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Lec 3

The document discusses reasons for adopting vacuum in metallurgical applications. Vacuum is used to process refractory metals and alloys as they are highly reactive with oxygen and nitrogen. Applying vacuum decreases gas pressure and displaces chemical equilibria to reduce impurity contents in metals. Vacuum also reduces reactions between molten metals and residual atmospheres.

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muhammad tayyab
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39 views10 pages

Lec 3

The document discusses reasons for adopting vacuum in metallurgical applications. Vacuum is used to process refractory metals and alloys as they are highly reactive with oxygen and nitrogen. Applying vacuum decreases gas pressure and displaces chemical equilibria to reduce impurity contents in metals. Vacuum also reduces reactions between molten metals and residual atmospheres.

Uploaded by

muhammad tayyab
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Vacuum Technology

Applied to

Metallurgical Applications
Reasons for adopting

Vacuum in Metallurgy

e.g Refractory metals / alloys


Reasons for adopting Vacuum in metallurgy

They are highly reactive with oxygen


and nitrogen .

Nb, Ta, Zr, Ti, Hf are refractory metals


and have high melting points .

•Their processing has to be carried out


under high vacuum conditions only.
Reasons for adopting Vacuum contd
•By lowering gas pressure in the reaction vessel, the concentration gradient
between gaseous reaction products & their dissolved components is increased
so that the reaction rate of degassing or volatizing is raised.
• By pumping off the gaseous products, chemical equilibria are displaced in
the direction of lower impurity contents in metals .
When the space above the liquid is saturated with vapour particles,
you have this equilibrium occurring on the surface of the liquid:
Liquid vapour H +ve

The forward change (liquid to vapour) is endothermic. It needs heat to


convert the liquid into the vapour.
According to Le Chatelier, increasing the temperature of a system in a
dynamic equilibrium favours the endothermic change.
That means that increasing the temperature increases the amount of
vapour present, and so increases the saturated vapour pressure.

Decreasing the vapours by applying vacuum takes away the vapours


thereby shifting equilibrium to right side , alteranitevely same effect can be
achieved at lower temp

Pump
Reasons for adopting Vacuum contd

•The low gas pressure in vessel reduces the extent of reactions between
the molten metals and the residual atmosphere to zero.

CHEMISTRY OF ZIRCONIUM
When Zr burns in air, the fire provides an extremely brilliant white
flame. Zirconium oxide and nitride are formed as per the following
equations :
Zr(s) + O2(g) → ZrO2(s) ∆Hf 298 =-258 , ∆Gf 298 =- 244 , in kcal/mole of oxide

Equilibrium constant, expressed as logKf for the above reaction is 179 and
the free energy of formation at elevated temperatures are ∆G f 1000 = - 216,
∆Gf 1500 = - 212, ∆Gf 2000 = - 173, kcal/mole of oxide, indicating that the
reaction is more favorable at lower temperatures.
2Zr(s)+ N2(g)→ 2 ZrN (s) ∆Hf 298= - 86 , ∆Gf 298=- 80 in kcal/mole of nitride

Equilibrium constant, expressed as logKf for the above reaction is 55 and


the free energy of formation at elevated temperatures are

∆Gf1000= - 64, ∆Gf 1500 =- 55, kcal/mole of oxide


Reasons for adopting Vacuum contd

Vapor pressures & Separation factors The separation factor


0.5 improves with decrease in
Pb 0.4
pressure resulting in higher
1.2
Pb
%
Zn purification.
p Zn/p Pb

1%
Zn 0.3 S F

Pb
0.5 0.2
%
Zn If we carry out purification at lower temp
then S F Is higher which can be achieved
0.1 by reducing pressure above molten liquid

500 1000 e.g at 1000 c SF is 0.1 where as at 500 C


Temp in 0C it is 0.4

Melting
10mm 100mm 400mm 2 atm
1mm 760mm point

Pb 970 1160 1420 1630 1740 1880 326

Zn - 590 730 840 907 970 420


Reasons for adopting Vacuum contd

ZrO2(s) + 2C (s) --- Zr (s or l) + 2 CO

ZrO2(s) + 2C (s) --- ZrC ( s or l) + 2CO

By improving vacuum equilibrium can be disturbed more effectively


there by taking away CO hence effective reaction

At higher temp ZrC formation is less favored, but CO pressure increases


Reasons for adopting Vacuum contd

Refining in a Vacuum using carbon

*The counter part of de-oxidation with carbon .


* In this process the affinity of C for O is made use of.
* This affinity is very high at low pressures & low O
levels compared with other de-oxidising agents.
Oxygen content

p1>p2
Standard pressure p1

Reduced pressure p2

Carbon content
Reasons for adopting Vacuum contd

Concentration ratio of liberated


Oxygen and Metal atoms during
degassing of Niobium and Tantalum

1.7
Atom ratio O/Nb and O/Ta

1.5
O / Ta
O / Nb
1.3

1.1
1600 1800 2000 2200 2400
Temperature (0C)

Therefore by applying better vacuum temp is low & O/M ratio improves
Reasons for adopting Vacuum contd
In processing of metals use of water-cooled crucibles excludes any
reaction between molten liquid and crucible(skull melting) and vacuum
excludes any reaction between molten metal and atmosphere above
molten liquid .
Electron Beam

Vacuum = 10-4mbar

Horizontally fed rod


M

Sub
CO ox
H2
N2 Super heated molten pool

Water cooled copper hollow


crucible

Water cooled copper retraction


device
Downwards retraction
of Cast Ingot

Note: Molten pool can be super heated and exposed to very high vacuum, for any desired
dwell time , to reduce the impurities level to equilibrium concentrations.

Electron Beam Drip Melting Process


(Purification Principles)

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