Phase Diagrams Material Science

MSE 280: Introduction to Engineering Materials D.D.
Johnson 2004,2006-2008
1
Phase Diagrams
MSE 280: Introduction to Engineering Materials D.D. Johnson 2004,2006-2008
2
Temperature vs. composition behavior of the various
alloy constitutes the phases.

Allows design and control of heat treatment by controlling
equilibrium and non-equilibrium structure.

Structure (phases and microstructure) often controls properties
of materials, and, therefore, depends on thermal history.
Objectives:
Read and evaluate phases present at T.
Determine composition of phases and phase fraction.
Know difference between types of reactions, e.g., eutectic, eutectoid,
proeutectoid.
3
Phase Diagrams: Issues to Address
When we combine two elements, what equilibrium
state do we get?
In particular, if we specify...
--a composition (e.g., wt%A - wt%B), and
--a temperature (T)
then...
How many phases do we get?
What is the composition of each phase?
How much of each phase do we get?
Solid-solution
Phase
Ordered
Phase
Phase B
Phase A
Nickel atom
Copper atom
4
Solubility Limit in Phase Diagram
Solubility Limit:
Max concentration for which
only a solution occurs.
Ex: Water-Sugar
Q: What is solubility limit at 20
o
C?
Answer: 65wt% sugar.
If C
o
< 65wt% sugar: syrup
If C
o
> 65wt% sugar: syrup + sugar.
Solubility limit increases with T:
e.g., if T = 100C, solubility limit = 80wt% sugar.
Sugar/Water Phase Diagram

S
u
g
a
r

T
e
m
p
e
r
a
t
u
r
e

(
C
)

0 20 40 60 80
100
C
= Composition (wt% sugar)
L
(liquid solution
i.e., syrup)
Solubility
Limit
L
(liquid)
+
S
(solid
sugar) 20
4 0
6 0
8 0
10 0

W
a
t
e
r

Adapted from Fig. 10.1,
Callister & Rethwisch 3e.
5
Components and Phases
Components: elements or compounds that are mixed initially
(e.g., Al and Cu)
Phases: physically and chemically distinct material regions
that result (e.g., a and b).
Aluminum-Copper Alloy
6
Temperature (T) and Composition (C) Effects
Changing T can change # of phases: path A to B.
Changing C
o
can change # of phases: path B to D.
water- sugar
system
70 80 100 60 40 20 0
T
e
m
p
e
r
a
t
u
r
e

(
C
)

C = Composition (wt% sugar)
L
( liquid solution
i.e., syrup)
20
100
40
60
80
0
L
(liquid)
+
S
(solid
sugar)
D (100C,C = 90)
2 phases
B (100C,C = 70)
1 phase
A (20C,C = 70)
2 phases
7
Criteria for Solid Solubility: recall Hume-Rothery rules
Crystal
Structure
electroneg r (nm)
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278
Both have the same crystal structure (FCC) and have
similar electronegativities and atomic radii (W. Hume
Rothery rules) suggesting high mutual solubility.
Simple system (e.g., Ni-Cu solution)
Ni and Cu are totally soluble in one another for all proportions.
8
Cu-Ni Phase Diagram: T vs. c (wt% or at%)
Tell us about phases as function of T, C
o
, P.
For this course:
--binary systems: just 2 components.
--independent variables: T and C
o
(P = 1atm is always used).
wt% Ni
20 40 60 80 100 0
1000
1100
1200
1300
1400
1500
1600
T(C)
L (liquid)
o
(FCC solid
solution)
2 phases:
(liquid)
(FCC solid solution)
3 phase fields:
L
L +
o
o
-- isomorphous
i.e., complete
solubility of one
component in
another; a phase
field extends from
0 to 100 wt% Ni.
9
Phase Diagrams: # and types of phases
Rule 1: If we know T and C
o
, then we know:
--the types of phases present.
Examples:
A(1100C, 60 wt% Ni):
1 phase: o
B (1250C, 35 wt% Ni):
2 phases: L + o
wt% Ni
20 40 60 80 100 0
1000
1100
1200
1300
1400
1500
1600
T(C)
L (liquid)
o

