Reprinted from
Welding and Metal Fabrication
March and April 1973
FURNACE BRAZING
A Survey of Modern Processes and Plant
J. D. Boughton and P. M. Roberts
Johnson Matthey Metals Limited, London
+MenOm
where Me = metal
and m = 1 Mole of oxygen.
Table 1 presents some data on the heat of formation
for a series of different oxides. As shown in the table,
metals like gold, silver and palladium possess low
values for heat of formation of their oxides. Thus,
from what has been said above, it is clear that these
oxides can be considered to be unstable and hence
can be readily decomposed. The oxides of metals
such as copper, cobalt, nickel, or cadmium, are
higher on the stability scale and are hence more
difficult to reduce. Higher still on the stability scale
will be found the oxides of chromium, tantalum,
aluminium, and beryllium. In fact, the various oxides
of beryllium have a far higher degree of stability than
those of virtually any other element.
Table 1
Heat of Formation of certain Oxides1
Type
Of
oxides
Au2O3
Ag2O
PdO
CuO
Cu2O
CoO
Co3O4
H2O (liquid)
H2O (gaseous)
NiO
CdO
FeO
Fe2O3
Fe3O4
MnO
ZnO
Cr2O3
Ta2Q5
TiO2
ZrO2
A12O3
BeO
Reaction
of formation
of oxides
2Au + 3/2O2
2Ag + 1/2O2
Pd + 1/2O2
Cu2O + 1/2O2
2Cu + 1/2O2
Co + 1/2O2
3Co +2O2
2 H + 1/2O2
2 H + 1/2O2
Ni + 1/2O2
Cd + 1/2O2
Fe + 1/2O2
2Fe + 3/2O2
3Fe + 2O2
Mn + 1/2O2
Zn + 1/2O2
2Cr + 3/2O2
2Ta + 5/2O2
Ti + O2
Zr+ O2
2Al + 3/2O2
Be + 1/2O2
Heat of formation
of oxides, related
to 1 mole 02:
in kcal
-7.3
14.6
42.0
75.0
82
115.0
98.2
115.6
136.6
116.8
124.4
129.0
130.0
133.8
185.0
166.8
179.6
199.6
219.0
258.5
266.6
294.6
2. Dissociation of Oxides
With increasing temperature, the free energy
associated with the formation of oxides decreases.
Hence dissociation of oxides becomes easier to
accomplish as the temperature within the furnace
increases (Fig. 2). The temperature at which the
oxides dissociate depends directly on the partial
pressure of the oxygen in the environment. If
the partial pressure of oxygen in the surrounding
atmosphere is 0.21 atmosphere or more, the
dissociation pressure of the oxide will, in most
known metals and alloys, exceed their respective
melting points. It is clear, therefore, that under these
conditions (where dissociation of the oxide coating
is relied upon to provide an oxide-free surface over
which the molten brazing alloy can wet and flow),
brazing will be impossible.
There are, fortunately, exceptions to this rule.
These are the oxides of gold, silver and platinum
or oxides of their alloys, where dissociation takes
place at temperatures below their respective melting
points. Thus, a decrease in the partial pressure of
oxygen in the surrounding atmosphere tends to
favour decomposition of oxides on these metals
and their alloys, and so increases the likelihood that
brazing can be completed successfully.
Reduction of the partial pressure of oxygen
contained in the gas atmosphere may be achieved
in two ways:
2Cr+3H2O
6. Reducing Atmospheres in
Common Use
As has already been shown, the prime essential of a
reducing atmosphere is that it shall be capable of both
removing the oxides on the workpiece and brazing
alloy and maintain the surfaces of these materials in a
clean condition throughout the duration of the heating
cycle. These conditions facilitate the proper wetting
of the work by the molten brazing material and also
ensure that the work is clean and bright when it is
removed from the furnace.
Since far and away the greatest amount of furnace
brazing involves the joining of mild steel parts with
copper, the commonly used reducing atmospheres will
be considered primarily in relation to this particular
brazing process. In the United Kingdom, reducing
atmospheres are most frequently derived from one of
six sources:
From ammonia: it being catalytically cracked
into its two constituent elements, hydrogen and
nitrogen.
