thestandard devlmions correspond to specific percentage points. For example a standard deviation of zero from' . the mean corresponds III the average size. The 'standard deviations and corresponding' cumulative percentage points arc listed in Table 2.6. , '. The log-normal particle size distribution is created by replouing the percentage P91nls ' from a cumulative distribution in terms of deviations. Such a plot is shown in the bottom of FiJure 2.21':' Many powders exhibit straight line behavior on the log-normal plot. Hence, the particle size distribution can be reduced to juS! two parameters. the slope and ,. ir.rcrccpt or slope and mean size. An advantage-in doing such a fit becomes evident when particle size distributions are compared by d(ffering measurement techniques. In Figure 2.22. the particle size dat;, from Table 2.5 have been plotted on a cumulative log-normal basi. The standard deviation points indicated in Figure 2_) 8 have been used to make this plot. giving a straight line for the distribution.

I'OWDl~ M.lllII.tUh'l,n( II NIt

/., '1'.'/./ f'.

""f"\'

"/.'1/'1/1, f1l

standard deviations
percent
I.

cumulative percent
95

frequency plot IIn~ar b)

2r----.--r-"".-rr.-----~
90 80
70

percent

frequency plot log c)

a
-1

60
50

40
30

20
10

cumulative percent

cumulative plot

5 -2 20
50 100

. ,
standard. devlatl~~..

-d)/
"" ' ~~----------~Iog

200

log

particle size, ~ m
Figure 2.22.'-The Ioq-norrnal particle size orstnbution plot of the data from Table 2.5 using the standard deviation points from Figure 2.18. . . that such comparisons (or data transfurm.uionx) are intercept ofa distribution are known. then the other translation. In 'transfonnarions. the slope remains Transformation ~f the data requires culcul.u iun of the Figure 2.23. To convert from a weight distribution relatively simple. If tl~e slope and distribution can be estimated by a constant on a log-normal basis. displacement parameter 8 shown in to a population distribution. the dis- .

log-normal plot

;i,. ,

FJgure 2.21. The particle size distribution shown on four different bases; a) the frequency versus particle size .on a linear scale. 'b) the frequency versus particle size on a log scale, c) the cul'!'lulative frequency versus log particle size. and d) the log-normal distribution showing the standard deviations as a function of the log particle size..
J',' :

standard deviations

Table 2.6. The Percentage Points and Stan~ard Deviations on a Cumulative Siu Distribution deviations percentage

Particle POPUlatiOn//! ,

-2.0

-1.5

-1.9.
-0.5
0.0

2.28 6.68 15.87 31.85

, ,

, ,,

median /' >l

, ,

50.00
69.15 84.13 93.32 97.72

0.5 ..
1.0

1.5
.2.0

, , ,

,/slope=m , ,

/\

s =6.908/m

x=log,o (particle size) "

Figure 2.23. The use of the log-normal particle size distribution to transform from a weight to a population basis. The vertical translation distance 0 depends on the slope of the distributi~n. . .. c'-_H~" -..

Reali the problem of comparing analyses taken from screening and microscopic 'measurements. Screening gives size data on a weight basis while microscopy gi les it on population buis. One of the fundamental attractions of the log-normal distribution is
(a

i_

POWDER

MET,AJ.LUI~GY SCIENCE

placement is upward and the magnitude

1) = 6,908'1 m

is dependent on the slope m 12,251

where D,. is the largest particle size. A similar distribution is the Dinger-Funk tion which uses both th~ smallest size Ds and largest size DL

distribb-.

whcn the panicle size is expressed on a base-l 0 logarithmic scale.I ore, 6.90R equals :I times the loge I O. where e is the basis for the natural logarithm and :I represents the size exponent in Equation 2.21. To convert from a population to a weight distribution. the displacement is negative (downward) with equal magnitude. Once the transformation is completed. determination of the median size is straightforward (zero standard deviations on the new distribution). On the other hand. mathematical detcrmination of the median size is possible. For a weight distribution the median size D., . is given as. 12.261 and then the median population size 0
D
/1111

F(D) = (0" - D") 1(;) 0 ~

")

12.lll

...

'Problems in Particle Size

A'"a'Y~is

is g~'~:~' as

"'I' .

/O'lh+oYm

12.271

where" is the intercept (the standard de'viation corresponding to the I prn panicle size) and 11/ is the slope, The steeper the particle size distribution. the smal!er 1) will be or. alternatively. the closer the median sizes by the two techniques. Other Size Distributions Generally. the log-normal distribution is the most useful when dealing with metal powders. Others arc sometimes applied to panicle size data.One is the Rosiu-Rammler distribution. given as follows:
F(D) = I - exp!-D"ID/)

where F(D) is the cumulative particle size distrib~tion and 0 is a characteristic size correspo~ding to D,l~'the 'panicle size a(::n%' ~;;"ihe di'stributio~.' The exponent 1/ indicates the W.ldth of thc distribution. A plotting basis takes the double logarithmto give a lincir equation. .
log,ofll/!I - F(D))) ;"
1/

log (D) - 1/ 10" (0 )

'U "'II II

12.291

where 1/ is the s'1 ope 0 f t he p If' 0 the left hand Side versus 10gio(D). , ot . . . . . The Andreasen panic I e size diistn 'b'unon has been linked to optimized packing proper. ties and IS sorn e t'imes . use fl' m working with high packing density metul powders. It is . .. , . . u given as follows: '
F(D)=AD"ID"
L