(FCC solid
solution)
B

(
1
2
5
0
C
,
3
5
)

A(1100C,60)
Cu-Ni
phase
diagram
10
Phase Diagrams: composition of phases
o
, then we know:
--the composition of each phase.
wt% Ni
20
1200
1300
T(C)
L (liquid)
o
(solid)
30 40 50
Cu-Ni
system
T
A

A
35
C
0
32
C
L
D
T
D
tie line
4
C
o
3
B
T
B
Examples:
At T
A

= 1320C:
Only Liquid (L) present
C
L
= C
0

( = 35 wt% Ni)
At T
B

= 1250C:
Both o and L present
C
L
= C
liquidus
( = 32 wt% Ni)
C
o
= C
solidus
( = 43 wt% Ni)
At T
D

= 1190C:
Only Solid (o) present
C
o
= C
0
( = 35 wt% Ni)
Consider C
0
= 35 wt% Ni
11
Phase Diagrams: wt. fraction of phases
0
, then can determine:
-- the weight fraction of each phase.
Examples:
At T
A
: Only Liquid (L) present
W
L
= 1.00, W
o
= 0

At T
D
: Only Solid ( o
) present
W
L
= 0, W
o
= 1.00
At T
B
: Both o and L present
73 . 0
32 43
35 43
=
=
= 0.27
W
L

=
S
R + S
W
o

=
R
R + S
Consider C
0
= 35 wt% Ni
wt% Ni
20
1200
1300
T(C)
L (liquid)
o
(solid)
3 0 4 0 5 0
Cu-Ni
system
T
A
A
35
C
0
32
C
L
B
T
B
D
T
D
tie line
4
C
o
3
R S
W = wt. fraction of phase out of whole.
12
The Lever Rule
Sum of weight fractions:
Conservation of mass (Ni):
Combine above equations:

W
L
+W
o
=1

C
o
=W
L
C
L
+W
o
C
o
moment equilibrium:

1 W
o
solving gives Lever Rule

W
L
R= W
o
S
wt% Ni
20
1200
1300
T(C)
L (liquid)
o
(solid)
3 0 4 0 5 0
B
T
B
tie line
C
0

C
L
C
o

S R
13
The Lever Rule: an interpretation
M
L
M
o

R S

M
o
x S = M
L
x R
Tie line connects the phases in equilibrium with
each other also sometimes called an isotherm
wt% Ni
20
1200
1300
T(C)
L (liquid)
o
(solid)
3 0 4 0 5 0
B
T
B
tie line
C
0

C
L
C
o

S R
What fraction of each phase?
Think of tie line
as a lever
L
L
L L
L
L
C C
C C
S R
R
W
C C
C C
S R
S
M M
M
W
=
+
=
=
+
=
+
=
o
o
o
o
o
0 0

14
Phase and Microstructure (equilibrium)
Example: Cooling in Cu-Ni Binary
wt% Ni
20
120 0
130 0
3 0 4 0 5 0
110 0
L (liquid)
o
(solid)
T(C)
A
35
C
0

L: 35wt%Ni
46
35
43
32
o: 43 wt% Ni
L: 32 wt% Ni
B
o: 46 wt% Ni
L: 35 wt% Ni
C
E
L: 24 wt% Ni
o: 36 wt% Ni
24
36
D
Consider microstuctural
changes that accompany
the cooling of a
C
0
= 35 wt% Ni alloy
From liquid, solid phase nucleates.

From solid, other phases can nucleate.

Like ice, many grains of solid form.

wt% of SOLUTE given by line dropped
from boundaries

Fraction of PHASES present given by
the lever rule.

Microstructure different depending on
cool slowly or quench.
15
Phases and Microstructure (non-equilibrium)
Upon cooling quickly (i.e. nonequilibrium),
microstructure has range of
composition depending on when it was
formed.

Inside nucleus of solid phase higher
composition (in Cu-Ni case) due to its
creation at higher T.

