Soldering and Brazing

comparing with
Diffusion bonding, Hot pressing,
and Solid phase bonding
Dr. Kunio TAKAHASHI
- Associate professor,
Dept. of International Development Engineering,
Tokyo Institute of Technology,Tokyo 152-8552, Japan
Phone/Fax:+81-3-5734-3915
E-Mail:takahak@ide.titech.ac.jp
http://www.ide.titech.ac.jp/~takahak/
Prior to this lecture...
Activities of Japanese welding community

Organizations and their roles

Japanese system of education and certification

Movement around Asian Welding Federation
About lecturers ...
Back ground
welding ( what is this ? )
Tokyo Institute of technology
http://www.titech.ac.jp/
Department of International Development Eng.
Network beyond the border of engineering field
(community) nation
http://www.ide.titech.ac.jp/

Welcome to Japan
Already, you have joined to our Network.
Welding Technology, as Inter-Field Engineering
based on
Plasma physics
Electronics/Electrical Eng. Power Source
Control (self-controlled is the best) = Heat sources
Thermal Eng.
Fluid dynamics
Material science
Fracture mechanics



Physics of phenomena Standard Industry

roles of Society
Plasma
e
-
-beam
Laser
Joules heat
etc
Steels
(Materials)
- Making
- Design
About this lecture Brazing and Soldering

Basic knowledge based on physics
Phenomena
Comparison with other welding processes
What is and what is not clarified, theoretically ?
Recent progresses for physical understanding.
so,
You will understand...
Why and How the process is used ? Experimental training
How the process can be modified ?
Definition of brazing and soldering
Examples
Comparison with other welding processes
Heat sources
Brazing filler metals and solders
Fluxes and atmosphere
Set up and joint shape
Phenomena in brazing and soldering
Wetting ( surface and interfacial tension )
Conduction of heat
Dissolution
Flow
Diffusion
Deformation
Oxidation - reduction reaction
Solidification -> microscopic structure
Exercise
Contents of
this lecture

Please remember
in your experimental
training (Sept.19 ?)
Definition of the brazing and soldering.


Joint is heated
distributing filler metal between base materials,
by capillary action
below solidus temperature of base materials.
Sometimes the joint is pressed.







example of brazing main engine LE7A H2A rocket
Filler metals

Brazing
melting point of filler metal > 723 K 450 C, 840 F

Soldering
melting point of filler metal < 723 K 450 C, 840 F

Capillary action

Wetting phenomenon


Surface tension
or
Surface energy
A g- Cu p h ase di agr am .
Solidus temperature

phase diagram

Equilibrium
phase

Lever rule
Solidus Liquidus
example

Soldering is key technology
in micro-electronics assembly
example

Soldering is key technology
in micro-electronics assembly
example flip chip technology

A ssessed Pb- Sn p h ase di agr am .
Solders for electronics
Eutectic phase
conventional solder
Sn-Pb
(Sn-38Pb 180C)

lead free solders
Sn-Ag
(Sn-3.8Ag 220C)
Sn-In
Sn-Bi
Sn-Zn
etc...
Wire bonding by Kaijo
by H.Miyazaki, S.Saito, et.al...
Pb ( lead ) problem for health

Mental development index age ->

Audition handicap - Pb in blood
Blood pressure - Pb in blood
(positive correlation)
A ssessed Pb- Sn p h ase di agr am .
Solders for electronics
eutectic phase
conventional solder
Sn-Pb
(Sn-38Pb 180C)

lead free solders
Sn-Ag
(Sn-3.8Ag 220C)
Sn-In
Sn-Bi
Sn-Zn
etc...
A ssessed A g- Sn p h ase di agr am .
Solders for electronics

conventional solder
Sn-Pb
(Sn-38Pb 180C)

lead free solders
Sn-Ag
(Sn-3.8Ag 220C)
Sn-In
Sn-Bi
Sn-Zn
etc...
Sn-Ag-Bi-Sb-Cu
Sn-Ag-In
Sn-Ag-Bi-Cu
...
A ssessed I n - Sn p h ase di agr am .
A ssessed Sn - B i p h ase di agr am .
A ssessed Z n - Sn p h ase di agr am .
Problems Pb free solder

Melting point
problems in processes almost solved
Viscosity


Corrosion still under R/D
Heating iron in iron soldering
Solder bath in reflow soldering
example Al brazing

example Ni brazing

example Ag brazing of Stainless and Ceramics

The highest technology is
never used for space
development.

