Powder & its Fabrication

Powder Metallurgy (FMD 401)

Module 2 (I)

Instructor: Dr. Madhumanti Bhattacharyya

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Powder Fabrication
• Almost all materials can be made into powder

• Knowing the fabrication method helps estimate powder properties

• Method selection factors … ????

Fabrication Methods
• Mechanical i/p Energy Surface energy
• Physical (electrolytic & > 30
atomization)
• Chemical Energy efficiency !!!!!
• Evaporation
• Special Techniques 2
Mechanical Methods

• 4 fundamental comminution processes

involved:
✓ Impaction
✓Attrition Deformation, cold
welding and fracturing
✓Shearing Usually combined during
✓Compression mechanical powder fabrication

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 Shape of the powder formed by mechanical methods is usually irregular

SEM images of the aluminum powder ground at different times 4

L.M. Rojas-Díaz et al. / Powder Technology 360 (2020) 301–311
Mechanical Methods: Milling

➢ Material is pulverized w/out any chemical change

➢ Applicable: electrolytic iron, Be, Bi, metal-hydride, chemically embrittled
materials like sensitized SS, oxide dispersion strengthened (ODS) alloys etc.

Objectives of Milling … ???

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Milling Mechanism
The general phenomena during size reduction in the
Griffith’s theory ? solid-state are based on fracture mechanics.

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L.M. Rojas-Díaz et al. / Powder Technology 360 (2020) 301–311
Milling Mechanism: 1
2𝐸𝑟 2
The impact stress required: 𝜎= E= Young’s modulus, r- defect size, D- particle size
𝐷

Limitations!!! σ and D

Sequence of events:
• Microforging Flattening to severely cold worked

• Fracture Crack initiation and propagation

• Agglomeration Mechanical Interlocking

Separation
• Deagglomeration 7
Milling Equipment: Jaw Crusher Gyratory Crusher Roll Crusher

• Crushers (metal oxides, reactive metals like

hydride form of Zr, Nb, Ta etc.)

• Mills (powder & powder mixture)

Attrition
Ball Mill Vibratory Ball Mill Mill

• Vibratory mills
• Even finer powder is produced by
attrition mills with less contamination

Rod Mill Hammer Mill

Planetary
Mill
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Courtesy: Angelo’s Book.
Milling Equipment:

• Dry vs. Wet !!!

• Grinding efficiency ??

• Mills with continuous and intermittent discharge of fines

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Mechanical Method-Attritioning: Suitable for ODS alloys (Ni-Fe, Al-alloys )

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Mechanical Alloying: Raw Material: Mixture of
Soft and hard powder (+PCA)

high-energy ball milling process

for producing composites with
a controlled, even distribution Fine randomly oriented
of a second phase in a metallic
matrix.
laminates of materials

Kneading Impact (of powders)

between balls
Stages:

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Courtesy: Angelo’s Book, ch 10.
Mechanical Alloying:

Mechanical alloying of Ni particles with dispersed smaller particles. As Ni particles are flattened between the
two balls, the second smaller phase impresses into the Ni surface and eventually is dispersed throughout the
particle due to successive flattening, fracture and welding events

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Limitations of Milling:

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Mechanical Methods: Fluid Energy Grinding:

• Kinetic energy of fluid makes the particles impinge

on each other and collide to fracture in fines

• Fluid media – air (0.7MPa), steam (2 MPa), N2, CO2 etc.

Important Parameters ??

Applicable: WC, graphite, Ceramics (ferrite,

BaTiO3), oxides (Mg, U, Zn)
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Mechanical Methods: Fluid
Energy Grinding
/ Jet Milling:

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[Link]
Other Mechanical Methods:
Machining
• Source ???
• Cheapest for production in bulk quantity
• Not a first choice ….. ???
• Mg, Be, Ag, solder and dental alloy powders are specifically made by machining.

Shotting
• Molten metal → vibratiory screen → Powder
• Mechanism ???
• Controlling parameters: ??
• Cu, Al, Zn, Sn, Brass etc.

Graining
• Similar to shotting with collection medium to be water
• Cd, Bi, Sb
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Physical Methods Cu - sulphate, chloride, cyanides
A - Cu , C – cast (Sb-Pb)
Electrodeposition
Fe – sulphate, chloride, cyanides
- Used extensively for Cu, Fe and Ni powder
A – armco-iron , C – stainless
- Feedstock ?? steel (SS)
- Powder Mg – sulphate
A – insoluble Pb , C – SS

Forms ???

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Electrodeposition (contd..)

Factors promoting powdery deposit…….. ???

Ch 2: Angelo’s Book
Ch 2: Upadhyay’s Book

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Electrodeposition (contd..)

