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Furnace Atmospheres No. 4
Brazing of Metals

Preface
This booklet is part of a series on process application technology
and know-how available from Linde Gas. The focus is on the
use of furnace atmospheres however a brief introduction is also
provided for each process. In addition to this work on brazing,
the series includes:

• Furnace Atmospheres No. 1


Gas Carburizing and Carbonitriding

• Furnace Atmospheres No. 2


Neutral Hardening and Neutral Annealing

• Furnace Atmospheres No. 3


Nitriding and Nitrocarburizing

• Sub-zero Treatment of Steels

• Soldering of Printed Circuit Boards

2
Contents

I. Brazing Principles 4
A. What is Brazing 4
B. Wetting and Spreading 6
C. Designing a Quality Brazement 6
D. Brazing Alloy 8
E. Cleanliness 8
F. Thermal Brazing Cycle 10
II. Furnace Brazing 10
A. Furnace Selection 10
B. Continuous Furnace Atmosphere Brazing 11
C. Batch Furnace Atmosphere Brazing 12
D. Vacuum Furnace Brazing 13
III. Atmosphere Basics 15
A. Functions & Major Composition 15
B. Atmosphere Influence on Wetting and Spreading 16
C. Principles for Atmosphere Control 18
1. The Atmosphere Oxygen Potential 18
2. The Atmosphere Carbon Potential 20
3. The Atmosphere Nitrogen Potential 20
4. Hydrogen Reactions 21
D. Atmosphere Control Systems 21
E. Vacuum as Atmosphere 22
IV. Atmosphere Generation and Supply 25
A. In-Situ Generation 25
1. Methanol Dissociation 26
2. Nitrogen, Argon, and Hydrogen Supply 26
B. Nitrogen and External Atmosphere Generators 27
1. Endogas (RX) 28
2. Exogas (DX) 28
3. Monogas (HNX) 28
4. Cracked ammonia 28
V. Brazing of Different Alloys 29
A. Steel Brazing 29
B. Stainless Steel Brazing 30
1. Atmosphere Brazing 30
2. Vacuum Brazing 30
C. Aluminium Brazing 33
1. Atmosphere Brazing 33
2. Vacuum Brazing 35
D. Copper and Brass Brazing 35
E. Brazing of Reactive Metals 36
F. Brazing of Ceramics and Glasses 36
G. Brazing of Cemented Carbides 37
VI. Safety Hazards and Precautions 38
A. Normal Operating Conditions 38
1. Explosion/Flammability of Atmosphere – Fire 38
2. Flux/By-products 38
B. Hazards Associated with Unexpected/Emergency Situations 38
C. Hazards Associated with Maintenance Operations 38
1. Confined Spaces and Oxygen Deficiency or Asphyxiation. 38
2. Pressurized Piping and the Gas Expansion Hazard 38
VII. Troubleshooting Common Problems 39
VIII. Terminology 40
IX. References 41
Appendix 42

3
I. Brazing Principles

A. What is Brazing

Brazing is a metal joining process that uses heat and a braze Table 1. Characteristics of joining processes.
alloy, often called filler metal, to create a metallurgical bond be-
tween two or more separate pieces without melting or substan- Soldering
tially modifying the materials structure. The materials being − Solder alloy, called solder, has liquidus below
joined, referred to as the base materials, are positioned so only a 450 ºC (840 ºF)
small gap separates the pieces. A braze alloy is positioned close − Forms bond with base material mainly by
to the gap and upon melting, the braze alloy is drawn into the mechanical adhesion
gap by capillary action. This forms a solid joint upon cooling. − Base metal remains solid
To be defined as brazing, the braze alloy melting temperature − Performed in air or nitrogen using a flux
must be below the melting point of the base material but above to break down surface oxides.
450 ºC (842 ºF).
Brazing
The commonly used joining processes are brazing, welding, and − Braze alloy, also called filler or filler metal,
soldering. Table 1 describes some of the defining characteristics has liquidus above 450 ºC (840 ºF)
that distinguish each process. − Typical processing temperatures: 540–1620 ºC
(1000 – 2950 ºF)
Brazing allows diverse configurations of parts, dissimilar metals − Forms metallurgical bond with base material
and non-metals of non-uniform thickness to be joined where by dissolving a very small amount of surface
other joining methods could not be economically used. Braz- material
ing is most commonly performed on metals including those − Base metal remains solid
that are wrought (sheet, bar, tubing and extrusions), cast (sand, − Performed in air, inert, reducing or vacuum
investment, die, shell and pipe), and powdered metal products. atmospheres
Joining of ceramics and glasses is also viable, and is experienc- − Fluxes may or may not be required
ing increased usage with advances in this technology.
Welding
There are different brazing methods such as torch brazing, − Weld alloy has liquidus above 450 ºC.
furnace brazing, induction brazing, dip brazing, and resist- − Part of base metal melts to join with braze alloy
ance brazing. In this booklet only furnace brazing is described. − Forms metallurgical bond with base material
Advantages and limitations of the furnace brazing process are
shown in Table 2.

Table 2. Advantages and limitations of the brazing process

Advantages Limitations

• Economical fabrication of complicated assemblies with • Base metals hardened via heat treatment or cold working
many joints may loose these properties during brazing.
• Distortion and warpage are relatively low. • The gap, or spacing, between the pieces largely determines
• High production rates can be readily accomplished using the strength of the joint. Control of the gap is a critical de-
commercially available equipment and process know-how. sign and production parameter.
• Dissimilar material combinations can be joined. • Parts must be held in a particular orientation and spacing
• Materials of varying thickness and cross sectional area can during heat-up, processing, and until solidification is com-
often be accommodated. plete.
• Complex geometries and multi-step joining procedures • Production of small quantities may not be cost effective.
can be designed. • Calculating the mechanical properties of an assembly can be
• Reproducible, high quality results can be obtained. difficult.
• Brazing can be combined with heat treatment in the same
cycle
• The process is well recognized and documented in design
handbooks.

4
Uniform heating, minimal distortion, no melting of the base
material, and the viability of both high and low volume produc-
tion contribute to the wide spread application of brazing as a
joining process. The wide variety of brazing applications is ex-
emplified in Figure 1.

Figure 1. Examples of brazed parts:


a) Heat exchanger of (Courtesy of Baxi AB),
b) Different automotive and other parts
(Courtesy of Mahler GmbH, Germany),
c) Turbine parts
(Courtesy of Ipsen International GmbH),
d) Electric couplings
(Courtesy of Ipsen International GmbH)

a.
b.

c. d.

5
B. Wetting and Spreading
Figure 3.
A braze joint is formed when the braze alloy (filler metal) is Schematic showing relationship of contact angle to surface
drawn into the space between two surfaces that are close and par- tension a) Effective wetting b) Poor wetting or de-wetting
allel. This movement is via capillary action and actually occurs in
three steps: adhesion, wetting, and spreading of the braze alloy. a)
The surface tensions acting on a drop of braze alloy are illus- Base metal
trated in Figure 2. Molten Filler Metal
Joint Clearance
θ

Figure 2.
Mathematical balancing of surface tensions for a drop of braze
alloy on a metal substrate.
b)
Base metal
γLV Braze Alloy
Molten Filler Metal
Vapor Joint Clearance θ
γSV θ γSL

Substrate
(base material)

γSV – Surface tension at the solid/vapor interface The wetting properties vary with different materials in the fol-
lowing way [1]:
γLV – Surface tension at the liquid/vapor interface
γSL – Surface tension at the solid/liquid interface – Difficult to wet:
Titanium, zirconium, ceramics, glass, and titanium
carbide.

– Fair wetting:
Wetting can be analyzed by mathematically balancing the hori- Aluminium, cast iron, tungsten, tungsten carbide,
zontal components of the surface tensions by using what is molybdenum, tantalum, and alloys with more than 5%
known as Young’s Equation. of metals forming refractory oxides.

γSV – γSL = γLV cos θ (Eq. 1) – Good wetting:


Copper, nickel, cobalt-alloys, steels, and precious
The contact angle θ provides a measure of the quality of wetting. metals.
To have good wetting the wetting angle, θ, must be substantially
smaller than 90°. θ<60° is in real practice required for good wet-
ting and for a proper joint to form. Equation 1 shows that θ<90° C. Designing a Quality Brazement
corresponds to the condition γSV > γSL . A decrease of the angle θ
resulting in improved wetting can be achieved by: The braze joint should be designed as part of the overall compo-
nent design. The joint configuration plays a critical role in the
– Increasing γSV mechanical and fatigue resistance, corrosion resistance, thermal
– Decreasing γSL and electrical properties and physical appearance of the final as-
– Decreasing γLV sembly. Certainly, consideration must be given to cost effective
manufacture.
Figure 3 shows the specific application to brazing. When:
Examples of common braze joints are shown in Figure 4 and
θ < 90°, there is wetting some basic comparisons between the types of joints are illus-
θ > 90°, there is no wetting or de-wetting. trated in Table 3.

If a reaction such as alloying occurs between the filler and base Butt Joints – The smaller the available bonding area, the low-
metals, the change of Free Energy due to that reaction contrib- er the strength of the joint. In a butt joint, the only available
utes to the wetting. bonding surfaces are the cross-sectional area of the pieces being

6
Table 3. Comparison of common braze joints

Feature Butt Joint Lap Joint Butt-Lap Joint Scarf Joint


Strength of Joint Lowest Good Moderate Moderate

Ease of Set-up May be difficult with Braze alloy is easy to Depends largely on Requires fixturing
thermally mismatched place complexity of component. to maintain gap and
materials Easy self-jigging or Might be self jigging or alignment.
self-aligning fixturing may require fixturing

Advantages Ease of preparation Load is transmitted in Single thickness Load bearing capacity
Low stress concentration shear rather than tensile Placement of braze between that of the butt
Single thickness stresses. alloy may be controlled. and lap joints.
of material Can control location Single thickness.
of stress concentration
points.

Disadvantages Load transmitted as Double thickness of Requires more Complicates part


tensile stress material due to overlap machining and fabrication.
Stress concentration preparation. Fixturing generally
produced at edge of lap May require fixturing. required
Complicates part fabri-
cation.

Butt/Lap Joints – Butt/lap joints combine the properties of the


Figure 4. Basic types of braze joint configurations two methods by machining a precision contour through the
thickness of the base materials to provide mating surfaces. The
Butt Joint increased amount of contacting surface offers increased me-
chanical strength. The profile minimizes stress concentration
and therfore reduces the risk of crack initiation. This type of
Single Lap Joint joint provides precision features for controlled gap spacing. The
added production steps of machining, cleaning, and set-up in-
crease the manufacturing cost.
Double Lap Joint
Scarf Joint – Scarf joints are an attempt to combine the smooth
surface of the butt joint with the increased strength for the
Butt-Lap Joint
lap joint. In a scarf joint, the faying surfaces are machined to
a precision angle to increase the contacting surface area. The
Scarf Joint
advantage obtained by maintaining a single thickness through
the joint must be evaluated against the difficulty in machining,
alignment and braze alloy placement. Scarf joints have higher
joined, so the strength of the joint is limited. The major advan- load bearing capability than butt joints because the stresses are
tage of this configuration is the smooth contour and the clean transmitted off-axis and the bond cross-sectional area is greater.
appearance. The major disadvantage is low strength, which
makes this type of joint fairly uncommon. The joint gap is of great importance for establishing a high
strength joint. Generally joint strength will increase with de-
Lap Joints – Just like their name, the pieces overlap to produce a creased joint gap. Table 4 gives some approximate recommen-
large bonding area, but create a change in the overall thickness dations for joint gaps for various braze alloy systems at ambient
of the assembly. Jigging and braze alloy placement are relatively temperature. It must be made clear that the gaps in table 4 are
easy in this configuration, and the orientation of the component just guidelines as, the joint gaps can vary a lot depending on
can often be controlled during the brazing process so the parts geometry, joint length, specific alloy composition etc.
do not move relative to each other. Lap joints are either of the
type single lap or double lap configuration.

