MME 3518 POWDER METALLURGY
• 2 Midterm Exams- 50 % • Pop-quizes-10 % • Final Exam- 40 %
1 COURSE MATERIAL
• Lecture Notes • G.S. Upadhyaya, Powder Metallurgy Technology
Suggested Readings • S. A. Tsukerman, Powder Metallurgy • R.M. German, Powder Metallurgy Science
2 Definition of Powder Metallurgy
• science of producing metal powders and utilizing them Powder metallurgy may defined as, “the art and OR • to make serviceable objects.” technique used to consolidate particulate matter i.e. Itpowders may also both be definedmetal and/or as “material non-metals processing OR • is a process whereby a solid metal, alloy.” or ceramic in the form of a mass of dry particles is converted into an engineering component of predetermined shape and possessing properties which allow it to be used in most cases without further processing. • Powder metallurgy is a forming and fabrication technique consisting of three major processing stages. – First, the primary material is physically powdered, divided into many small individual particles. – Next, the powder is injected into a mold or passed through a die to produce a weakly cohesive structure (via cold welding) very near the dimensions of the object ultimately to be manufactured. – Finally, the end part is formed by applying pressure, high temperature, long setting times during which self- welding occurs.
Powder Metallurgy (PM)
Metal processing technology in which parts are produced from metallic powders . PM parts can be mass produced to net shape or near net shape, eliminating or reducing the need for subsequent machining
. Certain metals that are difficult to fabricate by other methods can be shaped by PM . Tungsten filaments for lamp bulbs are made by PM . PM process wastes very little material ~ 97% of starting powders are converted to product . PM parts can be made with a specified level of porosity, to produce porous metal parts
. Examples: filters, oil-impregnated bearings and gears 6 Basic steps of the Powder Metallurgy Process. PM Parts
A collection of powder metallurgy parts. 8
Connecting Rods: Forged on left; P/M on right Powdered Metal Transmission Gear Warm compaction method with 1650-ton press Teeth are molded net shape: No machining UTS = 155,000 psi 30% cost savings over the original forged part 10 Industrial Machines Parts For Electric Motors PM vs. Other Fabrication Methods (casting, stamping or machining)
• PM is the choice when requirements for strength, wear resistance or high operating temperatures exceed the capabilities of die casting alloys. • PM offers greater precision, eliminating most or all of the finish machining operations required for castings. • It avoids casting defects such as blow holes, shrinkage and inclusions. Powder injection molding is coming out as a big challenge for investment casting. • However the PM process is economical only when production rates are higher, since the tooling cost is quite appreciable • The powder metallurgy methods starts with powders and the properties of the manufactured parts depend to a large extent on the properties of the initial powders.
Amongst powder properties, composition, size, form and structure of particle, specific surface, porosity and volume characteristics, fluidity, strength, hardness, permeability regarding liquids and gases, electric conductivity, compressibility and sinterability are of great importance in powder metallurgy.
Metal powders consist of separate small bodies the so- called particles from 0.1 µ up to several millimeters in size. — • In the majority of powders the size of particle varies from several microns— to 0.5 mm. Particles usually have internal pores, cracks and impurities. • Particle shape is widely varied and determined by the methods of production; the desired particle size is obtained by regulating the conditions of manufacture. Particles are divided according to their shape into three basic groups:
(1 ) hair or needle-shaped, the lengths of which considerably exceed their other dimensions; (2) flat (flakes or leaves) whose length and breadth are many times greater than their thickness; (3) equiaxed, which are roughly identical in all dimensions. Powders of the same chemical composition, but with different physical characteristics, are sharply distinguished by technological properties, i.e. by their behaviour during processing. Production methods and the fields of application for powders are determined with powder properties (shape,size)
Example: copper powder with particles in the form offtakes (flat) up to 1 µ thick and up to 50µ in diameter are used only as a pigment since any articles made from it contain cracks after pressing. Copper powder with particles of spherical form (globules) from 100 to 700µ in diameter is pressed only at very high pressures. A powder with irregularly shaped particles, so called dendritic, 40-45µ in size is easily pressed even at low pressures.
POWDER FABRICATION METHODS
Milling
It is a mechanical method for powder production, where the initial material is pulverized without any change in chemical composition. Reduction of particle size is beneficial for sintering, which depends on diffusion of atoms.
Most common milling method is ball milling - Generally balls are used for milling. Hardness of the balls must be equal or greater than the hardness of the powder will be milled. - Amount and size of the balls are critical for the final powder size. - Wet or dry milling can be applied. - From balls or barrel impurities may added to the powder (milling time and ball hardness) Milling
These processes are not much used as primary methods for the production of metal powders. Mechanical comminution is possible by methods such as impact, attrition, shear and compression. The formation of metal powders by mechanical methods relies on various combinations of these four basic mechanisms. Such methods have been used as the primary process for the following cases: materials which are relatively easy to fracture such as pure antimony and bismuth, relatively hard and brittle metal alloys and– ceramics. reactive materials such as beryllium and metal hydrides. common metals such as aluminium and iron which are required –sometimes in the form of flake powder. – Milling
• Milling is oldest in powder metallurgy and ceramics • Effective in brittle materials. • Less effective in metallic materials (ductile) • Alloys can be effectively grinded by mechanical means
Additionally, there are important mechanical disintegration process in powder metallurgy , in high- energy milling severe embrittlement of the metal may occur. Milling
The general phenomena during size reduction in the solid state are based on fracture mechanics: • the nucleation of cracks, • crack propagation • fracture, by which new surfaces are formed.
