Metals

Metallurgy How we get metals Bonding and structure of metals Alloys, composites Properties of metals and alloys Mechanical properties Electrical properties

OCCURRENCE OF METALS
Most metals are found in minerals. 1) Elemental Form e.g. Ag, Au, Pt noble metals. 2) Aluminosilicates and Silicates Metal + Al, Si, O e.g. Beryl = Be3Al2Si6O18 Hard to extract metals. 3) Nonsilicate Minerals Oxides Al2O3, TiO2, Fe2O3 Sulfides PbS, ZnS, CuFeS2 Carbonates CaCO3

Steps in Metallurgy
1) Preliminary treatment to concentrate ore: Floatation. Hindered settling Magnetic separation 2) Further purification and reduction to obtain the metal in its elementary state: Hydrometallurgy leaching. Pyrometallurgy roasting, smelting. Electrometallurgy. 3) Final purification and refining of the metal.

Hydrometallurgy
Metal is extracted from ore using aqueous reactions
Leaching: a metal is selectively dissolved Dissolution agent: acid, base, salt.

Example: Dissolve Au by forming complex ion with CN! 4Au(s) + 8CN!(aq) + O2(g) + 2H2O(l) " 4[Au(CN)4]!(aq) + 4OH!(aq) Kf[Au(CN)2]! = 2x1038 The gold is then obtained by reduction: 2Au(CN)2!(aq) + Zn(s) " Zn(CN)42!(aq) + 2Au(s)

Hydrometallurgy of Aluminum
Aluminum is the second most useful metal. Bauxite: Al2O3.xH2O. primary ore for Al impurities: SiO2 Fe2O3

Electrometallurgy
Electrometallurgy is the process of obtaining metals through electrolysis. Two different starting materials: molten salt or aqueous solution.

Bayer Process
Bayer process: bauxite (~ 50 % Al2O3) is concentrated to produce aluminum oxide. Dissolve bauxite in strong base (NaOH) at high T, P Al2O3 dissolves [Al(H2O)2(OH)4]!
hydrated metal complex

Electrometallurgy of Aluminum
Hall process electrolysis cell is used to produce aluminum.
Problem: Al2O3 melts at 2000C and it is impractical to perform electrolysis on the molten salt. Hall: use purified Al2O3 in molten cryolite (Na3AlF6, melting point 1012C). Anode: C(s) + 2O2!(l) " CO2(g) + 4e! Cathode: 3e! + Al3+(l) " Al(l) The graphite rods are consumed in the reaction.

Filter out solids Fe2O3, SiO2 do not dissolve Lower pH, Al(OH)3(s) precipitates Take advantage of amphoteric nature of Al

Electrometallurgy of Al
The Hall Process
To produce 1000 kg of Al, we need 4000 kg of bauxite, 70 kg of cryolite, 450 kg of C anodes and 56 # 109J of energy.

Electrometallurgy
Electrorefining of Copper
Because of its good conductivity, Cu is used to make electrical wiring. Impurities reduce conductivity, therefore pure copper is required in the electronics industry.

Pyrometallurgy
Pyrometallurgy: using high temperatures to obtain the free metal. Several steps are employed: Calcination is heating of ore to cause decomposition and elimination of a volatile product: PbCO3(s) " PbO(s) + CO2(g) Roasting is heating which causes chemical reactions between the ore and the furnace atmosphere: 1. Burns off organic matter. 2. Converts carbonates and sulfides to oxides: 2 ZnS(s)+ 3O2(g) "2ZnO(s) + SO2(g) 3. Less active metals are often reduced HgS(s) + O2(g) " Hg(l) + SO2(g)

The Pyrometallurgy of Iron

sources of iron: hematite Fe2O3 and magnetite Fe3O4. Iron Ore: Fe2O3 and SiO2

Add limestone and coke Coke is coal that has been heated to drive off the volatile components.

The blast furnace

Pyrometallurgy of Fe
Reactions
2C(s) + O2(g) " 2CO(g) + heat heat + C(s) + H2O(g) " CO(g) + H2(g) Fe3O4(s) + 4CO(g) " 3Fe(l) + 4CO2(g) Fe3O4(s) + 4H2(g) " 3Fe(l) + 4H2O(g) Coke: 1) heats furnace 2) reduces iron Why is limestone (CaCO3) added?

Pyrometallurgy of Fe
At high T CaCO3 " CaO + CO2 CaO
oxide basic

+ SiO2 " CaSiO3(l)

slag oxide acidic

Metal + nonmetal "

Limestone (CaCO3) removes SiO2 (and other) impurities slag floats on Fe(l); protects it from oxidation by O2 Slag: cement cinder block building materials

Pyrometallurgy of Iron
Product in blast furnace: pig iron brittle; not strong Bessemer Converter O2 (g) bubbled through molten iron to oxidize remaining impurities CaO slag still present to remove impurities Alloying elements added as liquid iron is being removed.