7
Table 4. Preferred gaps for different brazing filler metals [2]. ing alloy powder in a solvent and binder suspension agent and
The gaps given are just for guidance as they may vary with is commonly used because of its flexibility of application, wide
conditions. availability, and low cost. It is important to supply sufficient
paste to the joint to accommodate for the thermal expansion of
Brazing filler-metal system Joint clearance, mm (in.) the work pieces being joined and for loss of the vaporized braz-
Al-Si alloys 0.15-0.61 (0.006-0.024) ing paste solvents at elevated temperature. Braze alloy pre-forms
Mg alloys 0.10-0.25 (0.004-0.010) are solid forms of braze alloy as rings, sheets, shims, and wire.
Cu alloys 0.00-0.05 (0.000-0.002) Pre-forms can be put into place as part of the assembly process,
Cu-P 0.03-0.13 (0.001-0.005) and may allow complete assembly of a component prior to braz-
ing. Pre-forms may offer a cleaner application and be less labor
Cu-Zn 0.05-0.13 (0.002-0.005)
intensive than pastes, but they can be difficult to place correctly
Ag alloys 0.05-0.13 (0.002-0.005)
in the assembly.
Au alloys 0.03-0.13 (0.001-0.005)
Ni-P alloys 0.00-0.03 (0.000-0.001)
Braze alloys come in literally hundreds of compositions, many
Ni-Cr alloys 0.03-0.61 (0.001-0.024) of which have been developed to accommodate a particular end
Pd alloys 0.03-0.10 (0.001-0.004) user or product type. Most alloys melt over a temperature range,
not at a discrete “melting point” such as for a pure metal. This
melting range is an important parameter for selecting the ap-
There are a number of other factors that influence the brazing propriate filler. The lower temperature is called the solidus. This
success such as; the braze alloy viscosity and specific gravity, the is the onset of melting. The upper temperature where the filler
tendency of the filler metal to alloy with the parent metals, joint is completely liquid is called the liquidus. For braze alloys with
length, brazing temperature and base metal reactions [1,2]. eutectic composition, the solidus and liquidus are the same tem-
perature. This is called the eutectic temperature. In general, the
The strength of a professionally and succesfully brazed part sub- braze alloy must be fully liquid at the brazing temperature to
jected to tensile stress across the joint will be decided by the base flow and enter the joint through capillary action. Brazing tem-
material strength and not by the joint. Tensile tests of bars of a perature therefore as a general guideline is 20-30°C higher than
precipitation-hardening alloy have proven this. The tests were the braze alloy liquidus. The braze alloy liquidus temperature is
made in the as brazed condition and after additional aging to the minimum brazing temperature. Table 5 gives an overview
give precipitation-hardening affect of the base metal. The tensile of types of filler metals, their properties and applications.
strength of the brazed bars was substantially greater after aging
[3], which proves that joint strength was not the limiting factor for
the overall strength. E. Cleanliness

Wetting is negatively affected by the presence of surface oxides


D. Brazing Alloy and contaminates such as dirt, grease, lubricants, and deter-
gents. Poor cleanliness results in lack of wetting, incompletely
The braze alloy, often called filler metal, is the material used to filled joints, and low joint strength. The furnace atmosphere
bridge the gap between the two pieces being joined. Forming can remove limited amounts of surface oxidation by integrating
an effective bond requires the braze alloy to wet, spread, and enough amount of reducing gases such as hydrogen. However,
be drawn into the joint where it metallurgically bonds with the it is not advisable to use the brazing furnace, especially not a
surface in a continuous and binding way. If some of the braze vacuum furnace, as a cleaning machine. Vaporized dirt may in
alloy is soluble in or reacts with some constituent of the parent such cases condensate on cold furnace parts and create furnace
material, it is called alloying. The molten braze alloy can simply functionality problems.
dissolve the base metal forming an effective bond. Or the braze
alloy and base materials can interact metallurgically to form in- Mechanical cleaning may be performed by wire brushing, or
termetallics or precipitates. The molten braze alloy can penetrate blasting. Grinding or machining, requires the use of chemical
the base metal grain boundaries, or simply penetrate into surface cleaning to remove the machining fluids. Chemical cleaning
irregularities of the joint surfaces. Any of these effects will nor- methods will be determined by the type of surface contaminates
mally contribute to produce a strong joint. There is an exception likely to be found on the surface. Degreasing agents will remove
for those cases when brittle intermetallics form due to reactions hydrocarbon deposits from cutting oils, while aqueous clean-
between the braze alloy, the base metal, and the atmosphere. The ers work well to remove water based machining fluids. Plasma
risk to create unwanted precipitates increases with increased time cleaning and blasting with CO2 pellets would not leave any
at brazing temperature. residues if developed to be technically and economically viable
cleaning methods.
Braze alloy comes in a wide variety of forms including powder,
foil, paste, and solid metal pre-forms. Paste is a blend of braz-

8
Table 5. Major classes of braze alloys (filler metals) [2, 4, 5].

Alloy (filler metal) AWS Brazing Forms Base materials joined Major applications
family and type designation temperature, °C (°F)

Al-Si, eutectic BAlSi 555-645 (1030-1195) Preforms, wire, Aluminum to aluminum alloys, steel Car radiators, heat exchanges, hon-
rods, foil, powder, to aluminum, aluminium to beryllium eycomb aircraft structures, structural
RS foil (a) parts

Cu-X, solid solution BCu 1095-1150 (2000-2100) Preforms, wire, Copper to copper alloys, copper to Heat exchangers, structural parts, au-
910-980 (1670-1800) rods, foil, powder, mild steel, copper to stainless steel, tomotive parts
Cu-Zn, peritectic RBCuZn RS foil most ferrous metals combinations

Cu-P, eutectic BCuP 690-925 (1275-1700) Preforms, wire, Copper to copper, copper to silver/ox- Electrical contacts, bus bars, heat ex-
rods, foil, powder, ide powered metal composites changes
RS foil

Cu-Ag, eutectic BAg 620-980 (1150-1795) Preforms, foil, Most ferrous and non-ferrous metals, Most widely used utility filler metals
powder except aluminium and magnesium

TM-Si-B(b), eutectic BNi 930-1205 (1705-2200) Powder, tape(c), AISI 300 and 400 series steels and Aircraft turbine components, automo-
(Ni/Fe + Cr)-Si-B RS foil nickel- and cobalt-base super alloys; tive parts, heat exchangers, honey-
carbon steels; low-alloy steels; and comb structures, moulds, other tools
copper etc.
(Ni, Pd)-Si-B None Powder, tape, RS AISI 300 series stainless steels, ce- Honeycomb structures, cemented
foil mented carbide, super alloys carbide/polycrystalline diamond tools,
orthodontics, catalytic converters
(Co, Cr)-Si-B BCo 1175-1245 (2145-2275) Powder, tape, RS Cobalt-base heat-resistant corrosion- Aircraft engines, honeycomb marine
foil resistant super alloys structures

Au-Ni, solid solution BAu 890-1230 (1635-2245) Preforms, wire, Nickel-base heat-resistant alloys, Honeycomb structures, structural tur-
rods, foil, tape steels bine parts

Cu- (Ti, Zr)-Ni eutec- None Cladded strip, RS Titanium/zirconium-base alloys Titanium tubing, aircraft engines,
tic and peritectic foil honeycomb aircraft structures, aircraft
structural parts, chemical reactors

a) May be produced as rapidly solidified, ductile, amorphous/microcrystalline foil.


b) This group includes alloys based on transition metals (TM) such as nickel, iron, and cobalt.
c) Brazing filler metal is carried on a plastic-bonded tape

9
F. Thermal Brazing Cycle amount of fixture determine the pre-heat and holding time. Pro-
vide enough time for the temperature to stabilize.
A typical brazing process cycle is pre-heat (optional) including
holding, ramp to temperature, brazing, cool down and exit, as Ramp to temperature – The parts should heat quickly but uni-
illustrated in Figure 5. formly. The heating rate is therefore limited by the risk of cre-
ating distortion due to thermal stress build up. For parts with
Pre-heat and holding – Preheating is done up to a temperature complicated geometries, big dimensions, big differences in di-
which is below the filler metal solidus. Part thickness and the mensions, or crack sensitive materials, more than one holding
step and associated ramp may be required.

Brazing – Brazing time should be the minimum time that al-


Figure 5. Schematic of a typical brazing process cycle
lows the braze alloy to flow through the joint. Often one to two
minutes is enough to create a sound joint. Theoretical predic-
tions as well as actual measurements show that joint filling by
Brazing the molten braze alloy occurs virtually instantaneously in a time
of the order of 0,1 second [6]. Extended processing times can
Dwell Heating
lead to excessive interactions between the filler and base met-
Temperature

Cooling
al, grain growth, and recrystallization. However, in some cases
longer processing time is beneficial when the braze alloy inter-
action will lead to a modified braze alloy with increased melting
temperature which may be beneficial if the component will be
Preheat
brazed a second time.

Cool-down and exit - A controlled cool down allows the joint to


solidify. Cooling under a protective atmosphere down to a tem-
Time perature of about 150 °C (300°F) for steels will avoid discolora-
tion of parts exiting the furnace.

II. Furnace Brazing

A. Furnace Selection

A thorough knowledge of the product, material requirements, line. Continuous equipment offers some flexibility for changes
production volumes, and schedule are vital information when in atmosphere and/or temperature. For batch equipment, the
a company is purchasing a furnace or looking for a commer- entire furnace must undergo the process cycle even if only a few
cial brazing company. The types of brazing furnaces are gener- parts are in the load. If standardized loads are expected and the
ally classified as continuous, batch, or vacuum furnaces and are furnace will not be actively brazing at least 50% of the time (2
compared in Table 6. shifts 5 days per week), batch equipment may be a good choice.
An operator must be continuously present to load and unload
Processing requirements of the base material and the filler alloy parts from a continuous furnace, while for a batch furnace an
with respect to temperature and atmosphere are the most criti- operator need only be present to start and finish the process.
cal aspects of furnace selection. If oxygen, nitrogen, or hydrogen If flammable gases are used, then an operator must always be
can not be tolerated, vacuum processing will offer the highest present, but may be involved with other activities.
quality. Ceramics and reactive metals such as titanium, molyb-
denum, vanadium, beryllium, and tantalum must be processed Capital and Operating Costs - If the material does not require
in a non-oxygen bearing inert argon or helium atmosphere or in the use of vacuum, then continuous and batch atmosphere
vacuum. furnaces often offer a lower cost capital solution. Each facility
must determine which furnace offers the best cost of operation.
Production Levels – Critical production information includes If utility cost are high or are restricted, batch equipment may
the number, weight, and shape of parts. Other important in- offer a significant advantage. Reliability of vacuum equipment
formation is if the parts arrive at the brazing departments in has improved substantially over the past decade and the current
batches or should be brazed as part of a continuous production generation of equipment is easier to install, program, and main-

10
Table 6. Comparison of common types of protective atmosphere
and vacuum brazing furnaces
Characteristic Continuous Furnace Batch Furnace Vacuum Furnace
Scheduling/Production rates Continuous production Production in batches Production in batches*
Operator required in Operator required to Operator required to load and Operator required to load and
attendance? continuously load and unload furnace and to start unload furnace and to start
possibly unload parts and finish process. Operator and finish process. Operator
from belts or trays presence may be required if presence may be required if
hydrogen is in use. hydrogen is in use.