The kinetic energy within the milling aggregate is partially transformed into mechanical stresses in the material causing disintegration (break up). Milling
The forces acting in these processes cause; • compression • shear stresses applied by the milling balls during vessel rotation or by the rotating arms in an attritor. (impact) The limit of the minimum obtainable particle size depends on • the condition of the mechanical process • the material
• The smaller the particle size necessary shear stress increases on each particle in order to achieve further particle fracture.
• Small particles exhibit higher surface activity than larger ones and therefore, have a higher probability of being re-welded. The efficiency of mechanical size-reduction processes is generally very low. • Only about 0.1 % of the spent energy in the conventional ball milling process is found in the generated new surfaces of the fine particles. • The efficiency may be somewhat higher in high energy milling processes but is still less than 1 %.
The sources of lost energy: • elastic and plastic deformation of the particles • the kinetic energy of the particles in motion, impact and friction energy in the form of heat outside the powder, etc. The main cause of lost energy, however, is the generation of heat. Optimizing Milling Efficiency conventional steel ball mills, size and number of milling ballsup 40-50% of the vessel volume. size of the balls 12 and 16 mm( about 10-20 times larger than the initial size of the particles) other types of fine-milling equipments; planetary ball milling, centrifugal milling and attritor milling. Optimizing Milling Efficiency
Wet Milling instead of dry milling is often advantageous because liquids tend to break up agglomerates as well as reducing re-welding of powder particles.
As milling media, hydrocarbons (hexane, heptane), ethanol and other organic liquids, which help to avoid oxidation of the milled product, are often used. Impurities During the milling of hard and abrasive powders the level of impurities sometimes rises considerably, because of severe wear loss from walls and milling media.
Rubber liners and ceramic balls which cause less contamination are sometimes advisable. • Iron contamination can be removed by subsequent acid leaching, if the milled powder itself is acid- resistant. Impurities
• Rubber liners and ceramic balls (Al2O3 or ZrO2) which cause less contamination are sometimes advisable.
Cubic Zirconia has a rating of approximately 8 on Mohs hardness scale vs. a rating of 10 for diamond Alumina has a rating of approximately 9 on Mohs hardness scale vs. a rating of 10 for diamond
• The best but most expensive solution is to use liners and balls of similar composition to that of the material being milled (e.g., the milling of special ceramic
powders, like Si3N4) Attritor Mill
An attritor is a ball mill system in which the balls, together with the material to be milled are set in motion by a shaft with stirring arms, rotating 100-2000rpm.
Cylindrical vessel is usualy water cooled because of the considerable heat generated by the process. Dry,wet (water, inorganic liquids) milling is possible inert gas supply possible for reactive materials. More effective than conventional ball mill. • Dry wet attritorsinorganic pigment and paint production, hard metal industry. In these fields of application of very fine particulates are required.
• Several metals and alloys may become amorphous during extended milling. Amorphous alloys (glassy metals developed by this method) Mechanical methods Mechanical methods Roller Milling
For brittle materials a new size reduction technology become important, the high-compression roller mill,which operates with profiled rollers in the pressure range 50-500 MPa.
According to the working conditions products with narrow particle size ranges, between 200 and about 5µ are achievable. Mechanical methods Mechanical Alloying
Mechanical alloying is a high-energy ball milling process for producing composites with a controlled, even distribution of a second phase in a metallic matrix. Mechanical methods
• developing dispersion-strengthened alloys in which the development of special microstructures essential for achieving good high-temperature mechanical properties in multiphase powder metallurgy materials.
• the distribution of a non-metallic phase in a metallic, ductile matrix can be homogenized to a degree, which can be achieved otherwise only by chemical means.
• chemical reactions and formation of solid solutions can be obtained, in such cases the term 'reaction milling' is used. Mechanical methods Mechanical methods The process consists of long period milling of mixtures, in which the main component (matrix) is ductile.
• the ductile phase undergoes a continuous cycle of plastic deformation, fracture and re-welding processes, by which the fine dispersoids are implanted step-by-step into the interior of the ductile phase.
• Mechanical alloying is applicable to nearly all combinations of brittle phases (oxides,carbides, nitrides, carbon, intermetallics) and ductile metallic powders, which demonstrates the possibilities for extensive composite materials development. Chemical methods Chemical Methods These methods can be further classified as chemical reduction and chemical decomposition
Chemical Reduction Chemical reduction involves chemical compound most frequently an oxide, but sometimes a halide or other salt of the metal. This may be carried out;
. Chemical reduction from solid state . Chemical reduction from the gaseous state . Chemical reduction from aqueous solution
Chemical methods
Ellingham Diagram Chemical methods Chemical Methods
Chemical Reduction from the solid state (reduction of iron oxide with carbon or of tungsten oxide with hydrogen) Sponge iron powder produced by the Höganäs process is a typical example of this production method.
