08 - Other Significant Alloys

Suranaree University of Technology May-Aug 2007
Other significant alloys

Other significant alloys
Subjects of interest
Objectives / Introduction
Lead and its alloys
Tin and its alloys
Chromium and its alloys
Cadmium and its alloys
Antimony and its alloys
Bismuth and its alloys
Lecture 8
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Objectives
Objectives
This chapter provides basic information of other
significant non-ferrous alloys such as alloys of lead,
tin, chromium, cadmium, antimony, bismuth.
This includes its source, nature, properties which
are related to its applications.
Introduction
Introduction
Apart from alloys of Al, Mg, Cu, Zn, Ti,
Ni, there are a variety of other alloys,
which have been used for other
applications with however in a smaller
extent but still important.
There are for example: Pb, Sn, Bi, Sb, Cd
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Lead and its alloys
Lead and its alloys
-
- Applications
Lead sheet
Lead sheets are used in x-ray and gamma-ray
protection, building construction of roofing and
flashing, shower pan, flooring, vibration damping
and soundproofing.
Lead pipe
Lead pipes are made from pure lead
metal (99.97% min.) or lead alloys
- Readily fabricated by extrusion.
- Excellent corrosion resistance
applications in chemical industry.
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Lead
Lead
-
- Resources
Lead (Pb) is found in many countries but mainly produced from
USA, Australia, Mexico, Canada and Germany.
In Thailand, found in Kanchanaburi (cerussite).
Normally found in the forms below (or the combination of both)
1) Lead sulphide (PbS) or called Galena or Galenite.
2) Lead carbonate (PbCO
3
) called Cerussite.
Also found in the form of anglesite (PbSO
4
) and pyromorphite
(2Pb
3
P
2
O
5
.PbCl
2
) but not commercially significant.
Normally contain Ag, Zn, Ni, Co as impurities.
Galenite
Cerussite
webmineral.com
Anglesite
Pyromorphite
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Lead
Lead Extraction of lead
Concentrated Pb ore is produced
through flotation process and it is then
roasted at T ~450-700
o
C with air blow
to reduce sulphur.
2 4 2 2
7
2 SO PbSO PbO O PbS + + +
Other reactions also occur due to the
existence of Zn.
2 2 2
3
2 4 2 2
7
2
SO FeO O FeS
SO ZnSO ZnO O ZnS
+ +
+ + +
The obtained Pb ore (with decreased amount of
sulphur) is then reduced in the blast furnace or
reverberatory by mixing with coke or iron.
Ore (PbS)
Concentration
Flotation
Roasting
At T ~ 450-700
o
C
with air blowing
Blast furnace or
reverberatory
Lead
Mixed with coke
T ~ 900
o
C
Reduce
sulphur
Pyrometallurgical process
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Lead
Lead Reduction of lead in blast furnace
FeS Pb Fe PbS
CO Pb CO PbO
CO Pb C PbO
+ +
+ +
+ +
2
Reduction of lead is carried out in
a blast furnace at T ~ 900
o
C.
The obtained ore is mixed with flux
(limestone) and coke (~10%) which
will reduce PbO or PbS into lead.
Lead blast furnace
During reduction, matte or speiss
(mixtures of sulphide of Fe and Cu)
form on top of the molten lead.
The molten lead forms at the bottom
of the furnace is then drained out.
Charge hopper
Exhaust off-take to
afterburne
Charge
Cool water
Charge hole
Average level
of charge
Shalf
www.osha.gov
Hot water
Cold water
Hot water
Slag layer
Water jacket
Working height of
charge 2.4-3.0 m
Lead spout
Dam
Drain tap
Load layer
Slag spout
Crucible
Tuyere
Diameter at Tuyeres
68 120 cm
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Lead
Lead Refining of lead
As, Bi, Sb, Sn, Cu are typical impurities in lead high
hardness but low toughness.
Removal of Sn, Sb, As is called softening by heating at
500
o
C. They will form oxides (Dross) which float on the top of
lead due to their lower densities. easily remove.
Cu is removed by mixing molten lead with PbS to give Cu
2
S
and Pb.
Pb S Cu Cu PbS + +
2
2
Bi is removed via electrolysis process using PbSiF
6
and H
2
SiF
6
acid as
electrolyte, giving pure lead at cathode and the remained Bi at anode.
Desilvering is carried out using two methods : Pattinson and Parkes.
Pattinson: High purity lead is extracted at the eutectic temperature (304