12.301

There arc several problems with particle siz~ ao~ly~is.lt is quit~. difficult to resolve a: '~id.e ran~c of particle sizes simultaneously during an analysis. Almost all deviceshav~;i . lir.iitcd size range they can accurately resolve and .l.anatyze at one time. Often thnt Hmiia., tion results in a realistic dynamic ratio less thap th:e advertised runge. If the particle. size: distribution is broader than that, the methods are noi.accuraie. Additionally. each tech. ' nique has a range of optimal -uirability, For sieves ..it i~ generally above 38 jJm.,Optical.' microscopy is restricted l\l purticlcs aboveupproxlmutely lum. Techniques such a:~scdi-.' mentation arc only applicable l\l anarrow size r.ll}ge :~cause of limltations imPosed'by the fundamental physic. . . The particle shape problem was emphasized earlier in this chapter; more on shaPe analysis follows in the next section. The more irregular the particle shape.rhe more parol" meters necessary to size a particle. Most rncasurement techniques assume a srhcri~oll sl.apc, Accurate description of shape and its variation with size is tedious. It is notewor- '.' tll:' rh,u shape. like size. is a distributed property or" pOwder. . ..:,," , ; In general. the finer particle sizes arc poorly-characterized .by sieving techniques. Tli~. limited ;m;t1ysi~ range coupled with a bias toward weight based dimibutions results'ii\:, disregard for the filler particle sizes. In many instances; the disregard is not \\Iarr~ied. sin~e t~e fil~er particle, Il(l'~':'~ the greater su'rface .~rea and kinetic activity. Ai. a rauo '11 25. It takes 15625 Ill' the smallest particles 10 equal the malls of just one' ontlc':' largest pan icles. . . There arc common problems with automatic size analyzers. The finn is COincidence;" : When more than one particle i~ in the detection zone of IU1 analyzer. they are si~(fas one large particle. Conscqucurly. the particle size distribution becomes artificially skewet1' . toward the coarse particle sizes. To minimize the problem. lower the ccncerurationof powders inthe detector wile. For the streaming devices. that requires dilute conceritrl!~: tions of the powder in the carrier tluid. Secondly. agglomeration causes firie particles to' appear as coarser particles. Dcagglornenuion requires agitation. milling. and chemica) treatments to maintain particle dispersion. Another problem results from the relativCiy . 'fi . <' h IJn SpeCI IC gravity 01. most metal powders. Streaming techniques assume a uniform ~ random dispersion of particles in the feedstock for the detector. The measurements-can' become qi~~d because of preferential settling ofthe coarse particles. To aS5u~e minimum error from sell ling. it is good practice to pass the entire sample through the detector. ;t~ . Many examinations of particle size analyzers have been performed. Under critical assessment. it appears that the particle size distribution can be reproduced with.a 2 percent to 3 percent variation. Figure 2.24 illustrates the cumulative particle size distribution .. of a coarse spherical iron powder. Between instruments it is common to see at least a
>

~i~e:

-----.---------'------(,1)

._-_ .. _-

/01

1\)\V()1 II MllAllUI;C,y

\(11

Nll .

1'( 1\v1 II ,.', '1'\1"\' II 1I11A III IN'

-----------------------------------------~----------------.
cumulative 100 mass percent

r----~----_;:==_=~:;:iiI""'_,

Q.
~

spherical ~angUlar

80

Iron spheres 60 urn

c!) tear
. ~CUblc
~/' :.\t sponge

drop'

or

porous

/'CiCUI,ar

:Jjf~egular
"

;.''''

'e'

~yllndrical ... '~am,ental ~rous

fI.ake

20

-.

'();iPOlygOnal
O~'------~~~~~~~~~----~ 10 100
"

'. rffI:?

particle slze,llm FIgure 2.24. A demonstration of scatter for particle sizes analysis results using Ihe same powder and seven measurements of the size distribution with four laser scattering devices. The powder was nominally a 60 101m spherical iron. Note the variation at thp. 0'0 and 010 particle sizes. ' 10% difference in the median particle size. and many instruments will disagree by 30 percent to SO percent. It is inappropriate to assign high accuracy to panicle size distribu. tions. Figure 2.25. A cotlccuon descriptors. .

V dendritic

~ggregate .: . and the suggested qualitative

of possible

particle shapes

: :Partlcle Shape

Particle shape inf1uence~ packing. flow. and compressibility, provides information on the powder fabrication route, and help~ explain many processing characteristics. Because ,iUs difficult to quantify panicle shape, qualitative descriptors are frequently used to con. vey a sense of the shape. Figure,t.2S gives a collection of particle shapes and shows the .appropriate qualitative descriptors. Particle shape varies with size and manufacturing technique, A panicle size analysis which assumes I constant shape Could potentially have a large error. For many analyses, ~ . .a'simple quantitative shape desc~iptor proves adequate. The most straightforward
62

descriptor is th~ aspect ratio. defined as the maximum particle dimensio~ divided by the minimum particle dimension. For a sphere. the aspect ratio is unity, while for a ligament a value near 3 to 5 is more likely. A flake particle can have an aspect ratio in excess of 10. and in some instances can be as high as 2()(). Generally, microscopy techniques are most appropriate for quantifying shape. Consider the irregular shaped particle diagrammed in Figure 2.26. Various shape parameters result from the projected image. Particle shape can also be expressed by the ratio DjD A' where Do is the diameter or the .outer embracing circle and DAis the equivalent spherical diameter based on the projected area. By far. the microscopy based shape descriptors are the.easiest to understand and arc relatively easy to obtain from projected images. , , A more complex shape parameter can be generated from a profile analysis of a particle. If a radial coordinate system were centered inside a panicle. such as in Figure 2.27, then a plot of the surface profile could be constructed. The plot might look as shown on the right in Figure 2.27. The tracing of the surface position becomes a contour in terms

.
"
,I

POWDER

MET.A.l.LURGYSCtENCE

,....
, ,"
,

""-~---"""

;,

l' ~--- t; Do , "....

.J', '

,\
\ \

I' '/
I

I'

Do DA

= diameter

of "c;wl~r embracing circle

= diameter

of ctrcle with equal projected area

,. , particles. Useful because, it often correiates' with ,various ~;and ~etric chara~te'r~ istics. surface area provides. insight into the. powderbc:ha iordurinl chemical activity. catalysis. friction. adsorption. contamination', P.l'eSS~1 i9d Iintuina. However, the suiface i.ru of a powder lot tells nothing about the dlsttlbut10n In propcrtiea. pqwdcr texture or :n~ernal structure. So, it is combined with. C)thti'paramerers as part or an overall description' of the powder. Two main analysis techniquei ror measuring lurface area an: gas adsorption and s= permeability. ',' '. ' j,
"

'......

_--_ ..