The highest technology is the
combination of conventional
technologies.

Optimization & breakthrough
are based on scientific
understanding
Comparison with other welding or joining processes

melting base materials
ex. arc welding, resistance welding, etc

adding molten metals between base materials
ex. brazing, soldering, etc...

not melting base materials
ex. solid phase bonding, hot pressing, etc...

Diffusion bonding, Hot pressing,
and Solid phase bonding

Samples are
heated,
and
pressed.
Sometimes metal
sheet is inserted.




filler metal ?
in brazing
Another type of equipments
Hot Isostatic Pressing (HIP)

Example Ni alloy

Energy(arb.unit)
Activation Energy
Surface Energy
?
(b) Activated surface (c) Reduced surface
(equilibrium)
(a) Bulk or interface
Requirements for joining
to bring atoms near stable inter-atomic distance

Wetting
Heat transfer
Dissolution
Flow
Diffusion
Deformation
Oxidation
Reduction
Solidification

Phenomena

Soldering and Brazing

and also

Diffusion bonding
Hot pressing
Solid phase bonding

Heat sources for brazing and soldering

Oxyfuelgas flame :Torch brazing/soldering , braze welding
Arc plasma :Arc brazing, braze welding
Joules heat :Resistance brazing
Induction heat :Induction brazing
Hot iron :Iron soldering
Ultrasonic wave :Ultrasonic soldering
Infrared ray :Infrared soldering
Laser beam :Laser beam soldering
etc...
Other terminology for brazing and soldering

Atmosphere
Atmospheric brazing/soldering

Vacuum brazing

Furnace brazing

Dip brazing/soldering ex. of dip soldering
Metal bath brazing/soldering (in molten solder bath)
Salt bath brazing/soldering (in flux)
Other terminology

Procedure
Abrasion tinning & re-flow
Re-flow soldering
Diffusion brazing/soldering
Transient Liquid Phase bonding

ambiguous

Diffusion bonding ( Hot pressing ) ?
Liquid phase diffusion bonding : iso-thermal solidification
Eutectic bonding : no filler metal and
intent to melt base materials

ex. Re-flow used in electronics
A ssessed Pb- Sn p h ase di agr am .
Brazing/Soldering temperature
= Liquidus temp. + 50~100 K ( because of viscosity )
Brazing filler metals and solders
Brazing filler metals in Japanese Industrial Standards (JIS)
Al,
Al alloy
Mg,
Mg alloy
Cu,
Cu alloy
Carbon
steel
Cast iron
Stainless
steel
Ni,
Ni alloy
Ti,
Ti alloy
Be, Zr, V,
alloy
W,Mo,Ta,
Nb, alloy
High speed
steel
Al,
Al alloy
BA
Mg,
Mg alloy
---- BMg
Cu,
Cu alloy
---- ----
BAg, BAu
BCuP,
BCuZn
Carbon
steel
BA ----
BAg, BAu
BCuZn
BAg, BAu
BCu, BNi,
BCuZn
Cast iron ---- ----
BAg, BAu
BCuZn
BAg, BAu
BCuZn
BAg, BNi
BCuZn
Stainless
steel
BA ---- BAg, BAu
BAg, BAu
BCu, BNi,
BAg, BAu
BCu, BNi,
BAg, BAu
BCu, BNi,
Ni,
Ni alloy
---- ----
BAg, BAu
BCuZn
BAg, BAu
BCu, BNi,
BCuZn
BAg, BCu
BCuZn
BAg, BAu
BCu, BNi
BAg, BAu
BCu, BNi
Ti,
Ti alloy
BA ---- BAg BAg BAg BAg BAg **
Be, Zr, V,
alloy
----
BA(Be)
---- BAg BAg, BNi* BAg, BNi* BAg, BNi* BAg, BNi* ** **
W,Mo,Ta,
Nb, alloy
---- ---- BAg
BAg, BCu,
BNi*
BAg, BCu
BNi*
BAg, BCu
BNi*
BAg, BCu
BNi*
** ** **
High speed
steel
---- ----
BAg, BAu
BCuZn,
BNi
BAg, BAu
BCu, BNi,
BCuZn
BAg, BAu
BCuZn,
BNi
BAg, BAu
BCu, BNi
BAg, BAu
BCu, BNi,
BCuZn
---- ---- ----
BAg, BAu
BCu, BNi,
BCuZn
---- : No filler metal, * : modified (not standard) ** : not standard
s d p
1 2 1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6
H He
Li Be B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
f
1 2 3 4 5 6 7 8 9 10 11 12 13 14
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Fluxes and atmosphere