Outside part of growing solid phase
nucleus has lower composition due to
its forming at lower T.
Core-like development
16
Cored versus Equilibrium Phases
Slow rate of cooling:
Equilibrium structure
Fast rate of cooling:
Cored structure
C
o
changes as we solidify.
Cu-Ni case: First o to solidify has C
o
= 46 wt% Ni.
Last o to solidify has C
o
= 35 wt% Ni.
17
Cored structure gives rise to less than the optimal properties

As a casting having a cored structure is reheated, grain
Boundaries regions will melt first because they are richer in
Low melting component.
This produces a sudden loss in Mechanical integrity due to
the thin liquid film that separates the grain.
Further more this melting may begin at a temp. below the
Equilibrium solidus temp. carried out of the alloy
Coring may be eliminated by a homogenization heat treatment
Carried out at a temp. below the solidus point for the particular
Alloy composition.
During this process, atomic diffusion occurs Which produces
compositionally homogeneous grains
18
Recall: Mechanical Properties of Cu-Ni
Effect of solid solution strengthening on:
--Tensile strength (TS) --Ductility (%EL,%AR)
-Peak as a function of C
o
-Minimum as a function of C
o
T
e
n
s
i
l
e

S
t
r
e
n
g
t
h

(
M
P
a
)

Composition, wt% Ni
Cu Ni
0 20 40 60 80 100
200
300
400
TS for
pure Ni
TS for pure Cu
E
l
o
n
g
a
t
i
o
n

(
%
E
L
)

Composition, wt% Ni
Cu
Ni
0 20 40 60 80 100
20
30
40
50
60
%EL for
pure Ni
%EL for pure Cu
19
Binary-Eutectic Systems
has a special composition
with a minimum melting T.
Ex: Cu-Ag
3 single-phase regions
(L, o, |)
Limited solubility
o: mostly Cu
|: mostly Ag
T
E
: no liquid below T
E
.
c
E
: composition for min.
melting T (Eutectic).
Eutectic: direct from liquid to 2-phase solid upon cooling: L o + |
Cu-Ag
system

L (liquid)
o L + o
L + |
|
o + |
C
,
wt% Ag
20 40 60 80 100 0
200
1200
T(C)
400
600
800
1000
C
E

T
E

8.0 71.9 91.2
779C

Ag) wt% 1.2 9 ( Ag) wt% .0 8 ( Ag) wt% 9 . 71 ( | + o L
cooling
heating
20
For a 40wt%Sn-60wt%Pb alloy at 150
o
C, determine...
--phases present: o + |
--compositions of phases:
Example 1: Lead-Tin (Pb-Sn) Eutectic Diagram
Solder for electronics
Use the
Lever Rule
C
o
= 11 wt% Sn
C
|
= 99 wt% Sn
L + o
L + |
o + |
200
T(C)
18.3
C, wt% Sn
20 60 80
100
0
300
100
L (liquid)
o
183C

61.9 97.8
|
150
40
C
0

11
C
o

99
C
|

S R
-- relative amount
of each phase:
W
o

=
C
|
- C
0

C
|
- C
o
=
99 - 40
99 - 11

=
59
88

= 0.67
S
R+S

=
W
|
=
C
0
- C
o

C
|
- C
o
=
R
R+S

=
29
88

= 0.33 =
40 - 11
99 - 11

21
Example 2: Pb-Sn Eutectic System
C
o
= 17 wt% Sn
-- phase compositions
For a 40 wt% Sn-60 wt% Pb alloy at 220C, determine:
-- phases present:
-- relative amt of phases
W
o
=
C
L
- C
0