;,'
','

, ,

'

Figure 2.26. The projected Image of an Irregular particle and two forms of measuring the size 11'1 terms of the clrcular diameters.

,.

Gas Adsorpt~ltSurface Area Analysis .. . The gas adsorption approach starts with a clean powder surface achieved through vacuum or inert gas~Jkeout. The clean powder surface Is cxpolCd CO VlI)'inl partial pressures of known a!sl)roing vapors. A measurement Is made or the amounl or IU adsorbed on tho powder surface versus the panial pressure. The mcuUrcmcnl Is often referred to . as the BET specific surface area, after Brunauer, Emmett ancs Teller who developed the' concept in 1938. Under equilibrium. the rate of adsorption equals the rate or evaporation. As illustrated in Figure 2.28. the BET technique measures the qUJl\llty of iU needed CO saturate the powder surface. By assuming each gas molecule occupies a pRelsc area.the surface area of the powder can be calculated from the adsorptlon behavior. Leuinl P equal tbe panial

::':

....

',

.,

~'.
~'.:
;

',.

e
Figure 2.27. A two dimensional particle profile showing one appioach to particle shape ana/yala. The outer particle contour Is used to create a tunctlonal ralation between the radial length R and the angle
.'

e.

: ....

or the lWOcoordinates. Such an approach to conveying particle shape is a specialized al~lve 10 the microscopy techniques. While the qualitative and simple quantitati:ve leclulIques mlly provide too little detail. the profile based techniques have the opposite ~roblem - each particle is fully analyzed for shape such that witha large number of par1I7les there is too much information. Recent efforts have examined the use of fractal dlmen.sions as part of the shape characterization. where the apparent perimeter length of ,a. panicle increases in an inverse relation to the stepsize used to' circuit the particle. A Simple qualitative description coupled with a SEM micrograph is the most efficient particle shape ind' in routine use. . ~x

/.

. <;'
",'!

.;-

unsafurated
Figure 2.28. lIiustration of molecular adsorption ona surface and the usa of a monolayer' coating at saturation to assess the surface area.

Surface Area Analysis

1bc .surface area is in average measure of the external condition of a large number of

I'OWDFR

Mf1A1IIJl~(iY \( " Nt I

I', 1111111'.11'\1'

I' II 1,'1/" II! IN

--.------ ---_.
I

pressure of adsqrbale, f" equal the saturation pressure of adsorbate (which depends Oil the gu and temperature), X equal the amount ofgas adsorbed at a pressure P. X equal the monolayer capacity of the powder (the amount of gas necessary to form a saturated surface coating one atomic layer thick), and C equal a constant relating 10 the adsorption enthalpy. give~ P ,._1- [1+

signal

OUIpUI

time

L-

(C.I)]

12.:\21

X(P,;P]

X.C

P"

valves

Note the linear relation between the term on the left of the equalsign and the par.ial pres sure ratio PIP". The BET equatlon is generally valid for powders in the: pressure range PIP" from O.OS to 0.30. Equation 2.32 can be rewritten in a general form as.

flowmeter
'-bath

thermal stabilizer
...J powder

P IIX (PH' P)/. 8 + A PIP"

where .

ID:\I

X:''' (A + 8}'1

ID41

with A as the slope and 8 as the intercept of the linear Equation 2.:\:\. Finally. the specific surface area is calculated as
S X.N A.'( .M]

Figure 2.29. A schematic drawing 01 a nitrogen BET specific surface area analyzer. A clean powder sample is chilled to a tempera lure where adsorption will occur (liquid nitrogen temperature in this case). The helium and nitrogen flows are adjusted for a specific partial pressure .ratio. The gas sample is exposed to the gas mixture. resulting in a change in gas thermal conductivity as nitrogen is selectively adsorbed. The area 01 the adsorption peak provides a means of measuring the surface area.

12.:\51

,
x[{P 0 IP)-'] 800~-----.------~----~
tantalum powder 600 specific surface 2/g

using M IlS the molecular weight. of adsorbate, An as the average occupational area of an ud~orbule molecule, Nu Avogadro's number, and I<' as the sample weight. A schematlc example or a surface area measurement device is shown in Figure 2.2lJ. A glass holder immersed into a chilling fluid holds the sample. which has a gas inlet controlled for panial pressure. .Oases used for adsorption include nitrogen. krypton. carbon monoxide, carbon dioxide, water, and benzene. The sample temperature is adjusted to the gu condensation temperature through external cooling. Measurement, are made via a detector such lis a thennal conductivity bridge. In most instances. multiple partial pressures are used to extrac't both the slope and intercept for Equation 2.:\4. However. in some instances, single point detenninations are made with theassumption of a zero intercept, That approach is quick but less accurate. An example plot of theadsorption versus panlal pressure 'is shown in Figure 2.30. Those data were taken on a fine tantalum ;Ylw. der using nitrogen. u the ad$orbate. The boiling temperature for liquid nitrogen i~ -196'C where it hu a molecular occupational area of 1.62.\0.19 m!. By immersing l'le powder (in its holder) in liquid nitrogen, adsorption can be induced. The partial pressure of nitrogen in equilibriumwith the powder can be controlled by pressure regulators or gas mix'ing (midn, nitrogen wilh an inert gas such as helium). When the nitrogen isexposed to the cold powder. the amount adsorbed is detennined by the pressure drop,the weight increase of the powder. or the change in the thennal conductivity through the gas. Using

areaec.assrn
400

slope=2143 200 lntercepteso

O~----~------~----~ o O~

Figure 2.30. Example of data for 'the spccitic surface area of a fine irregular tantalum powder (mean size of 4.1 urn). The adsorption data have been plotted according to Equation 2.33. resulting in a specific surface area of 0.399 m2/g.