Fluxes
Shielding
Reduction of surfaces


Requirements
wettable
easily removable
never harmful

Shielding gas
Wettability
Set up and joint shape


Phenomena in brazing and soldering

Wetting ( Surface and interfacial tension )
Conduction of heat
Dissolution
Flow
Diffusion
Deformation
Oxidation - reduction reaction
Solidification -> microscopic structure
Wetting driven by
surface and interfacial tension

What determines equilibrium
( contact angle, meniscus, etc ) ?
surface and interfacial tension
Youngs equation
u o o o cos
l i s
+ =
Surface and interfacial tension
(Surface tension is interfacial tension between material and vacuum.)

Surface ( interfacial ) tension
ex. soap film
ex. soap bubble

Force on meniscus
Laplace equation


Effect of gravity on meniscus
on shape of fillet
Curvature changes with height.
|
|
.
|

\
|
+ =
2 1
l
1 1
R R
P o
Surface (interfacial) tension
and Surface (interfacial) energy

Internal energy and entropy


1st law and 2nd law of thermodynamics


For bulk,
therefore
Variables for unit area of surface


For arbitrary area of surface,


Therefore,
p, T
A
V
b
dA pdV TdS dU + =
b tot tot
s b tot
U U U + =
s b tot
S S S + =
b b b
pdV TdS dU =
dA TdS dU + =
s s
A U U

s s
= A S S

s s
=
( ) ( ) 0
s s s s
= +

TdS dU A dA TS U

s s
TS U =

s s
TdS dU =
p
T
S
|
.
|

\
|
c
c
=

s
}
|
|
.
|

\
|
c
c
=
=
T
p
dT
T
U
T
T U
T p TS T p U T p
0
s
s
s s
1

) , ( ) , ( ) , (

Relation between
Surface (interfacial) tension and Surface (interfacial) energy












Surface contribution of internal energy is important.
at 0 K,
}
|
|
.
|

\
|
c
c
=
=
T
p
dT
T
U
T
T U
T p TS T p U T p
0
s
s
s s
1

) , ( ) , ( ) , (

Surface ( interfacial )
entropy




dT
T
U
T
T
S
T
p
} |
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
=
0
s
s
1

Surface ( interfacial )
tension
Surface ( interfacial )
energy

s
U =
Theoretical approach for Electronic theory
surface tension at 0 K (quantum mechanics)
SCF-Jellium
Stabilized
jellium
Al
Zn
Mg
Pb
Ca
Li
Sr
Ba
Na
K
Rb
Cs
Shifted step potential
Effective electron density parameter r
m
(Bohr)
S
u
r
f
a
c
e

e
n
e
r
g
y

a
t

z
e
r
o

t
e
m
p
e
t
r
a
t
u
r
e

s


(
m
J
/
m
2
)
Be
Ga
Cd
In
Hg
2 3 4 5 6
500
1000
1500
2000
2500
3000
100
Shifted step potential
K.Takahashi, and T.Onzawa,
Physical Review B, 48, 5689 (1993)

Stabilized jellium
J.P.Predew, H.Q.Tran and E.D.Smith,
Phys. Rev. B, 42, 11627 (1990).

