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MTE 449 Powder Metallurgy

Chapter 3 Chemical and Electrochemical Production of powders


Nagy El-Kaddah

Electrolytic Production of Powders

This powder production route is used to produce high purity metal powders Applications include

Basic metals: Precious metals: Reactive metals:

Iron, copper, aluminum, chromium, zinc and magnesium Niobium, tantalum and silver Titanium and palladium

It involves two operations


Electrodeposition of the metal in spongy or powdery state Milling of the deposited metal

Electrolytic powders are in tens of microns size range, and typically have irregular, porous and dendritic shapes with poor packing characteristics

Electrodeposition of Metals

Fundamentals

DC power Source Current (I) + -

Electrochemical reactions
Cathode: A+ + e = A Anode: B = B+ + e Overall: B + A+ = A + B+

Electrons (e)

Free Energy of reactions

Electrolyte

Electrode: Goele = - n F Eele Eele = Eoele + RT/nF ln k Overall: Go = - n F E = (EoB - EoA) + RT aB+/ aA+ E = cell potential; Eele = electrode potential; k =Equilibrium constant n=valance of ion; F = Faradays number (96495 C/ g-equivalent)

Anode

Cathode

Typical standard potentials Eoele (v)


Cu2+ + 2e = Cu Fe2+ + 2e = Fe EoCu = 0.34 EoFe = - 0.44

Theoretical deposition rate, current efficiency


RA theortical = I MWA F nA gm / s

Efficiency =

RA RA theortical

100

Electrodeposition of Metals (cont.)

Technology

Electrodeposition is in essence a refining process of impure metal ingots It involves dissolution of the impure metal from the anode in an electrolyte and depositing the dissolved metal ions on the cathode. Industrial electrorefining cells use a set of 20 to 40 anodes and cathodes connected in parallel to the power supply. Cell tanks are 3-4 m long, 1m wide and 1m deep The cell voltage is low, typically between 1 and 2 volts, while the current density is quite high ranging from 300 to 4000 A/m2

Electrodeposition of Metals (cont.)

Process variables

Cell current and voltage Cathode-anode gap thickness Electrolyte concentration and temperature Intensity of bath stirring

Operating conditions favoring spongy and powdery deposits


High current density Large cathode-anode gap High bath temperature Low ion concentration of the electrolyte Minimal electrolyte agitation

Chemical Powder Production Techniques


Almost all materials can be produced in a powder form by chemical reactions Characteristics of the produced powder depends on state (gas, solid, liquid) and form of the reacting materials Chemical techniques are generally classified according to type reactions
Gas-solid reduction reactions Thermal decomposition of gaseous species Chemical precipitation in solutions Gas-Gas reactions Solid-solid reaction

Chemical Powder Production Techniques (cont.)


Gas-Solid reduction reactions
It is used for production of metal powders from oxides The reducing gas could be either hydrogen, carbon monoxide or both Typical reduction reactions NiO (s) + H2 (g) = Ni (s) + H2O (g) WO2 (s) + 2 H2 (g) = W (s) + 2 H2O (g) Powder production by this method is generally carried out in a fluidized bed reactor The size and shape of the produced powder are essentially that of the metal oxide The main advantage of this method is high production rate

Chemical Powder Production Techniques (cont.)


Thermal decomposition of gaseous species
It involve dissociation of gaseous metal compounds to metal by heating in presence of a catalyst Metal carbonyls are commonly used as precursor in this method Fe(CO)5 (g) = Fe (s) + 5 CO (g) Ni (CO)4 (g) = Ni (s) + 4 CO (g) The particle size is dictated by nucleation and growth kinetics of the condensed phase Carbonyl decomposition produce particles of sizes between 0.2 and 20 m Carbonyl processing is used to Fe, Ni, Cu, Cr, Rd, Co and Pt powders. The main disadvantage of carbonyl powder production technique is the toxicity of carbonyls

Chemical Powder Production Techniques (cont.)


Chemical precipitation in solutions
1. 2. 3. Precipitation of a dissolved metal in nitrate, chloride or sulfate solutions can be achieved by Reaction with another ionic solution
AgNO3 (l) + K2SO3 (l) = Ag (s) + 1/2 K2SO4 (l)+ KNO3 (l) + 1/2 SO2 (g)

Reaction with hydrogen


Co2+ (l) + H2 (g) = Co (s) + 2 H+ (l)

Reaction with solid metal particles


Cu2+ (l) + Zn (s) = Cu (s) + Zn2+ (l)

Particle size in the first 2 methods depends on nucleation and growth kinetics, typically in 1 m size range The powder produced by the third method has the same size of the reducing metal, and porous. This chemical processing apply to all metals including refractory and reactive metals

Chemical Powder Production Techniques (cont.)


Gas-Gas reactions
Gas phase reactions are used to produce extremely fine powders (submicron particles) of all type of materials (metals, oxides, carbides and nitrides). CuCl (g) + 1/2 H2 (g) = Cu (s) + HCl (g) Chemical reaction between gaseous species is promoted using electron beams, lasers, plasmas or mega frequency electromagnetic fields. This type of reactions is only suitable for production of intermetallic powders due to the high heat of the reaction in order to fuse metal particles Ni (s) + Al (s) = NiAl (s) The process involves mixing the constituents in a loosely packed bed and igniting the bed to initiate the reaction. This followed by milling the produced cake of the intermetallic. This technique is used to produce NiTi, Ni3Al, TiAl, TiC and WC powders

Solid-Solid reactions