The Höganäs process is based in the use
of quite pure magnetite (Fe3O4) ores. The iron ore is reduced with a carbonaceous material
Figure shows the steps involved in producing such powder Chemical methods 1. Reduction mix of coke and limestone 2. Iron ore; 3. Drying; 4. Crushing; 5. Screening; 6. Magnetic separation 7. Charging in ceramic tubes; 8. Reduction in tunnelkilns, approximately 1200°C; 9. Discharging 10. Coarse crushing 11. Storage in silos 12. Crushing; 13. Magnetic separation 14. Grinding and screening; 15. Annealing in belt furnace, approximately 800-900°C 16. Equalizing 17. Automatic packing of pressing powder, welding powder and cutting powder; 18. Iron ore; 19. Reduction mix Chemical methods 1. The ore is ground to a particle size distribution determined by each of the desired iron powder. 2. The ore powder is placed in the centre of cylindrical ceramic containers (‘saggers’ made of silicon carbide) surrounded on the outside (and inside) by a concentric layer of a mixture of coke and limestone. 3. The saggers are placed in layers upon cars which are pushed through a fuel fired tunnel kiln. 4. The carbon monoxide produced from the coke reduces the ore to iron. Total reduction time is of the order of 24 hours at a reduction temperature of 12000C. 5. The limestone serves to bind any sulphur in the coke and prevents its contaminating the iron. 6. The sponge iron is mechanically removed from the saggers, ground and the resulting powder magnetically separated from impurities. In a final reduction step the powder is carried through a continuous furnace in hydrogen atmosphere on a belt made of stainless steel.
The overall reduction Most of the powder is milled to particle size distributions suitable for powder metallurgy parts production, whilst some (particle size> 150 m) is sold for the manufacture of welding electrodes. Chemical methods Pyron produced from mill scale by reduction with hydrogen. Example2: ‘ iron powder’ is Mill scale, often shortened to just scale, is the flaky surface of hot rolled steel, consisting of the iron
oxides iron(II) oxide (FeO), iron(III) oxide (Fe2O3), and iron(II,III) oxide (Fe3O4, magnetite).
The mill scale is ground, magnetically separated and first roasted in air to convert the Fe3O4 to Fe2O3 (because the rate of reduction of Fe2O3 with hydrogen is faster than that of Fe3O4)
The oxide is reduced in a belt furnace at temperature near 980 ̊C. The reduction product is ground. Chemical methods
Example3: WO3 is reduced to tungsten powder with hydrogen. The important minerals of tungsten are wolframite
(FeWO4) and scheelite (CaWO4), often occurring with tin ores. • Scheelite ores are leached with HCl to form tungstic acid (H2WO4 or WO3.H2O) • Tungstic acid is dissolved and digested in ammonia solution (NH3) to give rise to ammonium tungstate solution (NH4)2WO4 • APT (Ammonium Paratungstate, (NH4)10(H2W12O42)·4H2O) is obtained from the crystallization of ammonium tungstate solution. • APT is then calcined to give blue oxide. Chemical methods • Tungsten is leached with caustic soda (NaOH) at elevated temperature under pressure to produce
sodium tungstate (Na2WO4) in solution. • the solution is purified using solvent extraction
• tungsten finally precipitated as pure WO3.
•
reduction from WO2 to tungsten at • 850̊ C,
The reduction of WO2 by hydrogen is catalyzed by tungsten metal. Chemical methods
GaseousChemical basedReduction fabricationsfrom the fabricate gaseous state powders from reactive metals and precipitate nanoscale particles. The powders are formed without melting or contact with a crucible, thereby avoiding a major source of contamination.
Obtaining Ti powders from Titanium tetrachloride vapour with molten magnesium the well-known Kroll Process – Chemical methods
Chemical Reduction from the gaseous state
Ilmenite (FeTiO3 ) is the most abundant titanium-bearing mineral and is comprised of about 43% to 65% titanium dioxide (TiO2 ). A second major mineral form of titanium is rutile, a crystalline, high-
temperature polymorph of TiO2 , containing about 95% TiO2 .
The chloride process is used to separate titanium from its ores. In this process, the feedstock is chlorinated at 1000 °C with carbon and chlorine gas, giving titanium tetrachloride. Typical is the conversion starting from the ore ilmenite:
2 FeTiO3 + 7 Cl2 + 6 C → 2 TiCl4 + 2 FeCl3 + 6 CO Chemical methods
Chemical Reduction from the gaseous state
In a separate reactor, the TiCl4 is reduced by liquid magnesium or sodium (15 20% excess) at 800 850 °C in a stainless steel distiller to ensure complete reduction: – –
2Mg(l) + TiCl4 2(l) + Ti(s) (T = 800 850 °C)
(g) → 2MgCl – Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method)
Example: Copper Low cost copper powder is produced from solution obtained by leaching (solve+filtrate) copper ores or copper scrap, where the precipitation of copper powder from an acidified solution of copper sulphate with iron is achieved.
Large quantities of this ‘cement copper’ are produced from the copper sulphate solutions which are a by-product of the copper refinery industry.
Therefore, copper sulfate is essential to reduce copper. Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method)
Example: Copper
A.E. Back, «Precipitation of copper from dilute solutions using particulate iron», Journal of Metals, 27-29, May 1967 Chemical methods Chemical Reduction from the aqueous state
Example: Copper
Anoher way of copper recovery from copper(II) sulfate solutions by reduction with carbohydrates*
Copper(II) in copper sulfate solutions can be reduced with various carbohydrates to obtain a copper powder. • Theoretically, the overall reaction for copper reduction with cellulose is:
*R.D. van der Weijden ,J. Mahabir,A. Abbadi,M.A. Reuter,» Copper recovery from copper(II) sulfate solutions by reduction with carbohydrates», Hydrometallurgy Volume 64, Issue 2, May 2002, Pages 131–146 Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method).
Example: Nickel
The method described for the preparation of extra high purity nickel powder is based on the reduction of nickel sulfate solution by hydrogen under pressure in an autoclave.
An autoclave is a pressure chamber used to carry out industrial processes requiring elevated temperature and pressure different to ambient air pressure. (similar to pressure cooker) Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method).