SCF-jellium
N.D.Lang and W.Kohn,
Phys. Rev. B, 1, 4555 (1970).
comparison by K.F.Wojciechovski, Surface Science, 437, 285-288 (1999)
}
|
|
.
|

\
|
c
c
=
T
p
dT
T
U
T
T U T p
0
s
s
1
) , (

trans. phase s, phonon s, electron s, s
U U U U + + =
Temperature dependence
of surface tension

Other contributions
( phonon, phase transformation )
=0, at 0 (zero) K.
T 0 T
m
Phase transf.
Phonon
+
Electron
T 0 T
m
Electron
S
u
r
f
a
c
e

e
n
e
r
g
y


U
S
u
r
f
a
c
e

t
e
n
s
i
o
n

Solid liquid

0,ext.
0
) , (
5
) (
4
F
2
electron s,
t
t

r K
m
k
T U
r

=
Temperature T (K)
Al
Li
Na
K
Cs
S
u
r
f
a
c
e

t
e
n
s
i
o
n

s


(
J
/
m
2
)
Rb
Bi
Hg
Pb
Sn
Zn
0 500 1000 1500
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.1
T 0 T
m
Phase transf.
Phonon
+
Electron
T 0 T
m
Electron
S
u
r
f
a
c
e

e
n
e
r
g
y


U
S
u
r
f
a
c
e

t
e
n
s
i
o
n

Solid liquid

0,ext.
0
SCF-Jellium
Stabilized
jellium
Al
Zn
Mg
Pb
Ca
Li
Sr
Ba
Na
K
Rb
Cs
Shifted step potential
Effective electron density parameter r
m
(Bohr)
S
u
r
f
a
c
e

e
n
e
r
g
y

a
t

z
e
r
o

t
e
m
p
e
t
r
a
t
u
r
e

s


(
m
J
/
m
2
)
Be
Ga
Cd
In
Hg
2 3 4 5 6
500
1000
1500
2000
2500
3000
100
Experimental
measurements of
surface tension

Experimental value
which theorists
have been used,
is
extrapolated

Data base of
Surface- and interfacial- tension
Experimental approaches
Cleavage method
Zero creep method
Thermal grooving method
Contact angle method
( sessile drop )
Adhesion force method
...
Theoretical approaches
Quantum mechanics
Thermodynamics
Molecular dynamics

!! No experimental method gives perfect information by itself.
!! No theory gives perfect information by itself.
Strategy by lecturer for...
Conduction of heat (1)

Fourier's Law
Heat flux (J/m
2
s)
Thermal conductivity (J/sKm, W/Km)
Temperature (K)

Diffusion equation
Latent heat (J/kgK)
Density (kg/m
3
)
Diffusion coefficient (m
2
/s)

Diffusion equation for Cartesian coordinate system

|
|
.
|

\
|
c
c
+
c
c
+
c
c
=
c
c
2
2
2
2
2
2
z
T
y
T
x
T
D
t
T
T grad k = q
( ) ( ) T D T
c c t
T
grad div grad div div
1
= = =
c
c

k
c
D =
Conduction of heat (2)

Solutions for special boundary conditions
Steady state (t=), one dimensional



Steady state (t=), axially symmetric



Steady state (t=), center symmetric


0
2
2
=
|
|
.
|

\
|
c
c
=
c
c
x
T
D
t
T
0
1
2
2
=
|
|
.
|

\
|
c
c
+
c
c
=
c
c
r
T
r r
T
D
t
T
0
2
2
2
=
|
|
.
|

\
|
c
c
+
c
c
=
c
c
r
T
r r
T
D
t
T
2 1
) ( C x C x T + =
2 1
ln ) ( C r C r T + =
2 1
1
) ( C
r
C r T + =
Conduction of heat (2)

Basic solutions of diffusion equation
one dimensional area heating
for heat input Q
Q (J/m)

two dimensional linear heating

Q (J/m
2
)

three dimensional point heating

Q (J/m
3
)