C
L
- C
o
=
46 - 40
46 - 17

= 0.21
W
L

=
C
0
- C
o

C
L
- C
o
=
23
29

= 0.79
o + L
C
L
= 46 wt% Sn
40
C
0

46
C
L

17
C
o

L + |
o + |
200
T(C)
C, wt% Sn
20 60 80
100
0
300
100
L (liquid)
o

|
L + o
183C
220
S R
22
Microstructure for Eutectic Diagrams: Pb-Sn
0
L
+ o
200
T(C)
C , wt% Sn
10
2
20
C
0
300
100
L
o
30
o + |
400
(room T solubility limit)
T
E
(Pb-Sn
System)
o
L
L: C
0
wt% Sn
o: C
0
wt% Sn
For alloys with C
0
< 2 wt% Sn
Result: at room temperature
-- polycrystalline with grains of
o phase having C
0
Note: liquid-to-solid creates
grain boundaries.
23
Microstructure for Eutectic Diagrams: Pb-Sn
For alloys with
2 wt% Sn < C
0
< 18.3 wt% Sn

Result:
at Ts in o + | range
-- polycrystalline with o grains
and small |-phase particles
Pb-Sn
system
L
+ o
200
T(C)
C , wt% Sn
10
18.3
20 0
C
0
300
100
L
o
30
o + |
400
(sol. limit at T
E
)
T
E

2
(sol. limit at T
room
)
L
o
L: C
0
wt% Sn
o
|
o: C
0
wt% Sn
Note: Solubility depends on T.
24
Microstructure at Eutectic
Light: Sn-rich
Dark: Pb-rich
For alloy of composition C
0
= C
E

Result: Eutectic microstructure (lamellar structure)
-- alternating layers (lamellae) of o and | phases.
Pb-Sn
system
L + |
o + |
200
T(C)
C, wt% Sn
20 60 80 100 0
300
100
L
o

|
L + o
183C
40
T
E

18.3
o: 18.3 wt%Sn
97.8
|: 97.8 wt% Sn
C
E

61.9
L: C
0
wt% Sn
160 m
Micrograph of Pb-Sn
eutectic
microstructure
25
Adapted from Figs. 10.14 & 10.15,
Lamellar Eutectic Structure
Diffusion local
26
For alloys for 18.3wt%Sn < C
o
< 61.9wt%Sn
Result: a crystals and a eutectic microstructure
Microstructure below Eutectic (hypoeutectic)
18.3 61.9
S R
97.8
S R
primary o
eutectic o
eutectic |
Pb-Sn
system
L +
|
200
T(C)
C, wt% Sn
20 60 80 100 0
300
100
L
o
|
L +
o
40
o

+ |
T
E

L: C
0

wt% Sn
L
o

L

o

W
L
= (1- W
o
) = 0.50
C
o
= 18.3 wt% Sn
C
L
= 61.9 wt% Sn
S
R + S
W
o

= = 0.50
Just above T
E
:
Just below T
E
:
C
o
= 18.3 wt% Sn
C
|
= 97.8 wt% Sn
S
R + S
W
o
= = 0.73
W
|
= 0.27
27
Solder: Lead-Tin (Pb-Sn) microstructure
For 50 wt% Pb alloy:
Lead-rich o phase (dark)
Lamellar eutectic structure
of Sn-rich | phase (light).
* Why is Liquid-phase ~62.9wt%Sn and o-phase ~16.3wt%Sn at 180 C?
* For fraction of total o phase (both eutectic and primary), use the Lever Rule.
o + |
o
L + |
L
|
28
Hypoeutectic & Hypereutectic
(Figs. 10.14 and
10.17 from Metals
Handbook, 9th ed.,
Vol. 9, Metallography
and Microstructures,
American Society for
Metals, Materials
Park, OH, 1985.)
29
Eutectoid one solid phase transforms to two other
solid phases
S
2
S
1
+S
3
o + Fe
3
C (For Fe-C, 727C, 0.76 wt% C)
intermetallic compound
- cementite
cool
heat
Eutectic, Eutectoid, & Peritectic
Eutectic - liquid transforms to two solid phases
L o + | (For Pb-Sn, 183C, 61.9 wt% Sn)

cool
heat
Peritectic - liquid and one solid phase transform to a
second solid phase
S
1
+ L S
2