ExampleThe methods: Nickel employed for removing the traces of impurities include cementation of the copper, hydrolysis of the iron salts, and chemical precipitation of the cobalt. Unlike commercial practice of the hydrogen reduction process, the reduction of the
purified nickel sulfate NiSO4 solution is carried out without a ferrous salt catalyst. Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method).
ExampleTo initiate: Nickel the reduction reaction, a small amount of
ammonium carbonate ((NH4)2CO3) is introduced into the system. Reduction is carried out at a temperature of 350°F (1760C) under a hydrogen pressure of 350 psi (2.4 MPa).
The ammonium carbonate presumably promotes the formation of a fine suspension of solid basic nickel
carbonate, NiCO3 which then plays the role of a catalyst and provides the nuclei on which the nickel precipitates.
N. Zubryckyj, W. Kunda and D. J. I. Evans, «Extra-High-Purity Nickel Powder from Nickel Sulfate Solution by Hydrogen Reduction», Journal of the Electrochemical Society, 1969 Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method).
Example 2: Nickel
Nickel powder produced by the Sherrit Gordon process is the typical hydrometallurgy method for production in which reduction of an ammoniacal solution of nickel sulphate NiSO4 with hydrogen under a pressure0 of 1.38 MPa (200 psi) and a temperature of 190–200 C in an autoclave is carried out. Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method).
Example 2: Nickel
A nickel salt solution is obtained by leaching complex Cu–Ni–Co ores. Before the nickel is precipitated as metallic powder the copper is removed from the solution by precipitation as sulphide (CuS). For the precipitation of the first nickel powder nuclei from the solution, catalyst, e.g. ferrous sulphate, is used. The very fine nickel powder nuclei are allowed to settle in the autoclave, the barren solution is decanted and a new batch of solution is introduced into the autoclave. Chemical methods Chemical Reduction from the aqueous state (hydrometallurgical method).
Example 2: Nickel
The nickel powder nuclei are suspended in the solution by agitation and the nickel in the solution is reduced with hydrogen at 1.38 MPa (200 psi) and precipitated on the existing nuclei. The process called densification is repeated many times, say 15– 30. Finally, the powder is removed from the autoclave, washed and dried. The process permits control of the size and shape of the nickel powder being produced Chemical methods Chemical Decomposition of Compounds
Under this category of powder production two methods are very common. These are : (i) Decomposition of metal hydrides (ii) Decomposition of metal carbonyls
Decomposition of metal hydrides This involves first hydriding the refractory metals like Ti, Zr, Hf, V, Th or U by heating the metal in the form of sponge, chip or turnings
or even compact metal in hydrogen. TiH2 is formed from titanium in the temperature range between 300 5000C. These hydrides are quite brittle and can be readily ball-milled into powder of the desired size. – Chemical methods
These may be dehydrided by heating them in a good vacuum at the same temperature at which the hydride was formed. Care must be
taken to avoid contamination of O2, N2 and C during hydriding or dehydriding.
Example Decomposition of metal carbonyls iron and nickel powder production.
The carbonyls are liquids at normal temperature with a low boiling point. These are formed by reaction of the metal and carbon-monoxide gas under pressure.
For example; iron carbonyl (Fe(CO)5) is formed at 70–200 atmosphere pressure and a temperature of 200–220 C̊ . The carbonyls can now be decomposed by heating at atmospheric pressure. Chemical methods
Decomposition of metal carbonyls Example iron and nickel powder production.
Care must be taken to have the decomposition take place in the gas phase and not on the surface of the reaction vessel, in order to obtain metal in the powdery form.
The usual carbonyl iron powder particles are spherical with an onion skin structure,
formed catalyze the decomposition of CO into C and CO2. because the iron powder ‘nuclei’ first Chemical methods
• This type of iron powder is quite pure with respect to metallic impurities, but contains considerable amount of carbon and oxygen (fraction of a percent). • The amount of such impurities can be reduced by adding ammonia during the decomposition of the carbonyl and by a subsequent annealing treatment. • But these would naturally enhance the cost. Carbonyl iron powder is usually spherical in shape and very fine (<10 µm), while the nickel powder is usually quite irregular, porous and fine. Physical methods Physical Methods
Atomization • Gas Atomization • Water Atomization • Cyrogenics Liquid Atomization • Centrifugal Atomization Physical methods Atomization
Atomization is the most important production method for metal powders. The process generally consists of three stages: melting atomization (dispersion of the melt into droplets) • solidification and cooling. • • additional processing becomes necessary before the powders attain their desired properties,( reduction of surface oxides, degassing, size classification, etc.) Physical methods Classification
For each of the process stages different methods can be used, resulting in a large number of variants. Physical methods Melting
• In this stage the most important criterion is whether melting and melt distribution require a crucible system or not. Crucibles are one of the main sources for contamination of atomized powders. • The second criterion is the heating source. Essentially all melting techniques known in metallurgy can be used, e.g., induction, arc, plasma, and electron-beam melting, but some of these may also contribute to contamination, as for example in arc melting. Physical methods Solidification
During the soldification and cooling stage, the cooling rate is the controlling parameter. Cooling rate depends on: • the dimensions of the liquid droplets or solid powder particles, • the type of heat transfer from the particles to the surrounding medium. The undercooling prior to nucleation and cooling rate are the controlling factors for determining the microstructure of the powder particles, as well as for the dimensions of the atomization unit.