( )
|
|
.
|

\
|

=
Dt
x
Dt
c
Q
T
4
exp
4
1
2

( ) ( )
|
|
.
|

\
|
+
=
Dt
y x
Dt c
Q
T
4
exp
4
1
2 2
q
t
( )
( ) ( ) ( )
|
|
.
|

\
|
+ +
=
Dt
z y x
Dt c
Q
T
4
exp
4
1
2 2 2
2 / 3
, q
t
-20 -10 0 10 20
X-AXIS
0
0.2
0.4
Y
-
A
X
I
S
A g- Cu p h ase di agr am .
Dissolution

increasing
temperature
heating
heat conduction
concentration
filler metal
diffusion
Solubility limit



Phase diagram

L
o
S
l
o
i
o
s
Flow

Wettability driving force

Viscosity dragging force






Approximation Liquid is always uniform.
Diffusion

Ficks 1st law, Ficks 2nd law, and Diffusion equation



Application of basic solutions





where

( )
|
|
.
|

\
|

=
Dt
x
Dt
c
C
4
exp
4
2
0

t
)
`

|
.
|

\
|
+ =
Dt
x c
C
4
erf 1
2
0
( ) ( )
}
=
o
| |
t
o
0
2
exp
2
erf d
-10 0 10
X-AXIS
0
0.5
1
Y
-
A
X
I
S
|
|
.
|

\
|
c
c
+
c
c
+
c
c
=
c
c
2
2
2
2
2
2
z
C
y
C
x
C
D
t
C
Diffusion

When material P is joined with
insert (filler) metal, change in
concentration profiles across
bond interface.



and if
below eutectic temperature
joint of P and Q at T
0
,
joint of P and Q at <T
eutectic
,
Q is inserted,...
etc...
)
`

|
.
|

\
|
=
Dt
x
c C
4
erf 1
s
Deformation : Deformation around joint

Elastic deformation
usually negligible
Plastic deformation
Creep deformation
Diffusional deformation
( diffusional creep )
surface diffusion
boundary diffusion
volume diffusion


Solid phase bonding
Surface
Void
Before contact
After plastic deformation
During creep deformation
L
h
00
(a)
Void
Volume diffusion
Boundary diffusion
Surface diffusion
(b)
X
800 1000 1200
Temperature T (K)
10
0
10
1
10
2
10
3
10
4
10
5
10
6
T
i
m
e

r
e
q
u
i
r
e
d

f
o
r

p
e
r
f
e
c
t

c
o
n
t
a
c
t


t
f
i
n


(
s
)
L=10 m, h
00
=1 m
L=1 m, h
00
=0.1 m
P
b
=10 MPa
0 5 10 15 20
Bonding pressure P
b
(MPa)
10
0
10
1
10
2
10
3
10
4
10
5
10
6
T
i
m
e

r
e
q
u
i
r
e
d

f
o
r

p
e
r
f
e
c
t

c
o
n
t
a
c
t


t
f
i
n


(
s
)
L=10 m, h
00
=1 m
L=1 m, h
00
=0.1 m
T=1000 K
Void
L
X
Time required for perfect contact by deformation
800 1000 1200
0
50
100
Bonding temperature T (K)
P
e
r
c
e
n
t

b
o
n
d
e
d

a
r
e
a


S

(
%
)
Plastic deformation
Creep deformation
Boundary diffusion
Volume diffusion
L=10m, h
00
=1m, P
b
=10MPa
0 10 20
0
50
100
Bonding pressure P
b
(MPa)
P
e
r
c
e
n
t

b
o
n
d
e
d

a
r
e
a


S

(
%
)
Plastic deformation
Creep deformation
Boundary diff.
Volume diffusion
L=10m, h
00
=1m, T=1000K
Void
L
X
Dominant mechanism

Elastic deformation
Plastic deformation
Creep deformation
Diffusional deformation
surface diffusion
boundary diffusion
volume diffusion