66

(.7

POWDER" Mr TAl It JI~(iY \( II NCI

the partial pressure and adsorption cept. which . gives X .11'. .

data, a least squarl's analysis gives the slope ;IIHIinterI~

Gas Permeability Surface Area Analysis The pcnncability of a gas:'passing through aporous structure is dependent on (hesurface area. assuming viscous flow of the gas, The Darcy equation for flow in a porous. material gives the tlow rate Q in m,l/s based on the pressur~l~rop M = Pu . PL and the gas viscosity T) as follows:
Q=MK"A/(LT)) 12,361

drop is IIII'aslln.'1I III d,'t\'rlllill,' Ilk' pcnlll.'ahility. llsin~ powder pIIRlllily an,llhcuMi~'al densily. Ihl' specific xurt.u'c area is calculated using Equation 2 .l1(. vCllcrnlly. the techniquc is restricted 10 p,'.rtic.:1l:sill the 0,5 to 50 um range. Often the measured surface otrea is converted into an equivalent spherical surface diameler and expressed in' mlUlllCr Ihis rather than as a surface area. This is commonly reported as lhe subsieve size. Either wuy. it i~ \1111)' approximate measurement 1601 since it docs nol IL~SCSS dead ended sur, an the f;ll'~ connected 'poruxity which contributes the 'BET surface area, However. because u.e permeability measurement isrelatively simple ~n(hhe devices are widely available. ~ the subsievc si~es arc used frequently to detail the properties of fine powders, " ;,'

to

.....

where the sample length Land cross-sectional area A are as shown in Figure 2.3 I, The parameter K" is known as the perrneability.cocfflcienr. The gas velocity exiting from the low pressure side isgiven as.
12.371

Surface Area as a Shape Index , ' The specific surface area is expressed in terms of the area per unit mau (ml/g), Fo;.,. monoxizcd spheres, the area per sphere A and the volume per sphere \I arc:,given as. :

\I = n 1)'/,6

12.401

with V equal to the flow rate per unit area (Q/A). Based on an analysis b), Kozeny and Cannan. the surface area of-the compact is related to the permeability through theporosity e as.
I s= _[ '
E,I
]1/2

Note the area per unit solid volume is 6/D, The weight W of a solid particle is calculated from the particle volume and theoretical metallic density P",
IV = P., V Consequently. .J=o/(DP.,J the area per unit weight (S = A/W) is given as "

12J!l1

12.411

P"'

5K("E)2

with PHI equal tothe theoretical density of the material. In Equat-ion 2.38 the porosity E is the fractional void' space out of the total volume: Surface area measurements based on the permeability of the powder use a subsieve sizer.A preweighed amount of powder isexposed to a known ,f1?W rate and the pressure ..' . . .

12.421, ..

----A

PI,.!)o PL toP

where S i~ the specific surface area, For a polydisperse powder (a powder with a wide' size range). the mean particle size on a population basis provides a first estimate for the di meter in Equations 2.39 through 2.42, Convenient units for size. surface area. and density are 11m.m2/g, and g/cnr'. respectively, When these units arc used. the conversion factors cancel in Equation 2.42. If a different particle shape is assumed'in Equation 2.42. then the relation between particle size and surface area would be different, A general fonn would be as follows:",: ,, S = k.' (D p J
, .' .. .':." ",

= Pu-

PL

.
.

\2,431 ,
,'.. j\":

powder

tube

Figure 2.31. The deterrnt r measuring the flow rat I~a Ion 01 powder surface area by gas permeability is possible by ferential. e a a gas through a packed powder bed at known pressure dita

where kJ is termed a particle shape factor, lr is possible to make a rough determination panicle shape by comparing independent measurements of particle size (on a populatlon ; basis) and specific surface area through theplculated proportionality constantk'. Use" simple shape models to determine the shape 1:onstant for a monosized powder, ' ',
: -.:

of,

68

69

POVJDER METN.LU~GY ~CI(NLI

"OW""." :

1"1'". " III/Allr)N

A shape factor Ie, tllat Iinkri panicle size and specific surface area can be calculated for most geometric shapes. It is influenced by the parameter selected to measure the particle size. Consider a cylinder shaped particle with a length twice the diameter D. Using the diameter as the size parameter measured by screening. thc ~urface area A is given as: '
A

= angle

of

= 2 1t [)1 + Tt D112 = 512 1t D!

tan(a) V.
(1t

repose

and the volume is

[)114)(2 D)

= hlr

= 1[/2

[)1

and the weight is the density times the volume P. V. Thui area S. is

the specific surface

S -, A

I (V P.)

= (512)

1t

D11/(//2)

P,. D'

Tt/

= 51 (D Pi

For screening, the particle will orient to pass through a mesh that is equal to or larger:than the particle diameter. Thus, the average particle size will be measured as the cylinder diameter D and the value of 1:,is 5,0. Aliernatively, If the particle size is obtained by measuring the equivalent spherical volume diameter DV' then,
Tt

"Figure 2.32, Theang:e of repose is a measure of the interparticle friction, It can be deter. mined from the height and radius of a powder pile passed thr?ugh a funnel.
~ " II,

D/ 16 D"

Tt
11 ,1

D' I 2 D Vfunnel " baffles

or Thus. combining equations gives

S

=3

=A

I (V P)

= 5 / (Pm D,.) = 5 3

11 1

I (PD,.)

which gives a Ie, value of 7.21. Half

density cup Scott

Interparticle Friction
Under the general heading or interparticle friction come two main concerns: powder flow and packing. The friction between particles is dominated by the surfacearea, surface roughness, and surface chemistry. As the surface area increases. the amount of friction in a powder mass increases. Consequently, the particles exhibit less efficient flow and packing. Those concerns are important to automatic die filling during powde! compaction, as well as packaging, transportation, blending. and mixing, ' Resistance to now il a main feature of friction. The density or packing properties decrease because of poor now past neighboring particles, Consequently, attention is given to measures of the interparticle friction. Apparent density. or bulk density. of a powder is the density (mus/volume) when the powder is in the loose state without agitation. Tap density il the highest density that can be achieved by vibration or a pcwdcr without the application of extemiJ pressure. 'Theoretical density corresponds to the hand70

Figure 2.33. The basic components of the Hallflowmeter and seen volumeter for mea. suring the flow and packing of powders.