Capital Cost Moderate to high Moderate High


Can produce reducing Yes Yes By dissociation
environment
Can produce oxidizing Yes Yes No
environment
Can produce very low oxygen Most cannot Most cannot Yes
environments
Environmental issues Emissions of CO Emissions of CO Minor emissions from oil
and excess heat and excess heat vapors from vacuum pumps
Can handle long parts and With difficulty Effectively Effectively
complicated assemblies
Can be shut-off or idled for Furnace would be idled Yes, but mostly maintained at Yes, can be completely shut off
off-production during off-production temperature
(Reduced atmosphere
and temperature)

Cleanliness of final product Clean Clean Very clean


* There are semi continuous vacuum furnaces for instance for aluminium brazing but batch vacuum furnaces dominate.

tain which leads to low operational cost. Vacuum brazing in


Figure 6. Parts entering a continuous atmosphere brazing
addition offers lower running costs for utilities such as for elec-
furnace riding on a mesh belt (Courtesy of Mahler GmbH)
tricity and gas. Stronger environmental legislation and direc-
tives may in the future lead to costs for cleaning and recycling
of effluents which will lead to even stronger economical benefits
with vacuum brazing.

B. Continuous Furnace Atmosphere Brazing

Continuous brazing is suitable for production with a steady flow


of incoming parts. The parts move through the furnace, either
as individual components or in trays or baskets. Mesh belt,
humpback, or pusher furnaces are generally used. A furnace is
typically brick or fiber-lined with a metallic muffle to assure con-
trol of the atmosphere and to minimize the amount of contami-
nation residing in the insulation. A continuous furnace offers
consistent part quality, readily integrates into to the manufactur-
ing material flow, and is easily adaptable for automation. Figure
6 shows individual parts entering a continuous atmosphere fur-
nace on a mesh belt and Figure 7 shows a typical small, mesh
belt furnace. speed of the conveying mechanism. To allow a rapid heating
to temperature, the heat input in the first section of the furnace
In a continuous furnace the parts to be brazed are transported must be high. A short dwell time at the brazing temperature is
on a conveyor. The temperature profile is determined by the followed by a cool down to solidify fast enough to avoid forma-

11
hydrogen consumption. Nitrogen is introduced at the entrance
Figure 7. Mesh belt furnace (Courtesy of Mahler GmbH) and exit to buffer the hydrogen-processing chamber from dis-
turbances from air ingress caused by product movement in and
out of the unit. Removing product that has fallen from the belt
or trays that get jammed is more difficult in a humpback than in
a flat belt or pusher due to its unique configuration.

C. Batch Furnace Atmosphere Brazing

As indicated by the name every batch or load is processed sepa-


rately. Depending on how the furnace is loaded they are called
pit furnace (loaded from the top), bell furnace (loaded from the
bottom) or box- or retort furnaces (loaded from the side, an ex-
ample is shown in Figure 9). As with continuous furnaces, a
metallic lining is used to isolate the atmosphere from the insula-
tion and potential contamination. This lining is may be called
a retort, muffle or inner cover depending on the type of furnace
being discussed. The furnaces are sealed using either a gasket
tion of precipitates and intermetallics that may cause embrittle- or seal made of sand or oil to keep the oxygen and moisture lev-
ment. The cooling section of the furnace must be long enough els low.
for the parts to reach low enough temperature, typically as men-
tioned before below 150 °C (300 °F) for steels, to avoid oxidation A typical cycle would include pre-heating, ramping to tempera-
upon exiting the furnace. ture, brazing and cool down.

Essentially, the thermal profile is determined when the furnace Step 1: The cycle begins by loading and closing the furnace.
is designed. The ratio of time spent during heat-up versus time
at brazing temperature is fixed due to the ratio of lengths of each Step 2: The load is heated to an intermediate temperature to
of the furnace zones. allow any surface contamination to off-gas and allow the load to
come to a uniform temperature.
Commonly, parts may travel on a mesh belt fabricated of met-
al, or of carbon composite for very high temperature applica- Step 3: If the atmosphere is inert, it may be introduced at this
tions. Most belts remain level through the furnace. Humpback point. If a flammable atmosphere will be used, the chamber
furnaces (Figure 8) are the exception. The belt in a humpback may be filled with an inert gas that will later be replaced with
furnace travels up an incline or ramp, flattens through the high the flammable atmosphere. Some furnaces will allow introduc-
heat processing section, and then descends through the cooling tion of a flammable atmosphere into a furnace containing air,
chamber. The distinctive profile gives the humpback furnace its if the furnace is above the auto-ignition temperature of the at-
name. The low density of hydrogen gas allows it to accumulate mosphere and the furnace was designed to be gassed up in this
in the elevated section of this furnace, thereby minimizing the manner.

Figure 8. Schematic layout of a Humpback continuous furnace


(Courtesy of Mahler GmbH, Germany)

Heating energy Cooling water


Waste water
Protective gas
Flue gas Flue gas

Loading table Inlet channel Furnace Cooling zone Unloading


with drive table

12
then the pressure is maintained at a low value. Heating in that
Figure 9. Two chamber front loading CuproBraze® batch
case will only be by radiation.
brazing furnace with purging/cooling vestibule and a convection
heating chamber (Courtesy of Seco Warwick Corporation)
Step 3: Heating of the load begins. The heating rate should
allow the parts to heat uniformly to minimize distortion. The
parts are held for a soak period at a temperature below the filler
alloy solidus temperature to assure that the whole load uniform-
ly reaches the braze temperature before going to Step 5.

Step 4: At the end of the holding time, vacuum pumping is ac-


tivated to give a low pressure. This is to lower the atmosphere
oxygen partial pressure and to efficiently remove all volatile spe-
cies originating from vaporized brazing paste vehicles and dirt
on the parts

Step 5: The temperature is increased to the brazing temperature.


The braze alloy starts to melt and is drawn into the joint.

Step 6: The pressure is increased if the base alloy has alloying


elements that have a tendency to vaporize. The soak time at
brazing temperature shall be just enough long to assure melt-
ing of all braze alloy in the entire load and too long time may
lead to embrittlement. The properties of the final braze joint are
Step 4: The furnace will ramp to temperature, hold at the select- influenced by the time at temperature. Grain growth, penetra-
ed brazing temperature, and then ramp down to cool the load. tion of alloy along grain boundaries, precipitation of carbides of
During the cool-down, flammable atmospheres must be purged intermetallic compounds, and diffusion of alloying elements be-
from the furnace for safety. tween the braze alloy and base metal must be considered. If the
intention is to re-braze the assembly during a later process, then
Step 5: The load may be removed when it is below a tempera- an extended time at the brazing temperature is required to al-
ture that will cause discoloration. low the lower melting point elements in the filler alloy to diffuse
into the base material.
D. Vacuum Furnace Brazing
Step 7: In this step, the temperature is lowered until all the braze
Brazing is a major vacuum heat treatment process and the asso- alloy is solidified.
ciated product value probably exceeds that of any other vacuum
heat treatment process [7]. Vacuum brazing is particularly used
in the aerospace and electronic industries for joining of met- Figure 10. Temperature and pressure cycles in vacuum
als and alloys that easily react with oxygen, nitrogen, and other brazing.
gases and for parts that cannot tolerate the presence of fluxes or
other impurities. Complex assemblies with blind passages, such Pressure
as in stainless steel heat exchangers, are increasingly brazed in Furnace temperature
vacuum. Such parts are almost impossible to braze with atmos- Part temperature center
phere flux brazing. The steps in vacuum brazing are schemati-
cally shown in Figure 10.

Referring to figure 10 the brazing process follows these steps:

Step 1: The load is charged into the furnace. A vacuum pump


(rough pump) removes much of the air that entered the furnace
with the load. Another pump (normally a diffusion pump) re-
duces the pressure further.

Step 2: Inert gas (nitrogen) is let into the furnace and the pres-
sure is increased to a pressure in the range 0,9-1,5 bar to allow
for convection heating (assuming that the furnace is equipped 1 2 3 4 5 6 7 8 Step
with a fan for improving convective heating). If there is no fan

13
Step 8: Fast cooling down to room temperature is normally air through vacuum leaks or contaminated back-fill gas or from
achieved by introducing inert gas into the furnace up to a cer- dissociation of surface oxides. Water is generally inadvertently
tain elevated pressure. Nitrogen with 1-6 bar pressure is com- introduced from the water-cooled heat exchange system. Water
mon. Furnaces for 10 bar and higher are developed for higher contamination often begins as extremely small pinhole sized
cooling capacities. The proper cooling rate depends on the risk leaks that only open at elevated temperatures, making it difficult
for distortion and if there are certain requirements on the cool- to locate these leaks before they begin causing considerable braz-
ing rate for obtaining the best material properties. ing problems. Occasionally, water is introduced with the parts
either from incomplete drying after cleaning or hygroscopically
Vacuum heat treatment means that the occurrence of gaseous attached to the part surface or the furnace interior. To assure the
molecules is so rare that there are no net reactions such as oxi- highest quality vacuum conditions, vacuum furnaces should
dation or carburizing with the metal surface. There is a “clean- have all doors closed and be kept under vacuum to minimize
ing” action from the vacuum principally based on vaporizing. moisture and air infiltration when not in use. Discoloration of
If the vapor pressure or partial pressure of a certain element at vacuum brazed parts may also be caused by hydrocarbons origi-
the actual temperature is higher than the actual vacuum pres- nating from residual lubricants on improperly cleaned parts, or
sure then that element will vaporize. This is mostly a beneficial more commonly, from pump oil that migrates backward (back-
effect because dirt or oxides remaining on the metal parts will streams) into the vacuum chamber.
vaporize. Parts exiting the furnace after a vacuum brazing cycle
therefore mostly are cleaner than upon entering. An important Leak testing should be done when required because of discolor-
effect of vaporizing and degassing is that the braze joints will ation of brazed parts and as a regular quality control. Helium or
be free from pores. Joint strength accordingly is improved by the lower cost alternative nitrogen/hydrogen mixtures are used
vacuum brazing. In some cases, vaporizing can be negative if for leak testing. The principle used is that helium or nitrogen/
alloying elements in the base metal are vaporized. Running with hydrogen gas is sprayed around sealings and couplings on the
increased pressure, “partial pressure”, can counteract this. In outside of the vacuum furnace and a He or H2 sensor is placed
addition this also yields a better cleaning effect. at the vacuum pump outlet.

Oxygen, water and hydrocarbons are the most common contam- Examples of vacuum brazing furnaces are shown in Figure 11.
inates in vacuum atmospheres. Oxygen can be introduced as

Figure 11. Batch vacuum furnaces for brazing: a) Single b) Single chamber furnace with rails for bottom car loading of
chamber furnace with diffusion pump and argon supply tank heavy parts (Courtesy of Ipsen International GmbH)
to the right (Courtesy of Seco Warwick Corporation),

14
III. Atmosphere Basics

A. Functions & Major Composition

To avoid oxidation carburizing, decarburization and nitriding carbon monoxide (CO) balances with the oxidizing and decarbu-
the atmosphere must be neutral with respect both to the base rizing effect from carbon dioxide (CO2). By keeping a constant
metal and the braze alloy. Neutrality implies that no net reac- balance between oxidizing and reducing or/and carburizing and
tions occur between the metal/alloy and the elements oxygen decarburizing species it is possible to exercise the atmosphere
(O) and carbon (C). Reactions with nitrogen (N) and hydrogen control.
(H) must be considered in certain cases. Figure 12 shows that
these four elements may be present in the furnace atmosphere The neutral or inert part (nitrogen or argon) of the atmosphere
as the gas molecules oxygen (O2), hydrogen (H2) and nitrogen should:
(N2) but preferentially as elements in gaseous molecules such as • Purge away oxygen or other disturbing gases
carbon monoxide (CO), carbon dioxide (CO2), and water vapor • Eliminate air ingress to the furnace by maintaining an over-
(H2O). In the industrial practice it is easier and more reliable pressure (positive pressure) inside the furnace
to analyze and control the concentrations of the multimolecular • Carry and bring the active gas in contact with the metal sur-
species CO, CO2, and H2O instead of directly analyzing the O2 faces
and C concentrations in the atmosphere. • Dilute the atmosphere concentration of flammable constitu-
ents to assure safety.