Properties of metals
Metals (75% of elements) Lustrous (reflect light) (almost) all solids malleable & ductile good conductors of heat and electricity oxides are basic ionic solids aqueous cations (n+) reactivity increases downwards in family

Bonding in metals
Free Electron Model
Metals are positive ions in sea of nearly free electrons Electrons bond metal ions together but are free to roam the crystal lattice. Explains malleability, ductility , and high electrical and thermal conductivity.

STRUCTURE and PROPERTIES of METALS

Important physical properties of pure metals: malleable, ductile, good conductors of heat and electricity. Metals are crystals every atom has 8 or 12 neighbors. There are not enough electrons for the metal atoms to make electron pair bonds to each neighbor.

Metal Crystal Structures

Body-centered cubic (bcc) 8 nearest neighbors Not close packed

Malleability of Metals and Alloys

Some metals are soft and ductile (Au, Ag, Cu, Al, etc.) Others are hard (Fe, W, Cr, etc.) Why? Crystal structure is important. Two types: body centered cubic (bcc) - 8-coordinate - hard close packed (fcc and hcp) -12-coordinate - soft

Close packed (hexagonal or cubic) hcp ccp

Close-packed planes slip easily

Non-close packed - speed bumps

Cu (fcc) Zn (hcp)

CuZn alloy (brass)

Mechanical Properties of Metals and Alloys

Hypothetical situation: Upon graduation, you go to work for Boeing. Your job select a high-strength Al alloy for jet airplanes.
Airplane: 500 tons } 50 tons cargo 150 tons plane structure 300 tons fuel

Defects in Metallic Crystals

Defects are responsible for important mechanical properties of metals: malleability, yield stress, etc. Non-directional bonding, large number of nearest neighbor atoms " metallic structures readily tolerate mistakes

If you can triple the alloy strength, you can triple cargo load (to 150 tons). Material Tensile Yield Stress (psi) pure (99.45%) annealed Al 4 x 103 pure (99.45%) cold drawn Al 24 x 103 Al alloy - precipitated, hardened 50 x 103 big improvement

But, perfect single crystal Al has a yield stress of ca. 106 psi!

vacancy (missing atom) point defect Not important

dislocation (extra plane of atoms) line defect Very important

Dislocations Move Under Stress

Hardening of Alloys
Structural alloys - e.g., girders, knife blades, airplane wings Need to minimize movement of dislocations. How?

shear force

Key point: Moving a dislocation breaks/makes a line of metal-metal bonds (easy) Shearing a perfect crystal means we have to break a plane of bonds (requires much more force)

1. Use annealed single crystals (expensive) Some specialty applications e.g. jet turbine blade Impossible for large items (airplane wings, bridges) 2. Work hardening - moves dislocations to grain boundaries planar defect (stronger under stress) Cold working or drawing of a metal increases strength and brittleness (e.g., iron beams, knives, horseshoes)

Hardening of Alloys (contd.)

Work Hardening and Annealing have opposite effects Annealing: crystal grains grow, dislocations move (metal becomes more malleable) 3. Alloying homogeneous or heterogeneous Impurity atoms or phases pin dislocations.

ALLOYS
Alloys: Mixtures of metals - often have improved physical properties
1) Homogeneous (Solution) alloy Mixed at the atomic level 2) Heterogeneous alloy non-homogeneous dispersions. (e.g. pearlite steel has two phases: almost pure Fe and cementite, Fe3C). 3) Intermetallic compounds compounds of two different metals having definite compositions: Examples Cr3Pt razor blades. Ni3Al jet engines, lightweight and strong. Co5Sm permanent magnets in headsets. Au3Bi, Nb3Sn superconductors for low temperature, high field magnets

SOLUTION ALLOYS
There are two types of solution alloy:
Substitutional alloy when one metal substitutes for another in the structure. atoms must have similar atomic radii elements must have similar bonding characteristics.

Iron and Steels

Below 900oC, iron has bcc structure - hard as nails Above 900oC, iron is close packed (fcc) - soft Can be worked into various shapes when hot Steelmaking: Carbon steel contains ~ 1% C by weight (dissolves well in fcc iron but not in bcc) Slow cooling (tempering): fcc Fe/1%C " mixture of bcc Fe and Fe3C (pearlite) Fe3C (cementite) grains stop movement of dislocation in high carbon steel - very hard material

Interstitial alloy when a non-metal is present in the interstices of the metal. Interstitial atoms are smaller The alloy is much stronger than the pure metal (increased bonding between nonmetal and metal). Example steel (contains up to 3 % carbon).

Amorphous (Glassy) Alloys

STEELS
Steel: Fe (pig iron) + small amounts of C Mild Steel: <0.2% C malleable and ductile used in cables, nails, and chains. Medium Steel: 0.2-0.6% C tough used in girders and rails. High Carbon Steel: 0.6-1.5% C very tough used in knives, tools, and springs. Stainless Steel: 73% Fe, 18% Cr, 8% Ni, 1% C.