o
C).
Parkes: Stirring Zn rod in molten lead to dissolve Ag on its surface. Let it
cool down to form crust and then remove.
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Lead
Lead - Physical properties and
application
Pb
Lead
CCP
207.2
Crystal structure Cubic closed packed
Atomic number 82
Atomic weight 63.546
Density (g.cm
-3
) 11.34
Melting point (
o
C) 327.35
Boiling point (
o
C) 1740.0
82
High density.
Good corrosion resistance
Low strength but high ductility.
Lubricating properties.
Lead ingots of 99-98 % purity can be
produced with Sb, Sn, As, Fe, Bi, Cu
as impurities.
Used in batteries, chemical
applications.
www.gravitaindia.com
Lead screws
Lead alloys
Lead alloys - Classification
Lead alloys can be classified as follows:
1) Calcium-lead alloys
2) Antimony-selenium lead alloys
3) Antimony-lead alloys
4) Copper lead alloys
5) Tin-lead alloys
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Classification - Antimony lead alloys
Antimony Sb is partially soluble in lead and give a eutectic
reaction at 250
o
C at 11.2% Sb.
+ L
Hypo-eutectic structure
(<11.2%Sb) consists of phase and
eutectic phase of + + + +.
Hyper-eutectic structure
(>11.2%Sb) consists of and eutectic
phases.
Sb addition gives higher eutectic
structure more strength / hardness.
Used in batteries and cable wire coating.
Sb-Pb phase diagram
6.5% Sb (Hypo) 12.25% Sb (Hyper) 11.5% Sb (eutectic)
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Classification - Tin-lead alloys
Tin Sn can form solid solution ( phase upto 19.2% Sn) with
lead and give a eutectic reaction at 183
o
C at 61.9% Sn.
Hypo-eutectic structure
(<61.9%Sn) consists of phase and
eutectic phase of + + + +.
Hyper-eutectic structure
(>61.9%Sn) consists of and eutectic
phases.
Sn addition also gives strength and
hardness and lower T
m ,
fluidity .
Used as soldering materials.
Sn-Pb phase diagram
70% Sn 50% Sn Eutectic 60% Sn
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Tin alloys
Tin alloys - Introduction
Tin is found in the form of oxide (SnO
2
) as vein tin or
stream tin. Its colour is in white and grey.
Found in Malaysia, Indonesia, (Thailand), Myanmar, China,
Australia. Note: Most resources are almost used up.
Easily extracted because it is already in its oxide form.
Used for applications such as in soldering metals.
Tin oxide
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Tin alloys
Tin alloys - Extraction
Ore(SnO
2
)
Concentration
Mixing with
coke and flux
T ~ 1350
o
C
Blast furnace or
reverberatory
Tin
2 2
2 2
2
2 2
2 2
2
CO Sn C SnO
CO Sn CO SnO
CO C CO
CO O C
+ +
+ +
+
+
The ore is first concentrated and then mix with
coke and flux (CaCO
3
) in the blast furnace
(reverberatory) at T~1350
o
C.
CaCO
3
will decompose at 1350
o
C to give CaO,
which will catch high melting point oxides (SiO
2
,
FeO) to form slag (low T
m
).
Molten tin at the bottom of the furnace is
drained out for further refining while slag on its
top surface is skimmed out Sn will be
separated again.
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Tin alloys
Tin alloys - Refining
Fire refining
Electrolytic refining
For tin with Fe <1%, fire refining
is carried out at tins melting point
232
o
C to give pure tin at the
bottom of the furnace.
Fe will from FeSn
2
compound
and can be separated from
molten tin (<0.01%Fe).
Give high purity of tin but expensive.
For a higher purity, poling
process (using fresh lump of
wood stirring in boiling tin)
allows impurities to float to the
surface and form oxides (slag).
If the impurity is Pb, flux
(SnCl
2
) is added at T~245
o
C to
form PbCl
2
(dross), which also
floats to the surface. Dross will
be skimmed out later.
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Tin
Tin - Physical properties
Sn
Tin
118.7
Crystal structure FC Tetragonal (white tin)
Cubic (grey tin)
Atomic number 50
Atomic weight 118.7
Density (g.cm
-3
) 7.298 (white tin)
5.765 (grey tin)
Melting point (
o
C) 231.9
o
C
50
High corrosion resistance.
Low strength but high ductility not suitable for
structural materials.
Lubricating properties.
Transformation from white to
grey tin occurs at T = 13.2