Figure 12. Schematic of the interaction between atmosphere The active gas should:
and metal • Influence reacting surfaces to result in good wetting and a
Gas Gas/surface Metal quality brazement.
N2 • Maintain reducing conditions with respect to the metal oxides
O2 that may form during brazing.
CH4 H
• Maintain a neutral carbon activity (for steel brazing) to avoid
CO H2 O O decarburization or carburizing.
NH3 N • React with flux vapors and eliminate their detrimental effect
CO2 on the brazing result.
C
For safety and economic reasons, the amount of reactive gas is
C 3 H8 H2
generally the minimum amount required to create a clean and
sound braze joint.

Although not a primary function, the atmosphere influences the


The furnace atmosphere principally can be divided into two heat transfer during heating and especially during post-braze
major parts, a neutral gas and an active gas. The neutral gas is cooling. The atmosphere composition, type of gas, pressure, and
generally nitrogen and the active gas will consist of one or sev- the flow velocity of the gas will influence the heat transfer rate.
eral of the gas species carbon monoxide (CO), hydrogen (H2)
and hydrocarbon (CnHm). As seen in Table 7, the reducing ef- Controlled atmospheres used for high temperature brazing
fect from hydrogen (H2) is balanced by the oxidizing effect from fall into three broad categories; vacuum, reducing and neutral
water vapor (H2O). The reducing and carburizing effect from atmospheres, as shown in Figure 13.

Table 7. Atmosphere constituents and their action

Active gases Neutral or inert gases


Reducing Oxidizing Carburizing Decarburizing
H2** H2O CO H2O N2*
CO CO2 CnHm*** CO2 Ar
O2 O2 He
* Nitrogen is neutral to most metals but is actively nitriding titanium, zirconium, stainless steels and some
other metals with high affinity to nitrogen. These alloys have to be treated in argon, hydrogen or vacuum
** Hydrogen is reducing oxides and is neutral to most metals but is reactive to form hydrides with certain
metals like titanium and zirconium
*** CnHm stand for a hydrocarbon: Most common is methane, CH4.

15
ting is improved by establishing a clean, metallic, and oxide free
Figure 13. Joining atmospheres
base metal surface, which has the effect to increase the surface
tension γ SL.
Controlled Brazing atmospheres
Area of spread is a way to measure wetting. A solid braze alloy
is placed on a strip of base metal. The assembly is put into a fur-
nace and the temperature is increased until melting and wetting
Gaseous atmospheres Vacuum
occurs. After cooling the diameter of the solidified braze alloy is
measured. Figure 14 shows principally how wetting, measured
as the area of spread, significantly decreases with increasing
oxidizing power of the atmosphere. Too reducing conditions (=
low value of the ratio H2O/H2) may lead to excessive wetting.
Inert or Neutral atmospheres Reducing atmospheres Hence the wetting angle θ approaches 0°, leading to excessive
(Argon, Helium, Nitrogen) (H2 , CO)
braze alloy flow, to the point that it flows out of the joint and cre-
ates discoloration. The effect is sometimes called flashing. The
oxidizing/reducing power of the brazing atmosphere, measured
by the H2O/H2 ratio, accordingly has to be controlled within
Truly inert atmospheres are made up only by the noble gases certain limits. The ”Process Window”, indicated in Figure 14, is
argon and helium. Nitrogen can be regarded inert to most alloys specific for each braze alloy/base metal combination, for a high
such as steels and copper alloys. However, it is not inert in con- quality brazement to be the end result.
tact with metals that have a high affinity to nitrogen, which leads
to nitride formation or nitrogen pick up. Titanium is the most
important example of such a metal. Argon or possibly helium Figure 14. Principal variation of “Area of spread” for copper on
must be used in those cases. Also a CO/H2 containing atmos- steel in atmospheres with various H2O/H2 ratios.
phere can be neutral with respect to oxidation or decarburiza-
tion if, as described in the previous section, the ratios CO/CO2
and H2/H2O are controlled to be maintained at required levels.
Area of spread (= wetting ability)

Too good
Reducing atmospheres not only prevent the formation of surface wetting
oxides on the base metal at the brazing temperature but can also (flashing)
reduce and eliminate residual surface oxides which were present
before brazing or formed during the low temperature stages of
the heating process. Hydrogen is the gas with the strongest re- Process window
ducing power. However, carbon monoxide (CO) does also have a for good wetting
strong reducing power.

Vacuum is in this context considered a controlled atmosphere. No wetting


Vacuum acts like an inert gas in the way that there are no gas H2O/H2 Control range
species that can cause detrimental oxidation or other reactions
Reducing Oxidizing
with the base and filler metals. Vacuum is active in the way that
remaining surface residues on parts to be brazed are removed
by vaporizing and the vapors are pumped out of the furnace. Atmosphere concentration ratio H2O/H2
At high enough temperature and low enough pressure, oxide
removal by dissociation is possible. Clean surfaces ensuring
good brazability are achieved in this way.
For wetting of ceramics and glass, oxidizing gases such as air,
B. Atmosphere Influence on Wetting and Spreading water vapor, or carbon dioxide are in some instances added to
the atmosphere to promote wetting by achieving what is called
An atmosphere with low oxygen and moisture levels will allow reactive brazing (see section V.F).
the filler metal to melt and flow into even very tight joint clear-
ances. Oxygen or moisture present in the joining environment Braze alloy suppliers can give guidance on the atmosphere
will negatively interfere with wetting. As the oxygen and mois- compositions that work best with their products. Additionally,
ture levels rise, they impede filler to flow and degrade the joint reactions with the base material, availability of the specified at-
quality and strength. With reference to Figure 1, the atmosphere mosphere and furnace compatibility must be taken into consid-
influences mainly the surface tension γSV (solid/vapor) and to eration. For example, a furnace must be configured for flamma-
some extent γ LV (liquid/vapor) but not γ SL (solid/liquid). Wet- ble atmospheres before hydrogen or carbon monoxide additions

16
can be introduced. Disregarding these precautions can produce Tables 8 presents a few examples of commonly used atmos-
unsafe working situations. Further information on this topic is pheres for some combinations of base metals and braze alloys.
presented in section VI on Safety in this work.

Table 8. Atmospheres for brazing (adapted from Ref. 2)

Atmosphere Atmosphere composition, vol% Braze alloy Base Metal


H2 N2/Ar CO CO2 H2O CH2

In-situ Gas Mixing


Al/Si Aluminum,
Nitrogen 100
Cu/Sn/Ni/P Copper
1-75 25-99 Cu/Ag, Cu/P, Copper, brass, carbon
Nitrogen + Hydrogen Cu/Zn, Cu, Ni and low alloy steels,
stainless steels
Nitrogen + Methanol or 2-20 70-97 1-10 As above Copper, carbon and low
Nitrogen + Endothermic/ alloy steels,
Exothermic gas
Carbon and low alloy
Nitrogen + Natural Gas 99.5–95 0.5–5.0 As above
steels
Steels, stainless steels,
Hydrogen 100 As above
brass
Titanium, zirconium,
Argon + Hydrogen 1-75 25-99 As above nitrogen containing
steels
Vacuum
Vacuum > 2,5 mbar Cu/Ag, Cu/P Copper
Vacuum 0,5-2,5 mbar Cu/Ag, Cu/P Copper, low carbon steel
Copper, low carbon steel,
Vacuum 0,001-0,5 mbar Cu/Ag, Cu/P
low alloy steel
Cu/Ag, Cu/P,
High alloyed steel,
Vacuum < 0,001 mbar Ni, Ag, Au, Al/
Aluminium, Titanium
Si, Ti
Be, Mo, Nb, Ta, V, Zr,
Vacuum Various
ceramics, carbides
Externally Generated
Cu/Ag, Cu/P,
Exothermic gas, lean 5 75 N2 5 5 0.5 Copper, low carbon steel
Cu/Zn
Exothermic gas, rich 15 75 N2 10 As above + Cu Copper, low carbon steel
Copper, low and high
Endothermic Gas 40 40 N2 20 0.3 0.7 As above + Cu carbon steels, low alloy
steels
Cu/Ag, Cu/P, Copper, brass, carbon
Monogas 7 87 5 0.5 0.5 Cu/Zn and low alloy steels
Copper, brass, carbon
Dissociated ammonia (NH3) 75 25 N2 As above + Ni and low alloy steels,
stainless steels

17
C. Principles for Atmosphere Control
Figure 15. Relation between oxygen partial pressure (logaritmic
As indicated in Table 7 it is possible to adjust the atmosphere scale) and temperature for metal/metal oxide equilibriums for
composition to achieve certain oxygen-, carbon-, nitrogen- and copper (Cu), iron (Fe) and chromium (Cr). [8] (See also figure
hydrogen activities. Of these four elements, oxygen is for practi- 21)
cal reasons the most important one, as the control of oxygen is
fundamental to achieve non-oxidizing conditions. Carbon con- 1,0E-06
Cu/Cu2O

Oxygen partial pressure (atm)


trol is essential for steel brazing to avoid decarburization. Ni- 1,0E-09
trogen control is required in a few cases, the most important 1,0E-12
ones being brazing of stainless steel and of titanium. Hydrogen 1,0E-15 Fe/FeO
is normally not controlled but has to be taken into account when 1,0E-18
Cr/Cr2O3
hydrogen embrittlement is a problem (see section C.4). 1,0E-21
1,0E-24
The reasoning in the following paragraphs on the atmosphere 1,0E-27
oxygen potential, carbon, and nitrogen activities are perfectly 1,0E-30
valid only in thermochemical equilibrium. For heat treatment 1,0E-33
at high temperature, say above 800 °C (1472 °F), for long enough 600 700 800 900 1000 1100 1200
time, of the order of at least 10th of minutes, and in N2/CO/H2- Temperature °C
atmospheres, this assumption is approximately valid and there-
fore control is performed on the basis of chemical equilibrium.
Residence time for the gas in the furnace must also be long
enough for the equilibrium concept to be valid.
As seen in the figure the three metals are profoundly different
For lower temperatures and/or short times or for N2/CnHm with respect to sensitivity to oxidation. Extremes are copper and
-atmospheres the equilibrium assumption is no longer valid. chromium. Copper is a fairly “noble” metal, which means it
The atmosphere control then must be based upon empirical re- does not easily oxidize. Atmosphere requirement for oxide free
sults and kinetics. brazing are therefore modest. Chromium oxidizes on the oth-
er hand at extremely low oxygen concentrations meaning that
highly reducing atmospheres, typically pure hydrogen must be
used to avoid oxidation. The use of chromium as a pure metal
1. The Atmosphere Oxygen Potential is rare but stainless steels have chromium as major alloying ele-
ment, which makes it important to regard the oxidation of chro-
Metals will oxidize when they are heated in air at elevated tem- mium.
peratures. If a metal will oxidize in a particular atmosphere at a
certain temperature can be determined by calculating the oxy- The partial pressures of oxygen needed to oxidize metals at braz-
gen partial pressure that causes a metal to oxidize for that tem- ing temperatures are very low, ranging from approximately 10–6
perature. The oxidation of a pure metal, Me, is expressed by the atm (=1 ppm) to 10–30 atm (=10–24 ppm). These very low values
chemical reaction: are unrealistic as measurable values in the sense that there are
no free oxygen molecules to be measured at partial pressure of
Me + 1/2 O2 ↔ MeO (A) the order 10–30 atm. (The oxygen content of the brazing atmos-
phere, even using cryogenic purity nitrogen as the source, may
with the equilibrium constant, exceed the acceptable level of oxygen to avoid oxidizing the sur-
face.) However, although there is no free oxygen present, there
1/2
KA= 1 / PO are substantial and measurable amounts of oxygen bonded in
2
the molecules CO, CO2 and H2O. By measuring and balancing
(Assuming activities of metal and metal oxide can be approxi- the atmosphere ratios of CO2 / CO or H2O / H2 it is therefore
mated to unity.) possible to maintain the atmosphere oxygen control.