book density for a powder: the density when there is no porosity present. The angle of repose is another friction index, It is the angle a formed by pouring a powder into a pile" as shown in Figure 2.32, where the tangent of a equals the height divided by the radius of the loose powder pile. The angle of repose is also observed by tilting or rotating powder to the angle 'where it naturally flows. Finally, the [low. rate is a measure of the rate a powder will feed under gravity through a small opening. Mos!.small, subsieve powders will not flow due to high interparticle friction. Such powderxarc termed non-free flowing and arc difficult to fonn, Various devices can measure apparent density, Examples of both the Hall flowmeter and the Scott volurnercr are given in Figure 2,:n, The Hall flowmeter is used for the
,

,.
/I

POWDER

METAllURGY

SCIENCE

coarser particles measuring both the flow rateand the apparent density. The Scott device is applied to smaller powders which do not freely flow because of a high interparticle friction, The Arnold meter minimizes powder flow by using a ring containing powder to directly fill a 20 ern? cylindrical volume. That technique best correlates with the filling. of die cavities in powder compaction operations., ' , The flow rate is usually expressed as the time for 50 g of powder to flow through the , Hall flowmeter. Short flow times indicate free flowing powders while long times indicate high interparticle friction. The apparent density and flow times are easily obtained with the Hall flowmeter by combining a precision volume cup with the funnel. he apparent T density is the weight of powder divided by the cup volume. The precision falls betweenI percent and 5 per~ent and .the, ypical apparent density is between 30 percent to 60 pert cent of the theoretical density. ' Another simple test for interparticle friction is the tap density. Powder is vibrated in a cylinder for IOOOto 3000 cycles at284 cycles per minute using '1 3.2 m~ throw from ~n eccentric cam. Usually the initial powder volume is 25 rnl. The occupied volume Will decrease rapidly with initial vibration and eventually reach a plateau value. giving the tap density as the weight divided by the final volume, It is higher than the apparent density, Both the tap and apparent densities can beexpressed as fractions of theoretical density. The pycnometer density is sometimes given to assess the theoretical densityof an unknown powder or the amount of closed-off (internal) porosity. A pressurized gas (usually helium) is used to measure the volume of pores in a powder of known mass. in a sample chamber of known volume V, but unknown powder volume VI" Initially. the chamber is at a pressure PI" As shown in Figure 2.34. there is a calibration chamber with volume V" connected to the sample volume. It is initially evacuated. After the connecting valve is opened. the pressure decreases to Pr Applying the ideal gas law gives.
P, (V - V ) = P, (V - V + V)
J

Thus. as the only unknown. the powder volume can'be calculated.

VI' = VJ'"+ V (I - PIP
:

)./

(2.45)

The powder mass divided hy the volume gives the pycnometer density. Since sealed pores in the particles can not beaccessed by the test gas, the pycnometer density can be lower than the theoretical density. The typical accuracy is 1%. , In most all applications involving powders, high packing densities are desired. Improved packing densities arc possible by adjustment of the particle size.. shape, and size distribution. The higher the packing coordination, the higher the observed powder oensity. The f.o;ordination number is the number of touching neighbors that any p~icle has in a po~tr ensemble. and is synonymous, with the number of nearest neighbors. Small particles will have more interparticle friction, giving a lower number of nearest neighbors. Everything else being equal, the smaller the mean panicle size, the lower the apparent density. For a coarse spherical powder, the packing fraction for loose p~cking' (corresponding to the apparent density) is usually near 60% of theoretical and the tap density is near 64* of theoretical. The cocrdinatlonnumber exhibits a distribution around a mean value. For louse packed, monosized spheres, the mean coordination is.. ' between six and seven. Generally. in random packing, spheres pack more efficiently than any other shape. . It is possible to assess particle shape and friction characterization through the apparent and tap densities. The ratio of the tap to apparent densities gives a signature characteristic of the interparticle friction. and is called the Hausner ratio. useful in categorizing relarive interparticle friction. For a spherical powder. the tap to apparent ratio will be slightly above unity. More irregular particle shapes undergo a larger density increase with vibra'ion. resulting in a higher Hausner ratio. .

\2.441

"

"

C;ompressibility
"," -,,' ' . 1

, pre!jsure sensor

/'"