Why it is called
diffusion bonding ?
800 1000 1200
0
50
100
Bonding temperature T (K)
P
e
r
c
e
n
t

b
o
n
d
e
d

a
r
e
a


S

(
%
)
Plastic deformation
Creep deformation
Boundary diffusion
Volume diffusion
L=1m, h
00
=0.1m, P
b
=10MPa
0 10 20
0
50
100
Bonding pressure P
b
(MPa)
P
e
r
c
e
n
t

b
o
n
d
e
d

a
r
e
a


S

(
%
)
Plastic deformation
Creep deformation
Boundary diffusion
Volume diffusion
L=1m, h
00
=0.1m, T=1000K
800 1000 1200
0
50
100
Bonding temperature T (K)
P
e
r
c
e
n
t

b
o
n
d
e
d

a
r
e
a


S

(
%
)
Plastic deformation
Creep deformation
Boundary diffusion
Volume diffusion
L=10m, h
00
=1m, P
b
=10MPa
0 10 20
0
50
100
Bonding pressure P
b
(MPa)
P
e
r
c
e
n
t

b
o
n
d
e
d

a
r
e
a


S

(
%
)
Plastic deformation
Creep deformation
Boundary diff.
Volume diffusion
L=10m, h
00
=1m, T=1000K
If you want to use
diffusion for precise
joining



popular
roughness



If carefully
prepared...

Void
L
X
Oxidation - reduction reaction between fluxes and metal

ex. Cu joint by Pb-Sn solder with HCl flux
Reduction of base metal surface


Shield of molten metal


Assist wettability


| + + O H CuCl 2HCl CuO
2 2
| + +
2 2
H SnCl 2HCl Sn
Sn CuCl SnCl Cu
2 2
+ +
Oxidation - reduction reaction between atmosphere and metal

ex. atmospheric brazing with hydrogen gas





depending on
Material (M)
Partial pressure of H
2
O Liquid N
2
trap, Silica gel, etc...
Partial pressure of H
2
Gas control

( ) ( )
0
2 2
O H M H O M G n m n
n m
A + + +
|
|
.
|

\
|
= = A = A A
2
2
2 2
H
O H
0 0
H
0
O H
ln ln
p
p
RTn K RT G G G
Solidification

Phase diagram


precipitation process


Microscopic structure


Mechanical property
materials
cooling rates ex. Fe-C system
A ssessed Pb- Sn p h ase di agr am .
ex. Pb-Sn solder eutectic phase
Ball Grid Array (BGA)
in flip chip technology














Eutectic phase can be seen.
Weakness of low melting point material
ex. Pb-Sn solder

Cracking








Thermal effect

150 C 100 hours
A ssessed Pb- Sn p h ase di agr am .
Brittleness of inter-metallic compound
ex. Fe - Al Although Al is low melting point material,...
A ssessed F e- A l p h ase di agr am .
ex. filler metal for Al: Low melting point precise heat control


A ssessed A l - Cu p h ase di agr am .
A ssessed A l - Si p h ase di agr am . A ssessed A l - M g p h ase di agr am .
A ssessed A l - Z n p h ase di agr am .
Weld metal solidification crack


ex. Al

at the end of the solidification,

the liquid vanish very quickly


lack of liquid crack
A ssessed A l - Si p h ase di agr am .
ex. Ti - Ti bonding with Cu film
A ssessed T i - Cu p h ase di agr am .
Exercise 1
Schematically, illustrate a concentration profile at 700 C across the
interface of diffusion couple (Ag/Cu), considering phase diagram.


A g- Cu p h ase di agr am .
Exercise 2
Cu samples are bonded using insert film of Ag by keeping joint at
900 C. After liquid metal vanished, the joint was cooled to room
temperature. Schematically, illustrate a change of concentration
profile across the interface.

A g- Cu p h ase di agr am .
Exercise 3
Choose a percentage of Sn in Pb-Sn solder.
And answer a soldering temperature.

A ssessed Pb- Sn p h ase di agr am .
Exercise 4
List up deformation mechanisms for solid phase bonding.
fin.



Conduction of heat

Application of basic solutions
Step distribution in t=0.

Area heating


Linear heating


Point heating

Thermal conductivity, Specific heat, Mass density
Temperature dependence Thermal diffusion coefficient
Surface and interfacial tension
(Surface tension is interfacial tension between material and vacuum.)

Meniscus between flat plane