The oxygen partial pressure threshold value, PO2, above which As hydrogen (H2) and carbon monoxide (CO) are added to a
oxidation occurs, and below which the metal stays non-oxidized, brazing atmosphere, they react with the oxygen and create water
is well known for each metal. That pressure is for each metal vapor and carbon dioxide, respectively, according to the follow-
oxide just a function of temperature, the explicit value is found ing reactions
in chemical handbooks, tables or databases. As an example Fig-
ure 15 displays the equilibrium oxygen partial pressure as a H2 + 1/2 O2 = H20 (B)
function of temperature for the metal oxides of copper, iron and CO + 1/2 O2 = CO2 (C)
chromium.

18
Chemical equilibrium in these reactions means that the atmos- Therefore by using the relation between oxygen partial pressure
phere oxygen partial pressure, PO , can be expressed alterna- and water vapor concentration, Figure 15 can be redrawn, to
2
tively by, show oxidation equilibrium as a function of the concentration
PO = Constant × (PH O/PH )2 ratio H2O/H2 as shown in Figure 16. The diagram type in Fig-
2 2 2
or by ure 16 has to be made up for a specific hydrogen concentration.
PO = Constant × (PCO /PCO)2 The figure gives examples for 1, 5, 25 and 100 % hydrogen re-
2 2
spectively. The water concentration is measured as dew point.
where P denotes partial pressure and is at atmospheric pressure An example is drawn in the diagrams with lines for the dew
equal to the quantity vol-% divided by the factor 100. Quantita- point –50 °C (–58 °F) and brazing temperature 1000 °C (1830 °F).
tive expressions for the equilibrium constants may be found in At the dew point, –50 °C (–58 °F) only the 100 % hydrogen at-
the Linde Gas booklet “Neutral hardening and neutral anneal- mosphere will theoretically be clearly reducing towards Cr2O3
ing”. (the two lines cross each other below the Cr2O3 curve. The 25 %
hydrogen atmosphere is just on the border to be reducing (on
At brazing temperatures, it is easier to measure the water con- the curve). 5 and 1 % hydrogen atmospheres will be oxidizing
centration (as dew point) than the oxygen partial pressure. (the lines cross each other below the Cr2O3 curve).

Figure 16. Metal/metal oxide equilibrium as a function of brazing temperature and the
atmosphere moisture content expressed as dew point for: a) 1% hydrogen b) 5% hydrogen,
c) 25% hydrogen an d) 100 % hydrogen (Calculated by Thermo-Calc [9])

Temperature [Fahrenheit] Temperature [Fahrenheit]


500 1000 1500 2000 2500 3000 3500 500 1000 1500 2000 2500 3000 3500
100 100
200 200
CuO CuO
150 SnO Fe2O3 150
50 SnO Fe2O3 50

Dew Point [Fahrenheit]


Dew Point [Fahrenheit]

100 100
Dew Point [Celcius]
Dew Point [Celcius]

FeO FeO
50 50
0 0
0
Cr2O3 0
Fe3O4
Cr2O3 MnO
Fe3O4
–50 –50 –50 –50

ZnO –100 ZnO SiO2 Al2O3 –100


MnO Al2O3
–100 SiO2 –150 –100 TiO –150
TiO
–200 –200
–150 –150
0 500 1000 1500 2000 0 500 1000 1500 2000
Temperature [Celcius] Temperature [Celcius]

a. 1% hydrogen b. 5% hydrogen

Temperature [Fahrenheit] Temperature [Fahrenheit]


500 1000 1500 2000 2500 3000 3500 500 1000 1500 2000 2500 3000 3500
100 100
CuO 200 CuO 200
SnO
Fe2O3 FeO
150 150
SnO FeO Fe2O3
50 50
Dew Point [Fahrenheit]

Dew Point [Fahrenheit]

100 100
Dew Point [Celcius]
Dew Point [Celcius]

Fe3O4
Cr2O3
Cr2O3 50 MnO 50
0 Fe3O4 0
MnO 0 0
ZnO SiO2

–50 SiO2 –50 –50 –50


ZnO Al2O3
Al2O3 –100 –100
TiO TiO
–100 –150 –100 –150

–200 –200
MgO MgO
–150 –150
0 500 1000 1500 2000 0 500 1000 1500 2000
Temperature [Celcius] Temperature [Celcius]

c. 25% hydrogen d. 100% hydrogen

19
One method to reduce the oxygen level accordingly is to increase tential leads to carburizing which may leads to surface hardness
the proportion of hydrogen in the atmosphere. Another way is increase and on the extreme leads to soot deposits.
to increase the total gas flow rate in order to dilute the water
concentration to a low enough level. The addition of flux is a 3. The Atmosphere Nitrogen Potential
third way.
When brazing metals sensitive to nitrogen pick up such as, mo-
Brazing without flux, however, has great benefits because fluxes lybdenum, titanium, beryllium, niobium, tantalum, vanadium
are environmentally troublesome and cleaning of parts may be and zirconium or stainless steels, nitrogen gas is not longer
required. Fluxless brazing therefore is preferred. neutral but may cause detrimental nitriding.

As illustrated in figure 14 too low oxygen potential may result The nitriding reaction:
in too good wetting (flashing) and too high oxygen potential in
poor or no wetting. Oxidation also may lead to discoloration. N2 → 2N (D)

2. The Atmosphere Carbon Potential means that a nitrogen molecule, N2, splits into two nitrogen at-
oms, 2N, which dissolve in the metal. This reaction can be ne-
Atmosphere carbon concentration control is important in steel glected in most cases, but not in stainless steels, where chro-
brazing to avoid decarburizing or carburizing. Similar to calcu- mium attracts nitrogen and remarkable amounts of nitrogen
lating the oxygen potential, the carbon potential can be calcu- may dissolve in the steel as shown in Figure 17. In theory, the
lated for a furnace atmosphere from the knowledge of the CO surface nitrogen concentration is approximately proportional
+ CO2, CO + H2 + H2O or CO + O2 atmosphere concentrations. to the square root of the atmosphere nitrogen concentration
These gas constituents are controlled by atmosphere analysis as long as nitrogen is going into solid solution in austenite.
using infrared analysis of CO2, dew point analysis for H2O or This corresponds to the curve marked γ in the left part of the
oxygen probe analysis for O2. Using chemical equilibrium for- diagrams. For a certain nitrogen activity a knick point is seen
mulas, we can express the atmosphere carbon activity, ac, in the in the diagrams at about a nitrogen activity corresponding to
following alternative ways: √(PN2) = 0.3 and √(PN2) = 0.8 respectively. √(PN2) = 0.3 corre-
sponds to a nitrogen concentration in the atmosphere of approx-
ac = KI . (P2CO /PCO ) imately 10 vol%. Above this nitrogen activity, there is a change
2

ac = KII . (PCO . PH /PH O)


2 2
Figure 17. Theoretically calculated equilibrium surface nitrogen
1/2
ac = KIII . (PCO /PO ) concentrations as a function of atmosphere nitrogen activity
2
after brazing of two stainless steels at 1050°C (1920°F) of
Expressions for the equilibrium constants KI, KII and KIII are a) an austenitic 18 % Cr / 8 % Ni stainless steel type AISI 304 and
found in the Linde Gas booklet ”Neutral Hardening and An- b) a ferritic 13% Cr steel type AISI 405 (Calculated by Thermo-
nealing”. These expressions are the basis for atmosphere carbon Calc [9])
concentration control systems. In brazing, the carbon potential 2.0
is more commonly used. The atmosphere carbon potential is de-
fined as the carbon concentration expressed in weight percent of 1.8
pure iron equilibrated with the atmosphere. See also the Linde AISI 304
1.6
Gas booklet ”Furnace Atmosphere 1: Gas carburizing and car- γ+ε 1050 °C
Nitrogen content mass%

bonitriding”. 1.4

1.2
It is possible to generate the carbon potential from any CO/H2
atmosphere with knowledge of CO2, dew point or millivolt value 1.0
from an oxygen probe. However, oxygen probes may not operate 0.8
well at brazing temperatures. It is important to observe that the AISI 405
proper atmosphere carbon potential is affected by alloying ele- 0.6 γ
γ 1050 °C
ments in the steel and corrections will be necessary for highly 0.4
alloyed steel chemistries.
0.2
γ+ε
Improper carbon potential control can have the same consequenc- 0
es as improper oxygen potential control as the carbon potential is 0 0.2 0.4 0.6 0.8 1.0
directly related to the oxygen potential. A too low carbon poten-
tial results in decarburization, which normally is negative for the PN2 (atm)1/2
hardness and the strength of the steel. A too high carbon po-

20
in the slope of the theoretical curve corresponding to ε-nitride
formation. In practice, the obtained nitrogen surface concen- Figure 18. Principal atmosphere controlling zones in a
trations are lower than theoretically predicted. This is because continuous brazing furnace related to HYDROFLEX®
residence time is so short that equilibrium is not reached. Any- nitrogen/hydrogen system for brazing
way the risk of detrimental nitriding has to be considered when
brazing stainless steels, titanium, and other metals that easily Temperature
form nitrides. The use of argon, hydrogen, mixtures thereof, or
vacuum then is recommended.
PO2
Too high nitrogen potential will for certain stainless steels lead A B C D E
to deteriorated corrosion resistance and to hardness increase.
Titanium and zirconium may become brittle if brazed in nitro-
gen containing atmosphere. Heating zone
Cooling zone

4. Hydrogen Reactions

Hydrogen brazing is common and generally results in excel-


lent brazements. However, in some cases hydrogen can cause Analysis
Flow train Nitrogen
unwanted reactions. Brazing of oxygen bearing copper (not Control
cabinet
deoxidised) in hydrogen gas can lead to a reaction with the ox-
ygen to form water vapor. Due to the high pressure of water Hydrogen
Nitrogen
vapor formed and enclosed in the copper, blisters and embrittle-
ment may be a detrimental result.

Certain high strength steels with an ultimate tensile strength


above 1050 MPa [10] can be sensitive to what is generally referred With reference to the letter notations A, B, C etc., in the upper
to as hydrogen embrittlement. The embrittlement does not ap- part of Figure 18 there are the following atmosphere require-
pear during normal mechanical tensile tests but during static ments in the different zones:
mechanical loading or during slow strain rate tensile tests. Hy-
drogen concentrations in the steel as low as 2–2,5ppm can dras- A: The atmosphere should support in eliminating hydrocarbon
tically reduce the steel ductility. The embrittlement is caused by containing vehicles in the brazing paste or surface contaminants
atomic hydrogen in highly supersaturated solution. Molecular in order to avoid the formation of soot deposits. This can be
hydrogen can form at voids or slag inclusions and thereby facili- done by burning off the hydrocarbons in an atmosphere slightly
tate crack propagation. Molecular hydrogen is, however, not the oxidizing with respect to the hydrocarbons. This principle can-
cause of embrittlement [10]. not be used for brazing of for instance stainless steels for which
the requirements are very strong with respect to reducing power
Titanium, zirconium, tantalum, and some other metals have of the atmosphere. Instead the use of 100% very dry hydrogen
such a high affinity to hydrogen that metal hydrides are formed. will facilitate vaporizing of hydrocarbons.
Generally this leads to embrittlement.
B: When the temperature exceeds approximately 500°C (930°F)
D. Atmosphere Control Systems oxidation rate is noticeable. The atmosphere accordingly must
be reducing to avoid oxidation and preferably also to reduce sur-
When the gases enter into the furnace they will react in a face oxides that were formed earlier.
number of different ways: with each other, with vapors from the
braze paste, with surface contaminants on the parts, with air en- C. The atmosphere should maintain reducing conditions and in
tering the furnaces through leaks or by drag in with the parts the case of steels also maintain carbon neutrality.
etc. The resulting atmosphere composition needs to be control-
led to ensure that high quality brazements are formed. Based D. Upon cooling, the risk of oxidation is increased because the
on the principles earlier described, an atmosphere control sys- oxygen equilibrium pressure over oxides decreases with de-
tem for realizing this must have: 1) a gas analyzing system and creased temperature (see Figures 15 and 21). The atmosphere
2) a flow and gas mixture control system that maintains the at- must therefore be highly reducing in this zone.
mosphere composition within set limits. In a continuous fur-
nace these atmosphere composition set points can be different E. Although the oxygen equilibrium pressure decreases with
in different zones of the furnace as depicted in Figure 18. In lowered temperature the rate of oxidation will be low at temper-
a batch furnace the atmosphere composition set points corre- atures below about 150°C (300°F). In this section it is therefore
spondingly can change with process time. enough to have a neutral and oxygen free atmosphere.