Metals are typically polycrystalline Amorphous alloys have superior mechanical properties because dislocations cannot move.

http://www.its.caltech.edu/%7Evitreloy/development.htm

Bonding in Metals
Band Theory
Atomic orbitals (AO) mix to form molecular orbitals (MO). Start with 2 AO, end with 2 MO Start with n AOs, end up with n MOs In metals energy difference between orbitals in valence band is small. Orbital form a continuous band of allowed energy states.

Conduction and Insulation

METAL: Conductor
Valence electrons do not fill available orbitals (not enough electrons)

Insulator or semiconductor
Valence band is full (or completely empty). Energy gap separates valence band from empty orbitals.

Bonding in Metals
Insulators: The energy gap is very large in some solids: these solids will be poor electrical conductors. Semiconductors: the energy gap may be smaller in some solids. The conductivity of semi-conductors can be increased with T, or applied fields.

SEMICONDUCTORS
Add impurities (dopants) to semi-conductor
If impurities donate extra electrons, then the semiconductor is n-type e.g. P impurities in Si. If impurities accept electrons, then the semiconductor is p-type e.g. B impurities in Si. n-type: negative charge carriers (electrons). p-type: apparent positive charge carriers (holes).

Silicon
Properties: shiny, silvery gray brittle Poor thermal conductor SEMI-METAL Uses: alloy (with Al, Mg) Silicone polymers Electronic applications for these applications very pure silicon (<1ppb) is required.

Zone refining to get pure Si

Diodes
A diode is a semiconductor with a p-type material bonded to an n-type material. Solar cells (photovoltaics) and light emitting diodes (LEDs) are both diode devices.

Diodes
A diode allows current to flow in only one direction Electrons can flow from n-type to p-type under forward bias In a solar cell, light excitation makes current flow in the opposite direction.

When no current flows Current flows when the diode is forward biased

Light Emitting Diode

LEDs: Light Emitting Diodes

LEDs are small light bulbs that produce useful light from the from the flow of electrons through a semiconductor diode. If the semiconductor used is a silicon based semiconductor the light produced is infrared. Used in TV remote controls LEDs producing visible light are typically made from doped AluminumGallium-Arsenide (AlGaAs) conductor. Changing the dopants changes the size of the depletion zone and the color of visible light produced

When electrons combine with holes, light is emitted. The energy of light (E = h$) is the same as the band gap energy Eg The band gap energy depends on the material used to make the diode.

LED Materials
Wavelength nm 700 660 630 610 590 565 555 Color red red red Material and structure of LEDs GaP: Zn-O/GaP GaAI0.35 As/GaAs GaAs0.35PO.65: N/GaP

LEDs: Light Emitting Diodes

orange GaAs0.25Po.75: N/GaP yellow green green GaAs0.15PO.85: N/GaP Gap: N/GaP GaP/GaP

More energy efficient than incandescent lighting LEDs producing visible light are typically made from doped Aluminum-Gallium-Arsenide (AlGaAs)

Where are LEDs used?

Ceramics

Ceramics
inorganic, nonmetallic, solids, can be covalent network and/or ionic bonded Properties: Crystalline or amorphous (e.g. glass), hard, brittle, stable to high temperatures, less dense than metals, more elastic than metals, very high melting. Examples: alumina (Al2O3), carbides (SiC, Ca2C), Oxides (BeO, ZrO2, Al2O3) Nitrides (BN).

Superconductivity
Superconductors show no resistance to flow of electricity. Superconducting behavior starts below the superconducting transition temperature, Tc. Meissner effect: permanent magnets levitate over superconductors. The superconductor excludes all magnetic field lines, so the magnet floats in space.

Superconducting Ceramic Oxides

Diodes
The depletion zone can be removed when the diode is connected to a battery. The n-type material is connected to the negative portion of a battery. The p-type material is connected to the positive portion of the battery.

COPPER CONTAINING ORES

Copper containing ore (CuFeS2) is stirred with aqueous H2SO4 + O2 2CuFeS2(s)+2H+(aq)+SO42!(aq) + 4O2(g) " 2Cu2+(aq) + 2SO42-(aq) + Fe2O3(s) + \ / + 3S(s) + H2O 2CuSO4(aq) %

Electrolyzed to Cu

Electrometallurgy
Electrorefining of Copper
Slabs of impure Cu are used as anodes, thin sheets of pure Cu are the cathodes. Acidic copper sulfate is used as the electrolyte. The voltage across the electrodes is designed to produce copper at the cathode. The metallic impurities do not plate out on the cathode. Metal ions are collected in the sludge at the bottom of the cell.

METALLURGY
Metallurgy is the science and technology of extracting metals from minerals. There are five important steps: Mining getting the ore out of the ground Concentrating preparing it for further treatment Reduction to obtain the free metal in the zero oxidation state Refining to obtain the pure metal Mixing with other metals to form an alloys.