o + L (For Fe-C, 1493C, 0.16 wt% C)
cool
heat
30
Eutectoid, & Peritectic
Eutectoid transformation o + c
Peritectic transformation + L o
Cu-Zn Phase diagram
31
Gibbs Phase Rule
This rule represents a criterion for the no. of phases that will coexist
within a system at equilibrium and is expressed as follows:
P + F = C + N . (1)
P = no. of phases present
F = no. of degrees of freedom or the no. of externally controlled
variables which must be specified to completely define the state of the
system.
C = no. of components in the system
N = no. of non compositional variables ( e.g temp. and pressure)
32
Demonstration of Gibbs phase rule
Let us demonstrate the phase rule by applying it to binary
temperature vs. composition phase diagrams for example
the coppersilver system.
Since pressure is constant (1 atm), the parameter N = 1
because temperature is the only non compositional
variable.
Furthermore C = 2 as it is a two component system. So the
gibbs equation (1) takes the form:
P + F = N + C
P + F = 1 + 2
F = 3 - P ..(2)
33
Case I: Consider the case of
single-phase fields on the
phase diagram (e.g. , and
liquid regions).
Since only one phase is
present in these regions so
we have P = 1 now the
equation (2) becomes
F = 3 -1 = 2
Cu-Ag
system

L (liquid)
o L + o
L + |
|
o + |
C
,
wt% Ag
20 40 60 80 100 0
200
1200
T(C)
400
600
800
1000
C
E

T
E

8.0 71.9 91.2
779C

This means that to completely describe the characteristics
of any alloy that exists within one of these phase fields, we
must specify two parameters; these are composition and
temperature, which locate, respectively, the horizontal and
vertical positions of the alloy on the phase diagram.
34
Case II: For the situation wherein two phases coexist, for example +
, + L and + L phase regions, the phase rule stipulates that we have
one degree of freedom since
F = 3 P = 3-2 = 1
Thus, it is necessary to specify either
Temp. or the composition of one Of
the phases to completely define the system.
For example, suppose that we decide to
specify temperature for the phase region +
L. The compositions of the and liquid
phases are thus dictated by the extremities of
the tie line constructed at T1 across the + L
field. Note that only the nature of the phases
is important in this treatment and not the
relative phase amounts.
35
This is to say that the overall alloy composition could lie
anywhere along this tie line constructed at temperature T1 and
still give C and CL compositions for the respective and
liquid phases.
The second alternative is to stipulate the composition of one of
the phases for this two-phase situation, which thereby fixes
completely the state of the system. For example, if we specified
C as the composition of the phase that is in equilibrium
with the liquid then both the temperature of the alloy ( T1 ) and
the composition of the liquid phase (C) are established, again
by the tie line drawn across the + L phase field so as to give
this C composition.
36
Case III: For binary systems, when three phases are present,
there are no degrees of freedom, since
F = 3 P = 3 3 = 0
This means that the compositions of all three phases as well as the
temperature are fixed.
Iron-Carbon (Fe-C or Fe-Fe3C) Phase Diagram
A
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L
+Fe
3
C
o +Fe
3
C
o
(Fe)
C, wt% C
1148C
T(C)
o
727C = T
eutectoid
4.30

A
L+Fe
3
C
Fe
3
C (cementite-hard)
o (ferrite-soft)
0.76
B
38
Iron-Carbon (Fe-C) Phase Diagram
2 points
- Eutectoid (B):

o + Fe
3
C
- Eutectic (A):

L + Fe
3
C
Result: Pearlite is
alternating layers of and Fe
3
C phases o
120 m
A
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L

+Fe
3
C
o +Fe
3
C
o
(Fe)
C, wt% C
1148C
T(C)
o
727C = T
eutectoid
4.30

A
L+Fe
3
C
Fe
3
C (cementite-hard)
o (ferrite-soft)
0.76
B
39
Hypoeutectoid Steel
Adapted from Fig. 10.34, Callister & Rethwisch 3e.
proeutectoid ferrite
pearlite
100 m
Hypoeutectoid
steel
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L
+ Fe
3
C
o + Fe
3
C
L+Fe
3
C
o
(Fe)
C, wt% C
1148C
T(C)
o
727C
(Fe-C
System)
C
0