21
An example of an atmosphere control set up that meets the fore- It is possible to achieve different atmosphere compositions
going requirements is also shown in Figure 18. The atmosphere along a continuous furnace by proper location of the gas inlets
analysis and control is for that system based on dew point analy- with respect to type of gas and flow. An example is shown in
sis in the hot zone and oxygen control in the cooling zone. The Figure 19, which shows a concentration profile that is possible
result of the analysis is registered in the Control Cabinet and to achieve by the injection of proper amounts of nitrogen and
compared with a set point value for each zone. The difference hydrogen respectively at the proper locations in a continuous
between the actual value and the set point is the control param- brazing furnace. A high reducing power is created in the hot
eter for the flow control in the flow train. With the closed loop part of the furnace, where it is needed, by injecting all hydrogen
control system shown in Figure 18 the brazing quality is ensured there. At the furnace in- and out-lets a non flammable atmos-
through proper atmosphere composition control of different phere is obtained by the dilution with nitrogen at these points.
furnace zones. In the hot brazing zone this is achieved either by
changing the total flow of nitrogen + hydrogen or by changing
the mixing ratio of nitrogen/hydrogen. In the cooling zone the
oxygen concentration set point is maintained by controlling the E. Vacuum as Atmosphere
nitrogen flow into that zone. The flow rate is minimized at any Vacuum brazing is used when the primary function of the at-
time based on the requirement that the atmosphere composi- mosphere is to minimize oxidation during the brazing process
tion is within set limits at each moment. cycle. This is accomplished by eliminating the atmosphere from
the vacuum furnace. So in simple terms, vacuum replaces any
Manual analysis is an alternative to automated atmosphere com- protective atmosphere in the brazing process. Anyway nitrogen,
position and flow control. It is less costly than the automated argon, and sometimes hydrogen and helium are important gas-
systems and serves well in cases where brazing and atmosphere es in relation to vacuum heat treatment.
conditions are stable and constant. Gas flow rate and mixing is
then changed and finally set to the flows that yield the atmos- After the first vacuum pumping, nitrogen may be introduced up
phere analysis set point. to about atmospheric pressure. A second vacuum pumping will

Figure 19. Adaption of gasinlet locations of nitrogen and hydrogen that results in a
concentration gradient along a continuous furnace.

N2 N2 +H2 N2 N2

Heating zone
Cooling zone

N2 N2 +H2 N2 N2

100 %
% H2

5%
Furnace length

22
lower the impurity, in particular oxygen, concentration inside. pheric pressure to approximately 3Pa (2 × 10–2 Torr). The booster
Although the gain in lowering the impurity level is highest after pump is a mechanical pump placed in series with the rough-
the first vacuum pumping it is possible to reduce it by repeating ing pump and designed to “cut in”, or start at around 9,5kPa
the backfilling/vacuum pumping sequences. (700 Torr). It is designed to provide higher pump-down speeds
in the pressure range of 1,3kPa (100 Torr) to 0,1Pa (1 × 10–3 Torr).
In modern vacuum furnaces heating is performed by convec- In this intermediate pressure range, the roughing pump is los-
tion with the objective to increase the heating rate as compared ing efficiency while the diffusion (vapor) pump is just starting
to heating by radiation in vacuum. Therefore heating is done in to gain efficiency. Finally, the diffusion pump is a type of vapor
a neutral gas, normally nitrogen or argon, at a low vacuum or pump and is used to help achieve even lower system pressures.
even up to a pressure slightly above atmospheric pressure. This The diffusion pump is capable of pumping gas with full efficien-
atmosphere is maintained up to a temperature, at which oxida- cy at inlet pressures not exceeding 3Pa (2 × 10–2 Torr) and dis-
tion rate starts to be appreciable. The vacuum then is improved. charge (or fore line) pressures not exceeding 65Pa (5 × 10–1 Torr).
The diffusion pump cannot operate independently; it requires a
When brazing is made of alloys containing metals that easily separate pump to reduce the chamber pressure to or below the
vaporize there is sometimes a need to run the process not at diffusion pumps maximum intake pressure before it will oper-
high vacuum but at a certain elevated pressure. The backfill gas, ate.
mostly being nitrogen, is then added to maintain the pressure at
the desired level. In general, the effects of evacuating the atmosphere from a vac-
uum furnace can be summarized as follows [11]:
An important function of industrial gases in vacuum brazing is
to remove or “break” the vacuum after braze joint formation at A. The effects of evacuating a vessel from 100 kPa (760 Torr)
the brazing temperature allowing the parts to cool at a controlled (atmospheric pressure) to 130 Pa (1 Torr):
or expedited rate. Instead of a continuous supply of industrial
gases to the furnace, the vacuum-brazing furnace therefore re- 1. Removing (high relative humidity) air
quires a discontinuous supply of protective gas provided almost 2. (Slow) change in the composition of the gas remaining.
instantaneously at elevated pressures and significant flow rates. a. Initially, air is the major component of the gas (certain
other contaminants such as oils, grease, and water exist
In order to create a vacuum within a closed container, or vessel, on cold surfaces such as vessel walls).
we need to remove the molecules of air and other gases that re- b. Eventually, almost all of the air is pumped out, the grease
side inside. This is done by means of a pumping system, which and water will continue to evaporate and their partial
includes the pumps and furnace, together with the associated pressure will constitute a much larger portion of the total
piping, valves, vacuum gauges/instrumentation and other com- pressure. This is called outgassing.
ponents of the vacuum system. Vacuum systems fulfilling this
can be classified by the pressure range achieved by their pump- B. The effects of evacuating a vessel from 130 Pa (1 Torr) to
ing system as shown in Table 9. 10mPa (1 × 10–4 Torr) are:

Table 9. Classification of vacuum systems (See Appendix regarding 1. The remaining gases in the vessel have a decreased ability to
conversions between pressure units) conduct heat.
2. The voltage required starting a discharge decreases, so arc-
Quality of vacuum Pressure range ing is more likely to occur. This will happen only if metal
vapor has condensed on furnace interior surfaces.
Pa Torr
Rough 1,3 × 102 –1,3 × 105 1 – 103 C. The effects of evacuation from 10mPa (1 × 10–4 Torr) to
Fine 1,3 × 10–1 –1,3 × 102 10–3 – 1 0,1mPa (1 × 10–6 Torr) are:

High 1,3 × 10–5 –1,3 × 10–1 10–7 – 10–3


1. Decreasing molecular density
Ultra-High <1,3 × 10–5 < 10–7 a. The mean free path of movement of gas molecules be-
comes greater. Therefore molecules collide with the sides
of the vessel as often as they collide with each other.
b. Sliding friction increases.

Different vacuum pumps are required to reach the various vac- A primary concern in vacuum processing is the vaporizing of the
uum levels. The systems are generally configured with three material being processed. The risk of vaporizing makes vacuum
pumps: a positive displacement mechanical (often called a brazing not to allow as wide a choice of brazing filler metals, as
roughing pump), a booster pump, and a diffusion pump. The does atmosphere brazing. The vapor pressure of an element is
roughing pump is used in the initial pump down from atmos- the pressure where the solid and vapor are in equilibrium with

23
each other and the vapor pressure varies with temperature. Fig- ides. Instead oxides can be removed by dissociation. The oxides
ure 20 shows the variation vapor pressure as a function of tem- will decompose into their constituent elements when heated to
perature for a number of metals. Cadmium, zinc, magnesium, sufficiently high temperatures with a vacuum level under the re-
bismuth, manganese, and also chromium are elements with quired pressure for oxide dissociation. The pressures that will
high vapor pressures as seen from Figure 20. Such elements va- lead to dissociation are the same as the oxygen equilibrium par-
porize more easily during vacuum. Vaporizing leads to negative tial pressures as was shown in Figure 15. That diagram is re-
effects both because of loss of material from the alloy processed drawn in Figure 21 to show the dissociation pressures for some
but even more important due to that vapors easily can condense common alloying elements present in base or filler metals. As
on cold parts in the furnace causing problems for functionality the metal and the oxygen in the metal oxide dissociate, the oxy-
and maintenance. Brass, which has zinc as the major alloying gen recombines into gaseous form and is evacuated through the
element, is an example of an alloy, which is not suited for vac- vacuum pumping system.
uum brazing because the zinc would vaporize. The only way to
avoid vaporizing is to use a pressure above the vaporizing pres- Vacuum is a relative state and does not imply freedom of gas
sure, although this is counteractive with respect to keeping the molecules. At an ultra high vacuum of the order 10–5 Pa (10–7
best vacuum for a good brazing result. Torr) there still are about 1015 gas molecules per cubic meter. Re-
gard a furnace originally filled with air. After pumping down to
In vacuum there is no reducing gas that can reduce metal ox- a vacuum of 10–5 Pa, assuming that 21% of those molecules are

Figure 20. Vapor pressure curves for metals as function of temperature (Calculated by Thermo-Calc [9]).
If the pressure in the vacuum furnace is below the vapor pressure curve for a certain element then that
element will vaporize. Example for the vacuum/temperature combination 100Pa/1000°C indicated in the
diagram: Mn, Al, Cu etc. are stable but Pb, Bi, Ca etc will vaporize.

Temperature [Fahrenheit]
500 1000 1500 2000 2500 3000 3500
1e+06

Hg
Cd Zn
10000 Mg
As
Pb
Ca Bi Ni
100 Co
Mn
Fe
Cr
Al Cu
Ti V
Pressure [Pa]

1
Pt
Zr
0.01

Nb W
C Ta
Mo
0.0001 Th

1e-06

1e-08
0 500 1000 1500 2000 2500 3000
Temperature [Celcius]

24
oxygen as in air, the oxygen partial pressure, PO will be about
2
Figure 21. Dissociation pressures (oxygen equilibrium partial 10–11 atm. From a theoretical equilibrium point of view this is
pressures) for some metal oxides an oxidizing atmosphere towards many metals at normal braz-
0 ing temperature according to Figure 21. If the furnace is purged
with nitrogen before the vacuum pumping then the resulting
oxygen partial pressure is reduced to about 10–16 atm. Still this
–10 Cu2O is oxidizing towards metals like chromium. Repeated nitrogen
NiO purging and vacuum pumping could reduce this further. That
is, however, not the practice so how could vacuum brazing result
–20
Mn in complete bright parts? One reason is that the rate of oxidation
Cr2O3
Oxygen partial pressure, log

FeO is very slow in vacuum. A more important reason is probably


–30 Fe2O3 that oxygen concentrations in reality are lower than predicted
with the foregoing simplified assumptions because oxygen is
ZnO consumed in the oxidation process primarily by the oxidation
–40 of graphite. The graphite used for heating elements, charging
SiO2
TiO bricks and furnace chamber will consume oxygen via CO forma-
–50 tion.