calibration chamber (volume

= V e)

~~~vacuum valve powder (volume

= V p)

sample chamber (volume

= V 5)

One of the main uses for metal powders is for fabricating complex shapes by compaction. Accordingly. the compaction behavior is an important characteristic. Compressibility. or compactability, measures the ability to densify a powder under an applied load. The typical test geometry is a sjmple cylinder or rectangle. The die is loaded with powder and the density is measured after compaction at a predetermined pressure. often near 414 MPa (corresponding to 30 ton/in1 or 60,000 psi). That is termed the green density and is the basis for expressing the compressibility. For a com~tion grade of iron or steel powders the green density might be 85 to 90% of theoretical. A parameter used in tool design is the compression ratio C/I'
r ,

12.46}

Figure 2.34. A schemSitic d' ' using a p cno t lag ram of the true volume measurement for a loose powder pressure ~ea:~eer. The powder of known weight is placed into the sample chamber. and ed calibration VOluments are made before and after equilibration with an initially evacuatme.
72

where \lL is the volume of the! loose powder, Vc' is the' volume of the compacted powder, p. is the green density. and P" is the apparent density. A high interparticle friction will give a low initial density. but other factors such 3S panicle size, chemistry, lubrication.
73

---------------------------------------------------------and metallurgical properties will determine the pressed density.

POWDER METAlLURGY

SCIENCE

1'0 vt)1 I; (

11;,i,,\lrERIZI\TI()N

. A'typic;!1 atomized iron powder has ,10 apparent density of 2.9 glcm \ and compacts to a density of 6.71( gjcm" at 414 MPa pressure. The compaction ratio is then.

c, = P, / p. = 6.7H /2.9 = 23-1

If the powder was compressed to a height of 18 rnrn, then the initial powder fill depth for uniaxial compaction would have to be42.1 mm (18 times 2.34).

A magnified cross-section through 'a powder reveals artifucts that indicate 1';lbriCltion conditions and possible processing problem's. Cro,ss-~ectional analysis provides inlonnation orliftlternol pores, segregation and can he Lsefu{ in detecting inclusions and oxidcv, Figure 2,:l~ shows Ihe internal structure of two powders. TIle first powder i~ a ~pheric;d .-.!!!l.oy pow.der,_1]le, ~Ich~d ~_r:os.s~~,C!!ol1 show~ a large gas-fjlle.(LW.fe and radial crack-, ~ The second powder iirregular in shape with con ble porosity in the panicles which ider inhibit!! packing. compaction. nnd attainment of high final properties. Such' microxtruclures indicate subsequent processing problems since internal pores arc difficult to climinate. To observe the internal powder structure, mix loose powder wit~l a metallurgical mounting epoxy resin. The particles seule during curing of the resin.Subsequent polishing and etching of the mount brings out the panicle microstructure. Tranxmiscion clccIron mi~mscopy ha. also been u~d to observe thesolidification events during powder

Powder Structure

Figure 2.36. The scanning electron microscope is a polent tool in characterizing metal powders. In example a) three layers are evident in the fractured particle. The picture also shows satellite formation and agglomeration In this gas atomized alloy powder, In example b) the fractured centrifugally atomized particle shows clear evidence of the solidification events (photo courtesy of. . Hawers). J production. III Ih;11c.r-c. rhc pll\\li.:r i-, cuu.uucd ill ;1 nickel ekt:troplatill!! d.:pn,il where il is ~uhst:qu.:nlly 'l'Clil1l1.:d .IIHI illil nul lvd rill' electron truuxparcncy. However. -uch efforts arc uvuallyrc-u'ictcd to the 'l'c'CI;dl\ powder, such as supcralloys .. In xumc ill~talln'. uuportanr micro-uucuu c iuform.uion can he gained hy SEM analy ~is. Fieurc 2..~6 illll'lr;IIl', one ilhlal1c, 1\ here the particle fractured to reveal I\VO vhclls around a ~mall p;Ir\lck core. '\ddllilll1;dl~, uuclc.uion ~il':~. cout.uuination. t:lllllill~ rail'. !!rill size. ;1I1d,..:!!rl!!;lIi'"1call he' a",'",11 Irom SEM examinations. Further information on the powder C;l;l I~' ~;Iin,d hy ,urran' ;l1l;dy,i~ tonlx. These arc appropriate 111 charthe al'leri/alilln 111' 1'"I\(kr, -cnxitivv 111'lIlll;lIl1il1;l!io1\,Thermal analysi providc-, another , imponan: mcan-, 111' a"c'"ing Iii..: I'",,,kr, Included in these techniques arc ditfcrcnriul thermal analvsi-, for detection or pha-c u'au-Ioruuuiou and melting events. dirrt;r':lltial scanning c;Ii;lriml'lry ror quantific.uion of endothermic and exothermic events. and thcrmogravimctric analy,i, for determination I\l'ight loss due to desorption and evaporation during hearing.

Chemica. Characterization
When di~cussillg their chemistries. powders must be subdivided into three groups, The elemental powders arc rel.uivc ly highpurity materials where chemical analysis focuses on the impurity concentration. Premixed powders arc combinations or two or more distinct powders that will diffusionally alloy in sintering. An example would be the use of mixed 'copper and tin powders 10 Iorrn a bronze a1l9)1.Impurity levels and proper compounding of the mixture arc chcmicul conccrns with tile premixed powders, The prealloyed powders constitute micro-castingx with multiple elements in a predetermined ratio. For the preulloycd powders. uucntion is given to the alloy composition as well as the impurity concentrations. Normal analYlical chemistry techniques are appropriate for all powders.

Agure 2.35. Two example micrographs of cross-sectioned metal powders showirg how Internal mlc:roauctutal details can help In characterization of, powders; a) cp.ntrifugally the atomized steel alloy powder. and b) water atomized Iron poWd8[1photos courtesy of J. ( O\napandJ ..~), . ,f',,,-

,.

POWDER METAlLURGY SCI[N(E

" 1\VIti

I I WII'.l

II .." AI ION