Depending on the parameters in each stage various disintegration methods are possible: Physical methods Disintegration/Dispersion
Disintegration step: The energy for disintegration introduced into the melt; by capillary forces (melt drop process), mechanical impact (impact disintegration), electrostatic forces (electrodynamic atomization), liquid or gas streams or jets (liquid or gas atomization) , centrifugal forces (centrifugal atomization), gas supersaturation of the melt (vacuum atomization), or ultrasonics (ultrasonic atomization) . Physical methods Gas Atomization
Air, nitrogen, argon or helium are used, depending on the requirements determined by the metal to be atomized.
Here, melted initial material is collapse with the gas within the chamber .
Heat is transfered from the liquid droplets to the surrounding gas. And liquid solidifies.
Atomization can be undertaken either Vertical atomisation unit in vertical or horizontal units. Physical methods Gas Atomization Production of Fine Particles; • a high velocity of the atomizing fluid • small melt stream (droplet) diameters • high density, and low viscosity and surface tension of the melt
The nozzle design is an important key to success or failure of a gas atomization system. Physical methods Gas Atomization
The mean particle size of gas atomized powders is in the range of 20-300 µm.
The particle shape is spherical or close to spherical. Irregular particle shapes can only be produced in systems where reactions between the gas and the liquid metal cause the formation of solid surface layers. This is the case, for example, in the air atomization of aluminium. Physical methods Gas Atomization
• Melt atomization by air is used in the production of the so-called 'Roheisen Zunder' (RZ) iron powder. This process starts from a cast iron melt. The surface oxides formed during atomization are reduced by the inherent carbon of the cast iron particles during a simple subsequent annealing treatment Physical methods Gas atomization
Inert gas atomisation is applicable for all metallic alloys which can be melted. The main application is for high alloy products such as stainless steel, tool steels, iron, nickel- or cobalt-base superalloy powders, as well as aluminium alloy powders.
Limiting factors are the availability of suitable crucible and auxiliary/helpful melting process materials. Powders from refractory metals with high melting temperature and highly reactive materials, such as titanium alloys, are usually produced by other methods. Physical methods Liquid atomization • Water atomization Cyrogenics Liquid atomization
Water atomization, Water atomisation is mainly used for the production of iron base powders. Figure shows a scheme for a water atomisation unit.
The starting material is melted and metallurgically treated in a separate furnace and then fed into a tundish. The tundish provides a uniformly flowing vertical melt stream, which is disintegrated into droplets in the focal area of an arrangement of several water jets. The impact from the high pressure stream of water leads to disintegration of the flowing metal
A high energy input to the water stream is needed. Scheme for a water atomisation unit. Physical methods Liquid atomization • Water atomization Cyrogenics Liquid atomization
In water atomization, a high pressure water stream is forced through nozzles to form a disperse phase of droplets which then impact the metal stream. In this method, large quantities of energy are required to supply the water at high pressure. This production method is significant for low and high alloy steels, including stainless steel. Because of oxide formation, water atomization is not likely to be used in the atomization of highly reactive metals such as titanium and the super alloys. In general, water atomized powders are irregular in shape, with rough oxidized surfaces. Physical methods Liquid atomization • Water atomization Cyrogenics Liquid atomization
In cyrogenic liquid atomisation,. The Krupp Company (Germany) introduced a novel version of atomization in which the melt is atomised with cryogenic liquid gas (argon or nitrogen) at –200 ̊C. During the process, the pressure of the liquid gas is increased up to 300 bar, while a recooling unit prevents the temperature from rising in spite of compression and prevents the cryogenic liquid from vaporizing instantaneously at the jet opening. Physical methods Liquid atomization • Water atomization: Cyrogenics Liquid atomization In cyrogenic liquid atomisation,. The resulting powder has the following properties: – It is much purer than the powder atomized with water and can be compared to the quality of the gas atomized powder. – The cooling rate is ten times higher than in gas atomization and almost reaches the quality of water atomization. Particles of 100 µm in diameter, for example, are quenched for approximately 106 K/s. – The powders are, as in gas atomization, spherical and have an average size of 6–125 µm. show satisfactory results in cold forming, while having a good flowability. Gas atomized powders have poor green strength Physical methods Centrifugal atomization The basis of centrifugal atomization is the ejection of molten metal from a rapidly spinning container, plate or disc.
• The material in the form of a rod electrode is rotated rapidly while being melted at one end by an electric arc. Molten metal spins off the bar and solidifies before hitting the walls of the inert gas filled outer container. Physical methods
The processC wasent developedrifugal primarilyatomiz forat theio natomization by high purity low oxygen content titanium alloys and superalloys.
Powder particles are smooth and spherical with an average diameter of ~200 µm; the size range is 50 400 µm. Typically, yields run to ~75% for 35 mesh powder. – – Physical methods Centrifugal atomization
Particle size distribution • Accurately controlled rotation of the anode is important so as to obtain in a desired range. • as the surface tension of the liquid metal, centrifugal forces (related to rotation speed) to some extent by the aerodynamics of the droplets trajectory through the inert cover gas. ‘ ’ Physical methods Centrifugal atomization
• Spherical metal powders made by either REP (rotating electrode process) or gas atomization are not well suited for cold pressing into green compacts to be followed by sintering. They are used in more specialized applications where consolidation is achieved by hot isostatic pressing (HIP) or some other high temperature method in which inter particle voids are more readily closed Physical methods ATOMIZATION
Solidification and Cooling The cooling rate the powder particle shape, and microstructure Cooling occurs by • heat transfer via radiation • heat flow through the medium which is in contact with the melt. The cooling rate during solidification depends on; • The melt volume • The heat flow Small melt volumes favor rapid cooling. Atomization under vacuum or reduced pressure conditions results in relatively low cooling rates Physical methods ATOMIZATION The microstructure of the powder particles is determined by nucleation and growth factors. • After nucleation has occurred, the relation of the growth rate of the solid from the liquid and the diffusion rate in the liquid determines the microstructure.