Hydrogen has positive effects on reducing power toward oxides


–60
Al2O3 and on cooling rate when used as cooling gas. A negative effect
is that hydrogen may react with graphite used as heating ele-
ments and other parts inside the furnace. Nitrogen, which is the
–70
cheapest and most common gas for purging, backfilling and
cooling, should not be used when there is a risk of detrimental
–80 nitriding reactions with the base alloy or filler metal.
400 600 800 1000 1200 °C
752 1112 1472 1832 2192 °F
Temperature

IV. Atmosphere Generation and Supply

Furnace atmospheres can be supplied to a furnace in two ba- Figure 22. Principle parts of the atmosphere system
sic ways. The first, called In-situ Generation, is by supplying
gases, such as nitrogen, hydrogen, and argon, directly to the Atmosphere furnace
furnace where they may be mixed or blended to create the cor-
rect composition. The second, called External Generation, is to
Mixing panel
react components (typically a fuel and air) to produce by-product Argon
gases that form the furnace atmosphere. This method can be
combined with the in-situ method.

Hydrogen
In-Situ Generation

With the in-situ atmosphere generation technique, gases and


media are supplied from separate sources and in separate pip- Vacuum furnace
ing to the furnace, where the gases are mixed, reacted and syn- Buffer tank
Nitrogen
thesized inside the furnace, Figure 22.

25
1. Methanol Dissociation Linde Gas supplies on-site solutions based on standard plants
under the trade name ECOVAR®. Depending on flow rate and
A CO/H2 atmosphere can be produced by in-situ cracking of required purity for the nitrogen, different standard plant pro-
methanol according to the reaction: duct lines are available. The ADSOSS®-N product line is based
CH3OH = CO + 2 H2 on the adsorption process and is suitable in the range 10-5000
By mixing cracked methanol with nitrogen it is possible to pro- Nm3/h with purity of 99-99,99%, Figure 24. Considering that
duce almost any N2/CO/H2 composition, thus also those obtained the MEMOSS® product line, based on the membrane process,
by endo-, exo- or monogas generators reaches a purity of 99,5%, it is normally not applicable for braz-
ing of metals.
2. Nitrogen, Argon, and Hydrogen Supply

Figure 24. ADSOSS®-N 500 plant for nitrogen production on


Nitrogen: There are five major supply forms for nitrogen:
site
a. Gaseous nitrogen in cylinders
b. Liquid nitrogen supplied by truck to the customer
container
c. Nitrogen produced onsite with cryogenic technology
(CRYOSS®)
d. Nitrogen produced on-site with adsorption technology
(ADSOSS®-N)
e. Nitrogen produced on-site with membrane technology
(MEMOSS®)

Nitrogen supplied in the liquid form has a high purity, with typi-
cal contamination levels of O2 + H2O at 5 ppm. Liquid supply is
common for a flow from 10 up to 100–200 m3/h. Liquid nitro-
gen is supplied by truck to the liquid nitrogen storage tank at the
manufacturing plant, as shown in Figure 23. The liquid nitrogen
supply form has the advantage that the amount of nitrogen sup-
plied to the furnaces can be varied within wide limits. The cus-
tomer takes just the amount needed at any time.

Figure 23. Storage tank and vaporizer for liquid nitrogen In cases when the purity requirement is above 99,99%, the CRY-
OSS® product line is a suitable choice. Nitrogen is separated
from air with a cryogenic process and a purity corresponding to
5 ppm oxygen and moisture content may be obtained. It is rel-
evant for flow rates from 100-7000 Nm3/h, Figure 25.

Figure 25. ECOVAR® system based on a CRYOSS® 550

Exchange photo pls. ”CRY-


OSS byt foto här

26
B. Nitrogen and External Atmosphere Generators
The ECOVAR® on-site systems normally include a back-up unit
consisting of a liquid nitrogen tank and vaporizors. The back-up Nitrogen based atmosphere systems, supplied by industrial gas
unit ensures continuous supply of product and may be used for companies, and atmosphere generators, which produce the gas
instant needs of higher flow rates. from reaction between air and natural gas (or other hydrocar-
bon), supplied by furnace producers, were earlier seen as sepa-
Argon is supplied either as gas in cylinders or as liquid in a tank rate alternatives each with its pros and cons. The development
very similar to the one shown in Figure 23. Purities are the same is now going in a direction of combining the two systems, tak-
as for the corresponding nitrogen supply methods, thus approx- ing the best out of each system, and bringing them together for
imately 5 ppm of O2 + H2O. optimal result. In this way it is possible to create widely varying
atmosphere compositions with 1) respect to the position inside
Hydrogen is supplied alternatively by: the furnace and 2) to the alloy being treated. The composition
and flow can also be adapted to the need at each moment
a. Gaseous delivery from cylinders, cylinder bundles or a
tube trailer; Generated gases include exothermic gas, endothermic gas, mo-
b. On site production by either: electrolysis of water, steam nogas-generators, and ammonia dissociators. These gases are
reformation of natural gas, ammonia dissociation or supplied separately through piping systems and possibly mixed
methanol dissociation. with nitrogen or hydrogen as they are introduced into the fur-
c. Liquid hydrogen supply. nace.

Examples of different supply methods for hydrogen are shown By bringing air to react with a hydrocarbon (propane or natural
in Figure 26. gas) it is possible to produce the generator atmospheres com-

Figure 26. Different supply forms for hydrogen. a) Cylinder bundle with hydrogen,
b) Hydrogen tube trailer, c) Installation of a container including a hydrogen electrolyzer,
d) Liquid hydrogen truck with production facility in the background

27
monly known as RX-, DX- and HNX-atmospheres or endogas, It is important to regularly maintain the ammonia cracker to as-
exogas, and monogas respectively. Cracked ammonia (DA) is sure proper dissociation of the ammonia. If not there is the risk
also made in a type of gas generator. Figure 27 shows schemati- that uncracked ammonia leaves the cracker and causes unwant-
cally the design of these generators. Each generator can vary the ed nitriding of parts in the furnace.
gas composition, but only within a range that is dictated by the
combustion process. Thus, the output flow rate can be varied
only within certain limits in turn limiting the types of materials Figure 27.
that can be brazed within that furnace. Schematic principles of a) exo- and b) endo-gas generators
and c) an ammonia dissociator
1. Endogas (RX)
As illustrated in Figure 27b air and a hydrocarbon, commonly
natural gas and sometimes as propane, are mixed and fed via Cooling and
drying Appr. 22
a blower into a retort heated to approximately 1000°C (1830°F). Appr. 7 Volume Volume Units
The retort is filled with a nickel catalyst to enable a complete Units Air Exogas
Combustion
reaction between the hydrocarbon and the oxygen in the air. The chamber
air/hydrocarbon ratio is chosen so that the hydrocarbon is main- 1 Volume Unit
ly reacted to CO and H2 according to the principal reactions: Natural gas

a. Exogas generator schematic


C3H8 + 7.2 Air = 3CO + 4H2+ 5.7 N2
for propane as the hydrocarbon
or 4,9 Volume Units
Endogas
CH4 + 2.4 Air = CO + 2H2 + 1.9 N2
for methane as the hydrocarbon.
Cooling
Endogas is a reducing atmosphere with a controllable carbon
concentration.

2. Exogas (DX) Retort with


Ni catalyst
For exogas, Figure 27a, production a higher air/hydrocarbon ra-
tio is used, which results not only in CO and H2 but also in H2O
and CO2 production. The reaction between air and hydrocarbon
2,4 Volume
is exothermic (produces heat) and does not require a catalyst. Units Air
Air/natural gas ratios vary typically from 7 to 9. The resulting
1 Volume Unit
exogas is dried to lower the water vapor concentration. Exogas
Natural gas
is the cheapest generator gas but the least reducing atmosphere
with the lowest carbon activity of all generator atmospheres. This b. Endogas generator schematic
means that it can be used for brazing of copper and of steels for
which there is no carbon control required.

2 Volume Units
3. Monogas (HNX) Cracked ammonia
Monogas is a high purity atmosphere with low concentrations
of water vapor and carbon dioxide. It is obtained by cleaning
exogas thoroughly with respect to these oxidizing gases. The
Cooling
equipment needed for that is costly and service demanding. The
resulting atmosphere composition is typically 2–20 volume %
CO+H2 the rest being nitrogen. It is reducing and has a control-
lable carbon concentration.

4. Cracked ammonia
An ammonia cracker, Figure 27c, consists of a heated retort, in
which ammonia dissociates to a 25-volume % nitrogen/75 vol- 1 Volume Unit
Ammonia
ume % hydrogen gas mixture by the reaction,

2NH3 = N2+ 3H2


c. Ammonia dissociator schematic

28
V. Brazing of Different Alloys

A. Steel Brazing Brazing in controlled atmospheres is dominating, vacuum braz-


ing being used only in very special cases. Specific for steels is that
Brazing is a widely accepted and standardized process for join- the atmosphere in addition to be non-oxidizing also for medium
ing steel components whether they are low carbon, low alloy, and high carbon steels preferably should offer carbon control to
high carbon steels, or tool steels. Also cast irons are success- avoid decarburization. Suitable atmospheres that offer carbon
fully brazed if proper pre-cleaning is made to remove graphite control are nitrogen/methanol, nitrogen/endogas or rich exother-
from the surfaces to be joined. Common brazements include mic gas. Most steel brazing uses anyway atmospheres that blend
consumer products such as in automobiles, bicycles, and a wide nitrogen with 5 to 30% hydrogen because hydrogen-containing
variety of other vehicles, frames, steel panels and shelving, tubu- atmospheres produce excellent brazements and because nitro-
lar frame furniture, cutting tools, knives, reservoirs, electronic gen/hydrogen systems are easier to set up and maintain.
chassis, etc.
Nitrogen/hydrogen systems can be run with very low dew points
Braze alloys from the silver, copper, or nickel families can be if the brazing furnace is tight and disturbances from air ingress
used for steel brazing. Copper-base filler metals are generally are minimized. This makes the atmosphere reducing towards
preferred because of its low cost and the high joint strengths metal oxides but also results in a low or negligible decarburiz-
produced. The use of preforms such as rings and foils is a ration- ing effect. The decarburizing rate is lowered with lowered dew
al filler metal placement procedure. The solidus of copper-base point. Atmospheres like endo- and exo-gas with a high amount of
filler metals is typically in the range 1095-1100 °C (2000-2010 °F), the active components CO, CO2, H2, and H2O are more difficult
which sets a requirement of a brazing temperature above this to control with respect to decarburizing because the carbon con-
temperature range. This can be used to advantage by combin- trol must be based on balancing the atmosphere concentration
ing brazing with a heat treatment cycle, for instance hardening. ratio (vol% CO) 2/(vol%CO2) or (vol% CO×vol%H2)/(vol%H2O)
A potential negative effect of the high brazing temperature is respectively (see section III.C.2). The ratio corresponding to
the risk for grain growth and for decarburization. Brazing time carbon neutrality varies with temperature. If the ratio is main-
therefore should be kept to the minimum required for melting tained to carbon neutrality at a specific point in a continuous
and wetting to produce a good joint. furnace it means that the atmosphere will be decarburizing for
positions with higher temperature and carburizing for positions
Silver-base alloys have lower solidus compared to the copper- with lower temperature. If the ratio gets a value corresponding
base filler metals. Silver base alloys are accordingly used when to decarburizing then the decarburizing rate will be greater than
the brazing temperature has to be below a certain temperature for the low dew point nitrogen/hydrogen atmosphere because
in order not to impair the steel properties obtained in a forego- of the high concentration of the decarburizing components CO2
ing heat treatment. and specially H2O. This can be illustrated with an example re-
ferring to Table 10. The water vapor concentration of endogas
To carefully consider how the brazing and heat treatment will in- (from methane) is 0,41 vol% for the case that the atmosphere is
teract can reduce the number of processing steps. For example, controlled to have a carbon potential of 0,4%C at the tempera-
low alloy pre-heat treated metals may use silver-based fillers with ture 1050 °C (1920 °F). A typical nitrogen/hydrogen atmosphere
liquidus temperatures below the steel transformation tempera- has no defined carbon potential but a water vapor concentration
ture to retain their heat-treated properties. Alternatively, brazing of 0,01Vol% thus 1/40 of the endogas water content. Decarburiz-
and heat-treating can occur concurrently if copper-zinc or certain ing rate can be assumed to be proportional to the water content
silver based filler alloys are used with their solidus temperature (and also proportional to the difference between the atmosphere
above the steel austenitizing temperature. Brazing of hardenable and the steel carbon activity). This means that if the endogas
high carbon steels is either done prior to hardening or as a step composition given in Table 10 is used for brazing of a 0,6%C
in the hardening process. For hardenable tools steels with tem- steel it will lead to a decarburizing rate 40 times faster than for
pering temperatures in the range 550-650 °C (1020-1200 °F) it is the nitrogen/hydrogen atmosphere with a dew point of –40°C
possible to perform brazing and tempering concurrently by se- (–40°F).
lecting a silver-base filler metal with enough low solidus.