o
C,
giving a change in density from
7.3 to 5.76 g/cm
-3
. tin pest.
Tin pest
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Tin
Tin - Applications
Tin is used as coating for structural steels for corrosion protection.
Used as an alloying element.
Soldering materials and in electrical applications.
Tin or tin foil for food containers and wrapping.
Tin alloys are also used as vases, candle stands, jewellery.
Electrical
applications
Soldering
Tin foils for capacitors
www.winter-wolff.com
Steel can coated with tin.
Tin as jewellery
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Tin alloys
Tin alloys Classification
Tin alloys are used as soldering materials.
- 30-50% Pb Sn alloy
- 5% Sb Sn alloy
- 5% Ag Sn alloy
Tin alloys (pewter) are used as vases, candle stands, etc.
- 7% Sb 2% Cu alloys (40% ductility, 9.5 HBN).
Tin alloys are used as bearing called Babbit
- 10-15% Sb 3-4% Cu 60-90% Sn alloys.
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Cadmium
Cadmium
Cadmium has a bluish white colour and appears
in a form of CdS.
Normally obtained from zinc extraction process.
Hardness Sn<Cd<Zn. Good toughness, readily
rolled into plates or wires at RT.
Used in automatic fire extinguishers, electrical
fuses, safety plugs.
Alloyed with Sn to produce soldering materials,
bearing.
Crystal structure HCP
Density (g.cm
-3
) 8.65
Melting point (
o
C) 320
o
C
Boiling point (
o
C) 769
o
C
Cd
Cadmium
HCP
112.41
48
Batteries Tapany Udomphol
Antimony
Antimony Physical properties and
applications
Antimony has a silvery white colour and found as stibnite Sb
2
S
3
.
Hard and brittle and cannot be deformed at RT.
React with oxygen at high temperature, giving Sb
2
O
3
(white powder).
Used as alloying element in Sn and Pb alloys, providing better
fluidity and hardness.
Applications: storage battery plates, soldering materials, shrapnel
bullets and bearing or babbit.
Sb
Antimony
121.76
Crystal structure Trigonal
Atomic number 51
Density (g.cm
-3
) 6.62
Melting point (
o
C) 630
o
C
Boiling point (
o
C) 1140
o
C
51
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Antimony
Antimony - Extraction
Ore(Sb
2
S
3
)
Liquation
Roasting
Blast furnace
Sb
T ~ 500-600
o
C
Antimony ore is concentrated by
liquation process (heating at 500-600
o
C)
to give low T
m
antimony (85-90%)
separating from the ore.
Roasting at 500
o
C to convert to oxide
Sb
2
O
4
, which is then reduced to Sb metal
by using charcoal with flux (Na
2
CO
3
) in
the blast furnace.
S, Pb and Fe appear as impurities in the
obtained Sn metal. good enough for
alloying.
Higher purity is achieved by electrolytic
process.
T ~ 500
o
C
Charcoal
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Bismuth
Bismuth Physical properties and
applications
Bismuth is found as native Bismuth in nature or
Bismuth ocher or Bismite (Bi
2
O
3
).
Low melting point used as alloying elements to
lower T
m
, soldering materials and thermoelectric
applications -fuses.
Provide thermal expansion during solidification.
Hard and brittle similar to Sb.
Bi
Bismuth
209
Crystal structure Monoclinic
Atomic number 83
Atomic weight 209
Density (g.cm
-3
) 9.80
Melting point (
o
C) 271
o
C
Boiling point (
o
C) 1436
o
C
83
Fuses
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Bismuth
Bismuth - Extraction
Bismuth ore (Bi
2
O
3
) is reduced using
charcoal and CaCO
3
with fluoride and
Na
2
CO
3
as flux.
Roasting should be applied if the ore is a
sulphur type.
Higher purity Bi is produced by liquation
to give molten Bi at the bottom of the
furnace.
For higher purity, bismuth is dissolved in
nitric acid to give Bi(NO
3
)
3
and then
precipitate as Bi(OH)
2
NO
3
. washed and
heated to give pure Bi oxide. reduced to
give Bi metal.
Ore(Bi
2
O
3
)
Reduction
Liquation
Bi
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References
References
. a.a. +..+..+ . :-. u.uu+..a..a+a. ISBN
974-582-155-1.
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08 - Other Significant Alloys

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Suranaree University of Technology May-Aug 2007

Other significant alloys

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