Partially burned fuel gas.
Catalytically cracked fuel gas.
Catalytic reformation of hydrocarbon vapours.
Bottled hydrogen.
Methanol-water hydrogen generators.
The atmospheres obtained from these various
sources will, therefore, contain some or all of the
following gases unless special precautions are taken
to remove those which might have a deleterious effect
upon the brazing operation:
Carbon dioxide.
Water vapour.
Nitrogen.
Hydrogen.
Undissociated hydrocarbons
compositions.
Carbon monoxide.
Compounds of sulphur.
of
varying
10
2C0 +4H2
nCO+(2n+1)H2
nCO2+nH2
11
7. Types of Furnaces
(Fig. 8).
Ultra-pure Hydrogen. Until relatively recently,
there has been no truly economic method of achieving
dew points much below about 60C. With the
development of inexpensive hydrogen diffusion units,
which operate on the principle of selective diffusion
of hydrogen atoms through heated membranes of a 23
per cent silver :77 per cent palladium alloy, dew points
which are better than 80C can be readily achieved
on a continuous basis. Diffusion units of this type are
designed to operate under all manner of hydrogen-rich
gases, but for brazing and heat-treatment applications
the gas source is usually one of:
12
13
cut into them which will permit the entry of the parts
to be brazed, but which can be efficiently purged
with the protective gas. Again, the gas issuing from
the furnace doors is ignited. Alternatively, where it
is either uneconomic or impossible, because of the
variety of parts to be brazed, to use contoured doors,
a curtain of asbestos string at the entry and exit can
be used.
While most continuous furnaces maintain the belt
in a horizontal plane, there are furnaces in which the
heating zone, and hence brazing zone, is raised a foot
or so above the entry and exit doors of the furnace.
This design is claimed to minimise the ingress of air
to the heating zone. This type of furnace is referred to
as a hump-back type (Fig. 10). With these furnaces,
the angle of the belt track is rarely greater than 15
from the horizontal on the entry side and, normally,
the angle of the belt track on the exit side of the
furnace is shallower than this. This arrangement is
necessary to ensure that there is sufficient time for the
brazed part to cool to a temperature where, as with
continuous furnaces, it will not oxidise once it leaves
the cooling chamber.
Pusher Furnaces. Pusher furnaces (Fig. 11) are
generally similar to continuous furnaces. While
continuous furnaces have open ends and a moving
belt on which to place the parts, the pusher furnace
comprises a purging chamber immediately adjacent to
the entry to the furnace heating chamber, and a second
purging chamber at the exit.
The parts to be brazed are loaded into heat-resisting
metal trays. These trays are placed on a platform at
the side of, and level with, the furnace track and the
furnace cycle is then commenced. On initiation of the
cycle, the outer door of the purging chamber opens,
a hydraulic ram fitted to the loading table pushes
the tray into the purging chamber, the door closes,
and purging is carried out. Once the purging cycle
has been completed, the door between the purging
chamber and the furnace is opened, a second hydraulic
ram pushes the tray into the throat of the furnace, and
the door closes. The furnace cycle then continues
automatically with loaded trays being pushed into
the purging chamber, purging being carried out and
the purged material being admitted to the furnace.
Every time the furnace door opens and a further tray
is pushed into the throat of the furnace, all other trays
already in the furnace are pushed along by a distance
equal to the length of individual trays making up the
furnace load.