A large undercooling increases the growth/diffusion ratio Low growth/ diffusion ratios result in dendritic microstructures as a consequence of segregation.
With increasing cooling rate, the particles tend to form microcrystalline structures, combined with other non-equilibrium states such as high defect concentrations or metastable phases, which promote sintering effectively. Even non-crystalline (amorphous) structures can be obtained. Physical methods
water atomisation (a), b
gas atomisation (c)
rotational atomisation (d)
Spherical particles result from the solidifying droplets in gas and centrifugal atomization as a result of surface tension. Water atomised powders can be produced with very irregular particle shapes for high green strength requirements, but particles close to spherical can also be produced if good flowability and tap density are required. Physical methods
Advantages of atomization, 1. Freedom to alloy 2. All particles have the same uniform composition 3. Control of particle shape, size and structure 4. High purity 5. Lower capital cost
Fine particle sizes are favored by: (a) Low metal viscosity (b) Low metal surface tension (c) Superheated metal (d) Small nozzle diameter, i.e. low metal feed rate. (e) High atomizing pressure Physical methods Atomization Sphericity of a metal powder is favoured by: (a) High metal surface tension (b) Narrow melting range (c) High pouring temperature (d) Gas atomization, especially inert gas (e) Long flight paths
Trends for Future Development • ultra-high purity ultra-rapid cooling rate ultra-fine particle size Powder Characterization Powder characterization and microstructure control in powders
The success of any powder metallurgical process depends to a great extent on the complete characterization and control of the metal powders.
These properties also influence the behavior of the powder during compaction and sintering, and the composition, structure and properties of the sintered material. Powder Characterization Chemical Composition and Structure
The levels of impurity elements in metal powders can be very significant to both the processing and properties of the final product. It is necessary to know whether such elements are present in their elemental form or whether they are present in the form of a chemical compound
• Practically any metal powder adsorbs significant quantities of gases and water vapour from the atmosphere during storage.
– The amount of such contamination increases with decreasing particle size and with increasing chemical activity of the surface. Some of Chemical Characterization Techniques ; - XRF - XRD - EDX or EDXS
XRF; X-Ray Fluorescence
X-ray Diffraction n=2dsin - Bragg s Law
’
Scherrer Equation Useful for particles less than 100nm X-Ray Diffraction Optical Microscope
The optical microscope method is applicable to particles in the size range 0.8-150 m. Below that, Electron Microscopy is needed. μ Optical Microscope There are image analyser programs to determine particle sizes and distribution from the optical (and/or electron) microscopy images Scanning Electron Microscopy It is also a direct method to measure particle size of the particles. Optical microscopy or electron microscopy can be used to determine particle size Scanning Electron Microscopy Energy Dispersive X-ray Spectroscopy Transmission Electron Microscopy Transmission Electron Microscopy Sieving Sieving is used to separate particles according to their particle sizes. Sieving Table shows sieve numbers and their corresponding openings in mm and inches. Sedimentation
If a particle with diameter d is dropped into a liquid, two forces act on it. Gravitational force and and the upward thrust of the liquid. (check the units)
Gravity sedimentation is useful for particle size range 0.2 100 m.
– After calculations, Reynold s number must be checked. If R<2, the result is real. If R>2, result is not real. Se’ dimentation
푑 푅 = = + +0.34 24 3 퐶푑 푅 푅 2 4푔 푝 − 푑 = 3 퐶푑
where; Cd is drag coefficient, is density of fluid, is settling velocity, is the viscosity, d is diameter of particle Surface Area Method Partice size can be calculated by measuring surface area of the particles. The surface area can be measured by adsorbing of surface a monomolecular layer of a gas. The pressure of gas before and after adsorbtion is measured. From the difference in pressure, mass of the gas adsorbed by the powder surface can be calculated. From this mass, total surface area can be calculated.
This method is called BET method. In this method, surface area is used to find the particle size.
2 푆푢푟푓푎푐푒 퐴푟푒푎 표푓 푎 푆푝ℎ푒푟푒 ∶ 퐴 = 4휋푟 ; S is total surface area, is density
푟 = 3/ 푆 Light Scattering and Diffraction Methods
The principles of these methods are based on the interaction of an incident optical beam with a single particle. This beam can either be absorbed, scattered, or transmitted. Scattering includes reflection, refraction and diffraction.
Particle size analysis by optical counting Particle size analysis by laser diffraction Metal Powder Characteristics
There are a number of powder characteristics which have great effect on the particle properties. These are;
. Chemical Composition and Structure . Particle Size and Shape . Particle Surface Topography . Surface Area . Apparent and Tap Density . Flow Rate . Compressibility . Green Strength . Pyrophorocity and Toxicity Metal Powder Characteristics
. Chemical Composition and Structure The levels of impurity elements in metal powders can be very significant to both the processing and properties of the final product. It is necessary to know whether such elements are present in their elemental form or whether they are present in the form of a chemical compound. For example, in reduced iron powder silicon is present as impurity in the form of silica, which is insoluble in most acids. The effect of impurity elements on the hardness of the particles and the degree of chemical reactivity during sintering will differ widely, depending on the actual form they are in. The annealing of the powder in a reducing atmosphere is an effective way of reducing oxygen contents. The microstructure of the crystalline powder has a significant influence on the behavior of powder during compaction and sintering and on the properties of the final product.