Beyond the bulk chemical information, the surface condition is an important property of the powder. Hence, there is concern with oxides, adsorbed organic films, and the prcs-, encc of surface coatings like silica todetermine appropriate cleaning treatments. A loss on reduction is reported to show the weight loss when heated in hydrogen at a low ternperature. This measures the surface oxidation as well as volatile organic content and reducible compounds and is less sophisticated as compared to thermogravimetric analysis. Likewise, the inclusion concentration ismeasured by acid dissolution. For some materials, the powder hardness provides a gross gauge of the impurity level andssures a that the powder has been annealed. Often the elemental iron powders are derived either from ores or metal scrap. The ore based elemental powders will usually have lesslot-tolot chemistry variations than the scrap based powders. On the other hand, the ore based powders tend to have higher inert or oxide inclusion contents. Powders fabricated by melting techniques provide greater opportunity for chemical refining. and can be expected to have higher purity. . Depending on the desired sensitivity. bulk chemical characterization 01 a powder (an be obtained from wet analysis. emission or name spectroscopy. atomic absorption. x-ray diffraction, x-ray fluorescence, or neutron activation analysis. Emission spectroscopy and x-ray fluorescence are typically used for routine analysis. with lower sensitivities of approximately 10 ppm (pprn is the standard abbreviation for parts per million or O'"), l Advanced techniques arc capable of extending analytical accuracy to 0.0 I ppm level. the Microanalysis by electron or ion beams is useful for characterizing the chemical composition in small volumes. The microanalysis techniques are not useful for routine analysis since they are typically semi-quantitative and slow. Finally. surface analysis is possible using Auger or other research techniques. Here low energy electrons arc stimulated from near-surface regions. These electrons convey infonnation related to the chemical species present on the powder surface.

Tablr

2.7, Puwdt'r Cha"'oIrh'ri1~lliclIIfur Ihr TunJ:.<ilen Powder Shown In "i~ur~2.-'7

Material = Tungsten Designation = -325 mesh Metallic Chemistry 99.99% W Impurities (ppm) = C (10), Cu (I I. Fe '(2), K (15), Mg (4), Mo 0(740), Si (2) Apparent Density = 4.37 g/cnr' (23%) Tap Density 8.05 g/cm' (42%) Flow Time for 50 g = not free flowing BET Specific Surface Area 0.12 m!/g Gas Permeability Surface Area O.02X m!/g

(10). N (100), Nu (6), .

Particle Size by Sedimentation DII 3.0 prn D". = 6.4 ~1l1 DVI 12~m

.= .=

Particle Size by Electrical Zone Scnving D." = 3.5 pm

0.".= 6.2
D",. = X.9

~1l1' ~1l1
I

A Minimum Characterization Battery

.It is rare that a full battery of measurements is either needed or warranted to charuc('d tenze a metal powd er, Th' typical goal .111 e powder metallurgy is to control the process to provi e a standardiz d ad . . e pr uct. Powder characterization isgeared toward performing the m1l11mum amount of t . . research dd estll1g necessary to ensure consistent feedstock tothe process. In evelopment a pp I" h ... .. and und an di icanons, c aractenzauon IS necessary for future repetition ersran 1I1gof the I F powder to resu ts. or that purpose. a few tests should be performed on a ensure control Oft h . powder cha .. . en t ey are relegated to the manufacturer who certifies the ractensllcs. In the characterizati f to perform and I' on 0 a powder, the test should be meaningful. accurate, and easy rep icare E h . bulk chemistry th d . mp am should be given to the powder chemistry. Beyond weight loss me~sur: egree o.f ~ontamination should be determined using hydrogen Typically, a scannin mC~ts. 11 IS I.mponant to obtain a reliable particre size distribution. parison to some S\angdedectroh micrograph will provide sufficient shape detail for comar S Add' . . uionahy, one or more of the simple tests for interparticle

(I

Figure 2.37. A scanning Table 2.7.

electron micrograph of the tungsien powder as characterized

In

---.--

------

II

POWDER

METAllURGY

S(IENC.l

-------------------------_. ---~~--------------------------International. Materials Park. OH. Il}X4.

iilld

1'(

I\VI

II I; I I II\I;AI

1/

/ill AliI IN

friction should be given to provide a relative assessment of now, mixing, and fnction behavior. Finally. in some materials. it may be necessary to examine the internal ~tructure via metallography techniques for pores. inclusions or second phases. In most instances, not all of these characteristics need be measured: however. in research situation!! a broad test battery is reasonable. Table 2.7 gives an example charae. terizatlon of the tungsten powder shown in Figure 2.:n. It is a high purity elemental powder with a specific surface area indicating an irregular panicle shape. as seen in t!"lescanning electron micrograph. The particle size distribution by twotechniques gives a median size near 6 11m.while the SEM shows individual crystals from 0.5 to 311m. The low packing densities. lack of flow, fine size. and irregular particle shape are consistent with one another and indicale an agglomerated. snail powder. Generally. the goal of such an analysis Is 10 obtain specific information of the panicle size. shape. friction and structure as well as lhe chemistry. The appropriate combination of tests will. of course. be modified for the Iype o~ powder under consideration.

H. D. Lewis. "Sm;J1I Panicle Statistics: The Analysis of Particle 'Size' Data." TesliD.!: Characterization of Powders and Fin~ Particles, 1. K. Bit and T. Meloy (cds.). Heyden. London. England. 1980. pro 1.t5-175. III Powder Surf;tce Arcaand P(lrosily. john

S. Lowell and J. E. Shields. Introduction Wiley and Sons. New York. NY. IlJX4.
G. Matei.

N. Claussen and H. H. Hausner, "Influencc of Relative Humidity on Flow of Metal and Ceramic Powders." Modem Dcvelopments in Powder Metallur~y. vol. K. H. H. Hausner and W. E. Smith (eds.), Metal Powder Industries Federation. Princeton. NJ, 1974. pp. 5-11. J. Powder Bulk Solids Tech .. 1978. Powders." ), Powder Rulk

T. P. Meloy. "Particulate Shape Characterization." vol. 2. no. 2. pp. 13-23.

Suggested References
A. Adler. "Flow Properties of Metal Powders." IDler: J. Powder Met" 1969. vol. 5. no. I. pp.7.20. T. Allen. Particle Size Measurement. 1990. J. K. Beddow. Particulate NY. 1980. fourth edition. Chapman and Hall. London. UK. Publishing. New York.

R. Meyer. '''Standardizing Test Method fill' Characterizing Solids Tech,. 1979. vol. 3. no. 2. pro 21-27.

M. J. Rhodes (editor). Principles of f>mnkr T.:chnology. John Wiley and Sons. New York. NY. 1990. L. M. Sheppard. "Automation 87R-883. of Particle Analysis." Ceramic Rull .. 1988. vol. 67. pp.
l.

Science and TechnQlo~y. Chemical

J. D. Stockham and E. G. Fochtman (elk Publishers. Ann Arbor. Michigan. 1977. L. Svarovsky.

Parlit:1e Size Analysis. Ann Arbor Science Science. London. UK. 19K7.

J. K. Beddow and T. P. Meloy. Advanced Particulale Momholo~y, Raton. FL. 1980. R. O. Grey and J. K. Bit, "On the Hausner Ratio and its Relationship of Metal Powders." Powder Tech 1969. vol. 2. pp. 323-326.