At the exit from the furnace, the procedure is
slightly different. In this instance, there is not
usually a door at the exit of the furnace chamber,
only a door at the side of the purging chamber. The
14
8. Vacuum Brazing
Vacuum is defined as a state which exists in a
completely sealed space from which all gases and
vapours have been removed. No method of producing
absolute vacuum has yet been devised and, even
the so-called vacuum of outer space (found to be
about 1 x 1027 torr), cannot be considered to be a
true vacuum since even in this environment one finds
concentrations of several hundreds of molecules per
cubic metre of space. Thus, progress towards the
goal of a true vacuum must be described in various
degrees of vacuum. Clearly, the pressure attained
is limited by the materials chosen to enclose the
space, the nature of the gases and vapours to be
removed from the space, and, the method of pumping
employed. The degree of vacuum attained in various
systems bears a definite relation to atmospheric
pressure. (At sea level, this pressure is taken to be
15
Table 2
The Relationship between the Degree of Vacuum
and Pressure5
Condition
Low vacuum
Medium vacuum
Fine vacuum
High vacuum
Very high vacuum
Ultra high vacuum
Pressure Range
760 to 25 torr
25 to 1.0 torr
1.0 to 10 -3 torr
1.0 x 10 -3 to 1.0 to 10 -6 torr
1.0 x 10 -6 to 1.0 to 10 -9 torr 1.0
x 10 -9 torr and below
Table 3
Relationship between Pressure and the Magnitude
of the Mean Free Path5
Pressure
(Torr)
No. of Molecules
per cm3
760
1.0 x 10-7
2.7 x 1019
2.7 x 109
Mean Free
Path (mm)
9.5 x 16-5
14 x 103
16
17
18
11.
Recent Developments
19
Table 4
A Representative List of the More Important Industrial Brazing Alloys
No.
Specification or
Description
Nominal
Melting
Range C
410 - 550
Typical Uses
BS 1942/2
88 AI-12 Si
550 - 570
3
4
5
50 Ag-Cu-Zn-Cd
34 Ag-Cu-Zn-Cd
23 Ag-Cu-Zn-Cd
620 - 630
612 - 668
616 - 735
6
7
92 Cu-2 Ag-6 P
80 Cu-15 Sg-S P
644 - 740
644 - 700
8
9
10
11
50 Ag-Cu-Zn-Cd-Ni
50 Ag-Cu-Zn-Cd-Ni-Mn
96 Cu-Ni-Si
85 Cu-Ni-Mn
634 - 656
639 - 668
1090 - 1100
965 - 995
12
56 Ag-In-Cu-Ni
600 - 711
13
14
43 Ag-Cu-Zn
85 Ag-15 Mn
689 - 788
960
15
80 Ag-20 Zn
725 - 785
16
67 Ag-Cu-Zn
70S - 723
Brazing of silver.
17
18
19
37.5 Au-Ag-Cu-Zn-Cd
58.3 Au-Ag-Cu-Zn-Cd
75.0 Au-Ag-Cu-Zn-Cd
695 - 715
703 - 730
633 - 705
20
Pure copper
100 Cu
1083
21
97 Cu-Ni-B
1081 - 1101
22
23
73 Ni-Cr-Fe-Si-B-C
81 Ni-Si-Cr-C
1060
1100
Brazing for service at elevated temperatures and for nuclear energy applications
(No. 23 only).
24
25
71 Ag-29 Cu
15 Pd-Ag-Cu
778
856 - 880
26
27
68 Au-Cu-Ni-Cr-B
82.5 Au-Ni
9S0 - 980
950
28
60 Pd -40 Ni
1237
29
Platinum
100 Pt
1769
30
Ti-Cored Ag/Cu
900*
* Working temperature.
20
Nominal Composition
12.
21
Table 5
Suitability of Various Brazing Alloy/Parent Metal Combinations for Furnace Brazing in Reducing
or Neutral Atmospheres7
Composition
Aluminium Alloys
Copper
No.
Magnesium Alloys
Copper Alloys
Silver Alloys
Gold Alloys
Carbon Steels
Stainless Steels
Cemented Carbides
Nickel Alloys
Cobalt Alloys
Titanium Alloys
Tungsten
Molybdenum
Tantalum
Niobium
Parent Metals
Mg-Al-Zn
Al-Si
3,4,5,8,9
Ag-Cu-Zn-Cd-(Ni,Mn)
13,16
Ag-Cu-Zn
6,7
Ag-Cu-P
12
Ag-Cu-In-Ni
10,20,21
Cu(Ni-Si,B)
14
Ag-Mn
15
Ag-Zn
17,18,19
Au-Ag-Cu-Zn-Cd
22,23
Ni-Cr-Si-B-C
24
Ag-Cu
25
Ag-Cu-Pd
28
Pd-Ni
26,27
Au-Ni(Cu-Cr-B)
29
Pt
Brazing Alloys
Notation:
O
N
P
R
=
=
=
=
Impossible
Not recommended
Possible but seldom used
Recommended and known to produce satsifactory results.