Fine grain size is always desirable, as it improves the mechanical properties apart from the sinterability and the uniformity of dimensional changes.
The grain size can be dependent on the powder particle size. The particular powder production method, e.g. rapidly cooled powder, would naturally give rise to small particles and also small grain sizes.
Microporosity associated with entrapped gases is also common. A cold worked powder e.g. ball milled, exhibits a high dislocation density which could be lowered by annealing. Metal Powder Characteristics
. Partice Size and Shape The shape of the powder is characterised by the dimensionality of the particle and its contour surface. Most powder particles are three-dimensional in nature and they may be considered as being somewhat equiaxed. Spherical particles represent the simplest and ideal example of particle shape. Porous particles differ from irregular ones because of the presence of the porosity, which itself may be very irregular in both size and shape. A large amount of porosity makes any shape characterisation very difficult. Metal Powder Characteristics
. Partice Size and Shape In a real mass of powder, all prepared in the same manner, all the particles will not have the same exact size, even though the shape may be essentially the same. Consequently, we must deal with size distribution when accurately describing powders.
In unimodal distribution, there is one high point or maximum amount of a certain critical size.
The polymodal distribution consists of two or more narrow bands of particle sizes, each with a maximum, with virtually no particles between such band.
The broad band distribution simply corresponds to a uniform concentration of particle sizes over a rather broad size interval with virtually no particles having sizes outside this range.
The irregular distribution represents a continuous and finite variation of particle sizes within a relatively broad range. Metal Powder Characteristics
. Partice Surface Topography A spherical particle may appear smooth, but on a closer examination at high magnifications the surface may actually consist of many protuberances. Reduced metal powder has a highly roughened surface.
Atomized metal powders, on the other hand, have finer degree of surface roughness, which are of rounded type rather than sharp and irregular.
Scanning electron microscope is a powerful tool for examining surface topography. Surface contamination of particles and agglomeration of fine particles can also be studied by this technique.
The exact nature of surface topography will influence the frictional forces between particles. These are important in the case of bulk movement of the particles, when the powder is flowing, settling or during compaction. Metal Powder Characteristics
. Surface Area
The actual amount of surface area per unit mass of powder is of great significance. Any reaction between the particles or between the powder and its environment starts at these surfaces. This affects sinterability. For a very irregular shaped particle with a high degree of surface roughness, the specific surface area can be very high.
The BET method of determining the specific surface is widely used for catalysts. Its use for metal powder is primarily for very fine powders, particularly those of the refractory metals and for characterizing the total surface area of porous powders. Metal Powder Characteristics
. Apparent and Tap Density
The apparent density of a powder refers to the mass of unit volume of loose powder usually expressed in g/cm3. It is one of the most critical characteristics of a powder, because of following reasons: (a) It determines the size of the compaction tooling and the magnitude of press motions necessary to compact and densify the loose powder; (b) It determines the selection of equipment used to transport and treat the initial powder; (c) It influences the behaviour of the powder during sintering
Other characteristics which have direct effect on apparent density are the density of the solid material, particle size and shape, surface area, topography and its distribution. Apparent density is determined by the Hall flowmeter, where a container of known volume (25 ml) is completely filled by flowing metal powder through a Hall funnel Metal Powder Characteristics
. Flow Rate
The standard method for its determination is by the Hall flowmeter, where the time necessary for 50 g of powder to flow through a prescribed small orifice is measured.
Very fine powders do not flow through a small orifice. This is a result of the drastic increase in the specific surface area as the size becomes very small.
For a given metal powder, the higher the apparent density, the lower the flow time. Metal Powder Characteristics
. Compressibility Compressibility is a measure to which a powder will compress or densify upon application of external pressure. Compressibility is reported as the density in g/cm3, rounded to the nearest 0.01 g/cm3, at a specified compaction pressure, or as the pressure needed to reach a specified density. Typically, a cylinder or rectangular test piece is made by pressing powder in a die, with pressure applied simultaneously from top and bottom. Compressibility of the powder is influenced by factors like: • inherent hardness of the concerned metal or alloy, • particle shape, • internal porosity, • Particle size distribution, • presence of nonmetallics, • addition of alloying elements or solid lubricants. Compressibility, alternatively, is defined in terms of the densification parameter, which is equal to:
Compressibility, in general, increases with increasing apparent density. A rather large amount of densification occurs at relatively low compaction pressure.
Another term, which is very important for tooling design, is the compression ratio. It is the ratio of the volume of loose powder to the volume of the compact made from it. A low compression ratio is desirable because of following reasons: • Size of the die cavity and tooling can be reduced • Breakage and wear of tooling is reduced • Press motion can be reduced • A faster die fill and therefore a higher production rate can be achieved. Metal Powder Characteristics
. Green Strength Green strength is the mechanical strength of a green i.e. unsintered powder compact. This characteristic is very important, as it determines the ability of a green compact to maintain its size and– shape during handling prior to sintering. Green strength is promoted by: increasing particle surface roughness, since more sites are available for mechanical interlocking; – increasing the powder surface area. This is achieved by increasing the irregularity and reducing the particle size; – decreasing the powder apparent density. This is a consequence of first two factors; – decreasing particle surface oxidation and contamination; increasing compaction pressure – decreasing (optimizing) the amount of interfering additives. – – Metal Powder Characteristics
. Pyrophorocity and Toxicity
Pyrophorocity is a potential danger for many metals, including the more common types, when they are in a finely divided form with large surface area-to-volume ratios.