• Advantages…. ??

• Disadvantages ……. ???

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Atomization

• The most important and commonly used production method.

• Stages ??

• High purity metals (Al, Fe, SS, Brass, superalloys), alloys (miscible &
immiscible) and intermetallics powders…. (reactive metals (Ti, Zr), polymer
and ceramic too..!!!)

• Types ??
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Atomization Unit:

Ch 10: Angelo’s Book

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Atomization Unit:

Atomizing nozzles Ch 10: Angelo’s Book

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Atomization Unit:
Atomizing media
Ch 10: Angelo’s Book

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Mechanism :

Thin sheet of metal

Stages ??
Ch 10: Angelo’s Book
Ch 3: German’s Book
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Mechanism of Atomization:

• Particle Size

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Mechanism of Atomization:

• Particle Shape

Ch 10: Angelo’s Book

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Important atomization parameters ??

Ch 10: Angelo’s Book

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Different Atomization Methods

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Inert Gas Atomization: • Production of high grade metal powders with
spherical shape, high bulk density, smooth
surface and flowability along with low oxygen
content and high purity
• P < 5MPa …… can range upto 18 MPa

• Parameters : ??

Horizontal Atomizer

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Inert Gas Atomization: Vertical Atomizer

• Superheat !!

• Back-pressure !!
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Gas Atomization
• Advantages

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 Gas Atomization
• Disadvantages

Özbilen, S. "Satellite formation mechanism in

gas atomised powders." Powder metallurgy 42,
no. 1 (1999): 70-78.

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Liquid/Water Atomization:

• Medium ???

• Rate ??

• Powder size range 150-400 μm

β- constat (material+ atomizer effects)

V – water velocity (m/s),
P – water pressure ,
α- angle between axes of melt & water jet

• 103 -105 K/s … impingement ??

• Compressibility ??? Noble metals, low-C steel, SS powders,

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Liquid/Water Atomization:

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Liquid/Water Atomization:

• Particle Size

Ch 2: Upadhyaya’s Book

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Liquid/Water Atomization:
• Particle Shape

SEM images showing characteristic morphologies of stainless steel powder: (a) gas
atomization,(b) water atomization

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Liquid/Water Atomization:

Advantages:
1. Freedom to alloy
2. All particles have the same uniform composition
3. Control of particle shape, size and structure
4. Lower capital cost.

Limitations: ??
-

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Liquid gas atomization:

• Atomization by cryogenic liquid gas.

• A stream of high ‘P’ cryo-liquid is used to atomize and solidify the melt

• Powder properties ???

Ch 2: Upadhyaya’s Book

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Soluble Gas Atomization:

Ch 10: Angelo’s Book

Alloys of Fe, Co, Ni, Cu, Al….. steels,

superalloys , metal hydrides (Ti) 39
Centrifugal Atomization:
• Mechanism??

• Cooling rate??

• Types: ??

Ch 10: Angelo’s Book

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REP/PREP high purity low oxygen content titanium alloys and superalloys

50,000 RPM

Ch 2: Upadhyaya’s Book
Ch 3 : German’s Book

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REP/PREP
• Powder size ??

Ch 3 : German’s Book

• Powder shape ??

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Centrifugal Atomization:

• Advantages … ??

• Disadvantages … ???

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Ultrasonic Atomization:

• High-pressure N2, Ar, He

through resonance cavity

• Particle size ??

• Primarily used for Al-alloys

Ch 10: Angelo’s Book 44

Ch 10: Angelo’s Book 45
Ch 10: Angelo’s Book

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Limitations of atomization:

???

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Chemical Methods:

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Gas-solid reduction Powders of Fe, Co, Ni, Cu, W, Mo, Ta, Th & Ti

• Reduction of ‘OXIDES’

• Gases used: ??.

MO + 𝐻2 ↑= M + 𝐻2 O ↑
MO + CO ↑= M + 𝐶𝑂2 ↑
• Sponge powders, control of size, shape and porosity

• Other methods??