Notes:
1. Brazing fluxes may have to be used in addition to a protective atmosphere when the parent metals brazed contain
alloy constituents forming refractory oxides (e.g. Cr, Ti, Al, Zn. etc.).
2. It is not recommended to furnace braze tantalum, niobium, and tough pitch or oxidised copper in hydrogen-bearing
atmospheres.
22
Table 6
Suitability of Various Brazing Alloy / Parent Metal Combinations for Vacuum Brazing7
Composition
Aluminium Alloys
Copper
No.
Magnesium Alloys
Copper Alloys
Silver Alloys
Gold Alloys
Carbon Steels
Stainless Steels
Cemented Carbides
Nickel Alloys
Cobalt Alloys
Titanium Alloys
Tungsten
Molybdenum
Tantalum
Niobium
Parent Metals
Mg-Al-Zn
Al-Si
3,4,5,8,9
Ag-Cu-Zn-Cd-(Ni,Mn)
13,16
Ag-Cu-Zn
6,7
Cu-Ag-P
12
Ag-Cu-In-Ni
10,20,21
Cu(Ni-Si,B)
14
Ag-Mn
15
Ag-Zn
17,18,19
Au-Ag-Cu-Zn-Cd
22,23
Ni-Cr-Si-B-C
24
Ag-Cu
25
Ag-Cu-Pd
28
Pd-Ni
26,27
Au-Ni(Cu-Cr-B)
29
Pt
Brazing Alloys
Notation:
O
N
P
R
=
=
=
=
Impossible
Not recommended
Possible but seldom used
Recommended and known to produce satisfactory results
23
Composition
Melting
Range
Usual
Joint Gaps
mm
Conforms
to BS 1845
Ag-Cu
Ag
Au
Pd
Pt
5 Pd-Ag-Cu
10 Pd-Ag-Cu
10 Pd-Ag-Cu
15 Pd-Ag-Cu
20 Pd-Ag-Cu
25 Pd-Ag-Cu
5 Pd-Ag
18 Pd-Cu
30 Pd-Ag
60 Pd-Ni
80 Au-Cu-Fe
62.5 Au-Cu
37.5 Au-Cu
30 Au-Cu
70 Au-Cu
82.5 Au-Ni
68 Au-Cu-Ni-Cr-B
75 Au-Ni
778
962
1064
1552
1768
807810
830840
824850
856880
876900
901950
9701010
10801090
11501225
1237
908910
930940
980998
9961018
10301040
950
950980
950990
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0750.2
0.0750.2
0.0750.2
0.0750.2
0.0750.2
0.0750.2
0.0750.2
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0250.1
0.0750.2
AG 7V
AG 8
PD 1v
PD 3V
PD 2V
PD 4V
PD 5V
PD 6V
PD 7V
PD 8V
PD 14V
AU 1V
AU 2V
AU 3V
AU 4V
AU 5V
AU 6V
71
REFERENCES
1 Kubashevskii, 0., Evans, E.: Metallurgical Thermochemistry
IL. 1954. (Translation from the Russian.)
2 Lustman, B.: Resistance of Metals to Scaling, Metal
Progress, 50, No. 5, 850, 1946.
3 Brooker, H. R. and Beatson, E. V.: Industrial Brazing, p. 58.
4 Hancock, P. F.: Metal Industry, February 11th and February
18th, 1949.
5 Schwartz, M. M.: Modern Metal Joining Techniques. WileyInterscience, 1967.
6 AWS Brazing Manual, 1963.
7 Sloboda, M. H.: The Selection of Brazing Alloys, Welding
and Metal Fabrication, October 1966.
8 Johnson Matthey Metals Ltd. Data Sheet 1100:200.
24
25
26
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