The toxicity of powder is normally related to inhalation or ingestion of the material and the resulting toxic effect.
The chemical reactivity of a material increases as the ratio of surface area- to-volume increases. For this reason, fine particles of many materials combine with oxygen, ignite and result in explosive conditions. Metal Powder Treatment
Only in exceptional cases metal or ceramic powders can be introduced directly into a powder metallurgy shaping operation.
Usually, additional treatments are required to make a powder suitable for further processing. These operations are often summarized by the term 'powder conditioning'. They depend on the nature of the powder, the size and shape of the final part, and the subsequent operations to be carried out. HEAT TREATMENT
Raw powders resulting from various production processes often exhibit a reduced compressibility, due to rapid cooling during atomization, work hardening from mechanical comminution, residual interstitial impurities such as oxygen, carbon or nitrogen, and to oxide layers formed during production or storage.
Annealing is therefore common for many metal powders, when a good subsequent compressibility is required. Annealing
The aims of annealing are: 1) to soften the powder 2) to reduce the residual amount of oxygen, carbon and/or nitrogen from the powder.
The annealing operation may be done in an atmosphere furnace or a vacuum furnace.
Annealing temperatures are kept as low as possible to minimize sintering. Powder Mixing
one component operation, whereas mixing involves more than one type of powder, e.g. mixing of Thesolid term lubricant ‘blending’ with isa metalstrictly powder applied or to powders a of several other metals. Sometimes the additive acts as lubricant as well as alloying addition, e.g. graphite in iron powder
Mixing efficiency is best when the powder volume is about 50% to 60% of the mixer volume. Optimum mixing time may be from between 5 to 30 minutes but this can be determined only by experience with a given mixture in a particular mixer. The aim is to mix the powders only as long as necessary to achieve a thorough mix and to fix a uniform apparent density of the mix from batch to batch. Particle Size Reduction
Suitable size reduction processes normally produce an increase in the surface area (as a result of decreasing the average particle size) with narrow particle size distribution This results in increased homogeneity of nonuniform mixtures, increased chemical reaction rate. The actual requirements of a suitable size reduction process are extremely varied and depend on several parameters.
(i) Crushing: The major equipments are mortar and pestle, heavy drop hammer, and jaw crushers. (ii) Ball Milling: Effect of single collision between two balls on trapped powder The ductile elemental metal powders are flattened, and where they overlap, the atomically clean surfaces just created weld together, building up layers of composite powder. At the same time, work hardened elemental or composite powders fracture. These competing processes of cold welding and fracture occur repeatedly throughout the milling, gradually kneading the composites so that their structure is continually refined and homogenized. Granulation
Fine hard particles such as tungsten, molybdenum and WC– Co are non-freeflowing and are difficult to press. Moreover the handling of such fine particles is also difficult. Consequently, large agglomerates are formed by granulation method. In this case, the continuous stirring of powder- organic slurry is used, while the volatile agent is removed by heating. Granulation
One of the better form of processing the slurry is known as spray drying. The slurry is sprayed into a heated free-fall chamber where surface tension forms spherical agglomerates. Heating of the agglomerate during free fall causes vaporization of the volatile agent, giving a hard dense packed agglomerate.
Three standard techniques are used to atomize slurry for spray drying:
1. single-fluid nozzle atomization; 2. centrifugal (rotating disc) atomization, 3. two-fluid nozzle atomization. The largest agglomerate sizes(600 m) are achieved by the single-fluid nozzle. The centrifugal atomizer yields agglomerate sizes up to 300 m, and the two- fluid nozzle produces agglomerates only up to about 200 m in size.
Suitable binder materials must be homogeneously dispersable (preferably soluble) in the liquid used to form the slurry. Plasticizers, e.g. ethylene glycol, may be used with binding materials that are hard or brittle and that tend to crack during drying.
Suspending agents, e.g. sodium carboxymethyl cellulose, may be needed to prevent solids from settling within the slurry.
Deflocculating agents, e.g. sodium hexametaphosphate, aids in the formation of slurry by preventing the agglomeration of fine particles.
Wetting agents, e.g. synthetic detergents, also may be used to maintain solids in suspension The atomized slurry is of maximum liquid content when it encounters the laminar flow of hot incoming air. The maximum product temperature is relatively low and the evaporation time is relatively short. The atomizer and the inlet for the drying air are positioned at the top of the dryer.
Fine products in the exhaust air are separated using a cyclone or bag filters. They may be used in some pressing operations, but are often recycled into the feed slurry. A major precaution in spray drying is the fact that the granules should not be so strong that it does not loose its identity during compaction.
A disadvantage is that the organic binder must be removed in the sintering cycle.
It is used generally for most ceramic powders and for hard metal powder mixtures Coating on Metal Powders In number of cases, the base metal powders may be coated by another chemical species. The purpose may be to produce a homogeneous mixing, e.g. W Cu, a hard surface or deposition of soft low melting point metals on ceramics to give better – compressibility during compaction. One of the simplest method may be the mechanical method, say ball milling of WC Co. However, the uniformity of coating in such case is questionable. Some– of the more common methods Electroplating, Electroless Deposition and Coating by Hydrometallurgical Process Applications of Powder Fabrication Techniques Characteristics of Fabricated Metal Powders Characteristics of Fabricated Metal Powders Production Cost