0
.
7
6

o
pearlite

o
o
o

Adapted from Figs. 10.28 and 10.33
40
Hypoeutectoid Steel
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L
+ Fe
3
C
o + Fe
3
C
L+Fe
3
C
o
(Fe)
C, wt% C
1148C
T(C)
o
727C
(Fe-C
System)
C
0

0
.
7
6

o
o
o
s r
W
o
= s/(r + s)
W
=(1 - W
o
)
R S
o
pearlite
W
pearlite
= W

W
o
= S/(R + S)
W

=(1 W
o
)
Fe
3
C
proeutectoid ferrite
pearlite
100 m
Hypoeutectoid
steel
41
Hypereutectoid Steel
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L
+Fe
3
C
o +Fe
3
C
L+Fe
3
C
o
(Fe)
C, wt%C
1148C
T(C)
o
0
.
7
6

C
0

Fe
3
C

proeutectoid Fe
3
C
60 m
Hypereutectoid
steel
pearlite
pearlite
42
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L
+Fe
3
C
o +Fe
3
C
L+Fe
3
C
o
(Fe)
C, wt%C
1148C
T(C)
o
0
.
7
6

C
0

pearlite
Fe
3
C

x v
V X
W
pearlite
= W

W
o
= X/(V + X)
W

=(1 - W
o
)
Fe
3
C
W

=(1-W
)
W

=x/(v + x)
Fe
3
C
proeutectoid Fe
3
C
60 m
Hypereutectoid
steel
pearlite
Hypereutectoid Steel
43
For a 99.6 wt% Fe-0.40 wt% C steel at a
temperature just below the eutectoid,
determine the following:
a) The compositions of Fe
3
C and ferrite (o).
b) The amount of cementite (in grams) that
forms in 100 g of steel.
c) The amounts of pearlite and proeutectoid
ferrite (o) in the 100 g.
Example Problem Steel
44
Solution to Problem

W
Fe
3
C
=
R
R+S
=
C
0
C
o
C
Fe
3
C
C
o
=
0.400.022
6.700.022
= 0.057
b) Use lever rule with
the tie line shown
a) Use RS tie line just
below Eutectoid
C
o
= 0.022 wt% C
C
Fe
3
C
= 6.70 wt% C
Amount of Fe
3
C in 100 g
= (100 g)W
Fe
3
C

= (100 g)(0.057) = 5.7 g
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L
+ Fe
3
C
o
+ Fe
3
C
L+Fe
3
C
o
C

, wt% C
1148C
T(C)
727C
C
0

R S
C
Fe C

3
C
o

45
Solution to Problem
c) Using the VX tie line just above
the eutectoid and realizing that

C
0
= 0.40 wt% C
C
o
= 0.022 wt% C
C
pearlite
= C
= 0.76 wt% C

W
pearlite
=
V
V + X
=
C
0
C
o
C
C
o
=
0.400.022
0.760.022
= 0.512
Amount of pearlite in 100 g
= (100 g)W
pearlite

= (100 g)(0.512) = 51.2 g
F
e
3
C

(
c
e
m
e
n
t
i
t
e
)

1600
1400
1200
1000
800
600
400
0 1 2 3 4 5 6 6.7
L

(austenite)
+L
+ Fe
3
C
o
+ Fe
3
C
L+Fe
3
C
o
C, wt% C
1148C
T(C)
727C
C
0

V X
C

C
o

46
Phase (T vs c) diagrams are useful to determine:
- the number and types of phases,
- the wt% of each phase,
- and the composition of each phase
for a given T and composition of the system.
Alloying to produce a solid solution usually
- increases the tensile strength (TS)
- decreases the ductility.
Binary eutectics and binary eutectoids allow for
a range of microstructures.
- Alloy composition and annealing temperature and time
determine possible microstructure(s). Slow vs. Fast.
- In 2-phase regions, use lever rule to get wt% of phases.
- Varying microstructure affects mechanical properties.
Summary
Phase Diagrams and Microstructures

Phase Diagrams Material Science

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MSE 280: Introduction to Engineering Materials D.D.

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