CRC Press. Boca to Some Properties

Powder Testing Guide. Elsevier Applied

..

J. F. Waus and T. J. Carney, "Surface ChclI~ical Characterization of Powders," P()\:dcr Metallurgy - An Overview. I. Jenkins and 1. V. Wood (eds.), The Institute of Materials. London. UK. 1991. pp. 7691.

M. Ghadiri, F. A. Farhadpour. R. Clift and J. P. K. Seville. "Particle Characterization: Size and Morphology." Powder Metallurgy - An Overvjew. I. Jenkins and J. V. 'Wood (eds.), The Institute of Materials. London. UK. 19<)): pp. 56-75. A. Guinier, G. Founet. B. Walker and K. L. Yudowitch, Small Angle Scanerjng. John Wiley and Sons. New York. NY. 1955. H. H. Hausner and M. K. Mal. Handbook OlCmical Publishing. New York. NY. 1982. of Powder Metallurgy. second edition. Verlag

Study Ouestions

2.1. A 200 sample is used to measure Ihe panicle size .of spherical nick~1 pO\~.dcr. It~ T average size is 120 11m.roughly how many particles arc IIIthe sample? (NI density IS X.1 g/crrr') 2.2. A powder with an ellipsoid shape (lcnglh = 120 11mand diameter. = 60 11m)is sized by screening. What panicle dimension will best correl~te to the mesh size? 2.3. For a cubic panicle of sides 3 urn. a) what is the equivalent spherical surface diameter. and b) the equivalent spherical volume diameter? ;.. ,

W. I. Huppmann and K. -Dalal, Meta!J0CC30hic Atlas of Powder Metallurgy. Schmid. Frieburg. Gennany. 1986.

B. H. Kaye, "Review' of New Methods for Characterizing the Shape and Texture ofFine Particles." I. Powder Bylk Solids Tech., 1982. vol, 6. no. 2. pp. 1-4.

Eo K1ar (editor). Powder MetaJltu:EY, vol. 7, ninth edition of Metals Handbook. ASM
I

2.4. Iron powder is screened into -'I&)/~2(i() m'~sh and -325 m~sh fractions. The apparent density of the coarse fraction is 2.6 g!cm \ and the line fraction has an apparent dc~slty of 2.3 g/cm'. When a blend is prepared using. 20% fine panicles in the coarse Iruction, the
,

18

POWOFR

MrTAltt JR(,Y \(JFN(

1\ "VIII /( U ~nRllATION

nt density is measured as 2.8 g/crn'. Explain the effect. appare 5 Air is penneated through a tube of I cm2 cross sectional area by I em lone contain~.. Iybdenum powder with an apparent density of 4.5 g/crn'. At one atmosphere presmg rno I" . differential (2 atmospheres to I atmosphere) the measure d fl ow ve ocuy IS 0 " I 'i sur/c. What is the equivalent spherical diameter'! (air viscosity = 1.8 10' gicm/s. Mo em s. . , . heoretical density = 10.2 g/cm )

I.

prn. However. the other properties are quite different as noted below: [l9wder A powder B specific surface area. m~/g 0.26 0.12 apparent densuy, g/cm' :U 4.5 tap density. g/cm ~,6 8.1 a) Explain why there might he a difference in surface areas. b) What equivalent sp~erical dial.Heler woul~ give the same surface area.~for each powder'! c) What differences might explain the packing propenies? d) What addiuonat information would be useful? 2.17. ~alculate th: upward gas Ilo~"'.velocit~ for air so that a 10 urn panicle of le'l2 will be levlt~ted (held IIIa constant posinon) against gravjty, (air viscosity 1.8.10-1 giS/em. arr density = 1(;1 /cm', Pb theoretical density = 11.4 g/cm') g

2 ., E xplain why the flow time (in the Hall flowmeter) is observed to increase with the 6 ratio of the tap density to apparent density?

2.7. The' oxide on the surface of aluminum powder can be used to form a dispersion :or strengthening the consolida~ed powder. For. a 10 11mparticle di.amet~r and ~ ;5 nm thick oxide surface layer. what will be the consolidated percent of OXIde dispersoid?

2.8. What powder characteristics might cause the surface areas to differ when measured by permeability and by gas adsorption?

2.9. The Reynolds number must be below approximately 1.0 for Stokes law to be valid in performing a sedimentation analysis for particle size. For aluminum spheres settling in water, what is the maximum particle diameter forwhich sedimentation is valid? (density of AI = 2.7 g/cm', density of water = 1.0 g/crrr'. viscosity of water = I0 ~ gis/cm)

2.10. Set up a quality control flow chart for testing incoming powders at a P/M parts plant. The flow chart should include the minimum. but necessary. steps needed to ensure an acceptable and repeatable powder. Nominally. the powder is -I()() mesh iron.

2.11. The ratio of the tap to apparent densities has been proposed as a particle shape index. Discuss such a ratio and the possible combined influence of particle shape and size. 2 '.12. A polydisperse powder sample is analyzed for particle size using optical microscopy, giving a mean size of 13 urn. Asecond analysis is performed using scdimentat~on. giving a mean size of 28 11m.Give some possible reasons for the difference in mean sizes. 2..13 Calc~late the shape index k in Equation 2.43 for a regular parallelepiped wit han axial ratio of 1:2:8. J panicle

2.1 It Data arc collected by sedimentation 2.7 g/crn:') as follows: siz-: r;J.nge. pm weit:hl,:,: o to I (1.O I to 2 0.4 2 to 4 5.5 4 tu X ., 2.l4 8 to 12 IlJ.O 12 to 20 17.6 20 to 32 5.lJ 32 to 44 1.1 44 to XX 0 ..1 over XX 0.0

for an aluminum powder (theoretical

density

a) Give a particle size distribution plot showing the cumulative weight percent versus the 10glOof the particle size. . b) What is the mean panicle size 1111 a weight basis? c) Estimate the mean panicle size on a population basis. d) What techniques could be applied tll the size analysls of this powder?

'2.14. Two laborator' d . laborat res con uct sieve analyses of an irregular shaped powder. The first a few ;~i~I~;s the mean size as 54 11m, while the second claims it to be 75 urn. Offer ypotheses Why the values differ. 2.15. Approximatel h . mesh iron powd y ow ma~y panIcles are contained in a 10 gsample of +325/-270 er and what IS th . .. g/cml) . e estimated surface area? (theoretical density = 7.86 2.16. Two different tun rste panicle size using g ~ powders (theoretical density = 19.3 g/crrr') arc analyzed for a stream IIlg t h . cc ruque and found to have an equivalent mean size of 5 no

2.19 ':A spheri~al .20 11mpart ide lIf ~itallium (theoretical density 4.5 glcm1) has a ~ urn spherical VOId 111 ItS center. What will be the terminal settling velocity for this particle in< I water? .How d.oes that com.pare to the terminal velocity fora pore-free particle of the ' same diameter? (water density I g/cm:', viscosity 10.2 glcm/s)

2.20. How might mixed P'~~;ides of copper and tin be separated from one another?

(.

III