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Gas-solid reduction

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Gas-solid reduction
• Production of Sponge Iron powder by-

➢Höganäs Process : Fe3O4 + coke+ limestone 1200°C, 24 h Sponge Iron

Air Roasting 980°C

➢ Pyron Process : Fe3O4 Fe2O3 + H2 Sponge Iron

• Production of W from WO3

Important parameters:

Atmospheric condition Temperature & Time Moisture content in the gas

Pressure & flow rate of the gas Thermodynamic & kinetic aspects
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Thermodynamics

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Kinetics

t50%, min
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Thermal Decomposition: Carbonyls
• Powder generation by
➢Condensation of volatile metal compound
➢Purification of condensed liquid
➢ Its decomposition
• Examples: carbonyls of Co, Fe, Ni, Mo, Cu, Cr, Rh, Au and W
Carbonyl decomposition
Carbonyl formation 200-220°C
Fe + 5CO → Fe(CO)5↑ Fe(CO)5 → Fe + 5CO↑

Ni + 4CO → Ni(CO)4↑ / Ni3S2 + 4Cu + 12 CO → 3Ni(CO)4↑ + 2Cu2S Ni(CO)4 → Ni + 4CO↑

W + 6CO → W(CO)6↑ W(CO)6 → W + 6CO↑

2Co + 8CO → Co2(CO)8↑ Co2(CO)8 → 2Co + 8CO ↑

Ether, dichloroethane Mo(CO)6 → 2Co + 6CO ↑

2MoCl5 +5Zn+ 12CO → Mo(CO)6 + 5ZnCl2 54
Thermal Decomposition

Factors ??

Applications:
❑ Electrodes of alkaline battery, fuel cell
❑ Fe-powders: soft magnetic material, magnetic cores
❑ Fe-Ni alloy powders in manufacturing high permeability cores for communication
applications.

Disadvantages:
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Thermal Decomposition: Hydrides

• 2–stage process:
➢ Conversion of metals to hydride
➢ Decomposition of crushed hydrides

Hydriding Dehydriding

Ti + H2↑ → TiH2 TiH2 → Ti + H2↑

3H2↑+ 2U → 2UH3 2UH3 → 3H2↑ + 2U

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Precipitation from a liquid:
• Wet chemical method:
precipitation (hydroxide, carbonate, oxalate form ) + decomposition & reduction

2AgNO3 (aq) + 2K2SO3 (aq) → 2Ag+ + 2NO3- +4K ++ 2SO32-

2Ag (s) + 2K2SO4 (aq) + 2KNO3 (aq) + SO2 (aq)

• Metallic ions + H2 → metallic precipitates

• High purity powder, 1 µm size with poor flow and packing

characteristics 57
Precipitation from a liquid:

• Provision for alloy/composite powder.

• One phase is used to nucleate the precipitates, e.g. ThO2, TiO2 & WC are coated
with Co, Ni, Fe

• Precipitation technique is also applicable for reactive metals, Zr, Ti etc.

Co-precipitation:

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[Link]
Precipitation:

Other Examples:

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[Link]
 Spray Pyrolysis
• Metallic Ion containing solution is sprayed in a heated chamber

• The solution is thermally decomposed (pyrolysis) and gives powder

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[Link]
 Hydrometallurgical Precipitation

• Precipitation of metals (from aq. solution/slurries) by gaseous reductants

aq. solution Ammoniacal soln.

• Optimum reaction rate achieved through high T, P in an autoclave

• Commercially produced: Cu, Ni and Co

• For refractory metal powders:

❑ W, Ta, Ti etc.
❑ Ta from K2TaF7 by sodium reduction in inert atmosphere
❑ The product formed as cake is post-treated to obtain pure Ta powder
❑ Ti from Ti(Cl)4
❑ Zr precipitation from fused salt mixture of Zr(Cl)4 + KCl + Mg
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Precipitation from a gas:
• Reactive metal powders precipitated as nano-scale particles

• Starting material is the gaseous form of the metal compound

𝟏 𝟏
𝐂𝐮𝟑𝐂𝐥𝟑 (𝐠) + 𝐇𝟐 → 𝐂𝐮 𝐬 + 𝐇𝐂𝐥(𝐠)
𝟑 𝟐
• Novel???

• Powders are generally spongy, spherical and polycrystalline

• Use ???

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Solid-solid reactive synthesis:

• solid-state reaction.

• Mixing of constituent powders → ignition →compound formation + heat.

𝐍𝐢 𝐬 + 𝐀𝐥 (𝐬) → 𝐍𝐢𝐀𝐥 𝐬 + 𝐡𝐞𝐚𝐭
• ‘T’ Control??

• If reaction heat is extracted properly → Porous end product

• Mostly used for ceramic powder production

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 Summary of various powder production methods

we must have
to draw these
two tables.

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Evaporation Techniques:
• Homogeneous nucleation from vapour phase

• Nanoscale powder

• Low ‘P’ vaporization, vapour gets supercooled away from the heat source

• Particle soot collected on cold substrate

• Cu, Co, Fe, Ag, Zn etc.

• Further modification to oxides/ nitrides etc.

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[Link]
Other Techniques for nano-powder:

• Controlled precipitation using microwave heating

• Mist spraying and evaporation….. Mostly for oxides

• Chemical methods

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