Table 10. Comparison of endogas and nitrogen/hydrogen atmosphere compositions with respect to water content

Endogas with carbon potential 0,4%C


Temp. °C Vol% CO Vol% H2 C-pot., %C Vol% H2O Vol% CO2 PO2, atm
1050 20 40 0,4 0,41 0,1 1,5×10-18
Nitrogen/hydrogen atmosphere with dew point –40°C (–40°F)
Temp. °C Vol% CO Vol% H2 C-pot., %C Vol% H2O Vol% CO2 PO2, atm
1050 0 5 0 0,01 0 1,3×10-19

29
Figure 28. Locations of gas inlets and analyzing points for a
HYDROFLEX® atmosphere control system
N2 N2 + H2 N2 N2

Heating zone
Cooling zone

Dewpoint(C)/ H2 (%) O2 (ppm)

It is not possible to maintain such a low dew point as –40°C 1. Atmosphere Brazing
(–40°F) if there is substantial ingress of air into the furnace. De-
spite the shortcomings just described it will in such cases be ad- The atmosphere should be reducing to the chromium oxide
vantageous to use nitrogen/methanol or endogas as such atmos- and for that hydrogen with a very low dew point is required to
pheres have a higher buffering capacity as a result of their high promote wetting, see Figures 15 and 16. Atmospheres of 100%
concentrations of CO and H2 compared to nitrogen/hydrogen hydrogen or blended with up to 25% nitrogen (alternatively
systems with typically 5-10% hydrogen. cracked ammonia) are effective for most stainless steel braz-
ing. If nitrogen pick up is to be avoided then a 100% hydrogen
With the nitrogen/hydrogen HYDROFLEX® atmosphere control system or an argon/hydrogen system must be selected. Carbon
system it is possible to maintain a constant atmosphere compo- control is generally not an issue with the low carbon content in
sition thereby assuring a stable quality of brazed parts. The HY- stainless steels.
DROFLEX® atmosphere control system can be made to meet
different requirements as related to cost and functionality. In Hydrogen brazing meaning brazing in dry 100% hydrogen has
all cases the atmosphere composition is regulated by adjusting a number of benefits:
the inlet flows of nitrogen and hydrogen to yield the required • It has the highest reducing power of all atmospheres leading
dew point and oxygen concentrations of the atmosphere as de- to shiny and oxide free high quality brazements.
picted in Figure 18. Figure 28 shows typical positions of analyz- • The atmosphere buffering capability (the ratio H2/H2O) in-
ing points and locations of the gas inlets. The ratio of H2O/H2, creases with increased share of hydrogen. Increased buff-
which is a measure of the oxygen potential (See section III: C1), ering capacity makes the atmosphere less influenced by air
is the control parameters for the hot zone and free oxygen is an- ingress and leads to that less gas is needed to maintain the
alysed in the cooling zone. The closed loop atmosphere control atmosphere quality.
allows both the nitrogen/hydrogen mixture and the total flow to • Elimination of ammonia handling.
vary with oxygen potential in the hot zone. In the cooling zone • Nitrogen pick is completely eliminated.
free oxygen (ppm) is in closed loop control with the nitrogen
flow. A HYDROFLEX® atmosphere system for pure hydrogen as de-
scribed in Figures 18 and 28 assures quality and minimizes the
B. Stainless Steel Brazing gas consumption.

Brazing is one of the easiest means to assemble stainless steel 2. Vacuum Brazing
components; however the chromium content of stainless steels
makes them much more difficult to wet than wetting of carbon Vacuum brazing for stainless steels is increasingly used for com-
steels. Copper, nickel, and silver-based braze alloys are the most plex assemblies like heat exchangers. Either nitrogen or argon is
commonly used filler metals. Silver-brazed joints are not but used as backfill and cooling gas. Vacuum is effective in stopping
nickel brazed joints are suitable for high temperature service. the chromium oxide from forming at the elevated vacuum braz-
Exercise care when selecting the braze alloy since diffusion of ing temperatures. However, it may be remarked that even with a
certain elements may have a negative impact on corrosion and very good vacuum it is unrealistic to reach the low oxygen partial
mechanical properties. Nickel-base fillers metals may form brit- pressures required from a chemical equilibrium point of view.
tle intermetallic compounds with the base metal. This is because The oxygen equilibrium pressure over chromium oxide is of the
the filler metal component boron (B) may react with nitrogen to order 10–25 to 10–30 atm at normal brazing temperatures, see Fig-
form boron nitrides (BN) and the component silicon (Si) may ure 15. Such low pressures are not reached even after double
react with the metal to form silicides. The brittle compounds are vacuum pumping. So – how could such excellent results be ob-
formed at the centerline of the joint and are sometimes referred tained in vacuum brazing of stainless steels? One reason is the
to as centerline precipitates. slow kinetics. If as an example the oxygen partial pressure is of

30
the order 10–24 atm it means that there are just five free oxygen brazing, form a joint with the apexes of the underlying/overlying
molecules per m3. Thus the available oxygen molecules are rap- corrugation from another sheet. All sheets were put into place,
idly consumed and oxidation processes are therefore stopped. and then held together during the brazing cycle. The braze filler
An additional proposed mechanism that may lead to reduction metal was in the form of a 0.04 mm thick foil.
of the chromium oxide passive layer on stainless steel is that car-
bon dissolved in the stainless steel reduces the oxide according Figure 30 shows the load of heat exchangers.
to the reaction,

MO + C = M + CO Figure 30. Heat exchangers loaded for brazing. The load to the
left was brazed in argon vacuum. The load to the right was
where M denotes the metal and C denotes carbon dissolved in brazed in argon/hydrogen vacuum.
the steel [3]. Anyway vacuum brazing results in very good wet-
ting of the base alloy by the filler metal.

Stainless steels with higher manganese contents (200 series)


require more extensive cleaning and preparation because man-
ganese forms an oxide that is difficult to reduce, see Figure 21.
Some stainless steels, particularly the unstabilized grades of
austenitic stainless, can be sensitized to intergranular corrosion
when processing occurs between 425 – 815 ºC (800 – 1500 ºF).
Extended times in this temperature range therefore should be
avoided. When brazing martensitic stainless steels a primary
guideline is to ensure that the brazing and the heat treatment
cycles are compatible both if made separately and concurrently.
Brazing was done with a pulsating pressure between 0,005 and
Adding hydrogen to the backfill gas is a potential way to lower 0,5mbar controlled by the supply of argon and argon/hydrogen
the oxygen partial pressure in vacuum brazing. This was done mixture respectively. Figure 31 shows schematically the gas
in a research project, reported in reference [12], with small heat supply system to the vacuum furnace.
exchangers as the application studied. Stainless steel sheets with
a thickness of 0.3 mm were pressed into a corrugated chevron
pattern. The heat exchangers were produced by building up al-
ternating layers of steel and braze foil, with each new layer of Figure 31. Argon and argon/hydrogen mixture supply to the
steel turned 90° relative to the previous layer, see Figure 29. vacuum furnace used for brazing
Thus, the apexes from each corrugation of one sheet will, during
PI

Figure 29. Corrugated steel sheets with chevron pattern and


braze alloy foil.
P

Steel sheet Vacuum furnace

Ar Ar/H2

Braze foil

The heat exchangers brazed in the different atmospheres (Ar-


vacuum and reducing Ar/H2 vacuum) were pressure tested. The
results of the pressure tests showed that brazing in the reducing
Ar/H2 vacuum gave an improvement of more than 10% over the
vacuum brazed samples in burst pressure performance.

The heat exchangers brazed in reducing Ar/H2 vacuum at-


mosphere were cleaner in appearance than those brazed in Ar

31
Figure 32. Macroscopic images comparing the brazing atmospheres.
Reducing atmosphere c) and d) gives a cleaner and smoother surface
appearance, than vacuum atmosphere.

a) Brazed in vacuum b) Brazed in vacuum

c) Brazed in reducing atmosphere d) Brazed in reducing atmosphere

vacuum, as shown in Figure 32. Furthermore, the brazed joint 4%H2 in the reduced atmosphere. The hydrogen gas mixture
surface is rough when brazed in vacuum and smoother when will increase the cooling rate compared to pure Ar, which may
brazed in a reducing atmosphere, as seen in Figure 32 b) and d). be the reason for the finer structure for the 96%Ar–4%H2 mix-
However, no observable difference regarding the degree of wet- ture. In the research report [12] some additional reasons for the
ting between the two brazing atmospheres was observed, when finer structure are discussed.
the sectioned joints were studied using light optical microscopy.
Examples of braze joint microstructures for a highly alloyed
It was observed that the last solidified phases in the samples austenitic stainless steel designated 254SMO are shown in Fig-
brazed in vacuum were coarser than those formed under braz- ure 33. The joint in Figure 33a was brazed with a thin brazing
ing in reduced atmosphere. This was true for all joints observed gap and the joint in Figures 33b with a thick brazing gap. Large
(approximately 45 joints). Coarse phases are more susceptible to precipitates are seen through the joint with the thick gap.
cracking than the finer phases, thus a risk leading to an earlier
failure. Such cracking was observed in the samples brazed in A new vacuum brazing process called AlfaFusion utilizes a spe-
vacuum, but in only 3 of all the joints. cial stainless steel filler metal, which is claimed to yield both im-
proved corrosion resistance as well as mechanical strength [14].
Coarser phases are formed at slower cooling rates, fine phases
at more rapid cooling rates. In both brazing processes the fur- Leakage test of brazed parts can be made with helium or with a
nace was flushed with gas, during the cooling cycle. This gas at- less costly nitrogen/hydrogen mixture, see section 2D.
mosphere was pure Ar following the vacuum braze and 96%Ar-

32
Figure 33. Photomicrographs of joints in 254SMO stainless steels brazed with BNi-5:
a) showing the thin end of the joint with some precipitates.
b) showing the thick end of the joint with precipitates and eutectic structure. [13].

a b

C. Aluminium Brazing joint and reduces the amount of flux required. The fluxing agent
mostly used and specially developed for nitrogen brazing is the
Aluminum brazing to manufacture automotive radiators, heat NOCOLOK® flux. The flux is applied as a liquid solvent onto
exchangers for refrigerators and industrial applications, and the parts before brazing. A drying step is required before load-
household goods is now a mature technology. The development ing the parts onto the brazing furnace conveyor (see Figure 34).
of brazing technology for aluminum in the 1970’s has advanced
the use of aluminum radiators in automobile production, where
their decreased weight offers reduced vehicle fuel consumption Figure 34. Aluminium heat exchangers entering a CAB-furnace.
and significantly reduces the environmental impact. (Courtesy of Seco Warwick Corporation)

Furnace brazing can be performed in air or nitrogen or as vac-


uum brazing. Controlled atmosphere brazing (CAB) has grown
more than vacuum brazing mainly due to its adaptability to high
volume serial production. Vacuum brazing is very demanding
as regards brazing gap clearances, which have to be within close
limits to result in good brazements. Vacuum brazing has clear
environmental advantages in the absence of hazardous and ag-
gressive fluxes and also in the cleanliness of the brazed parts.

Aluminum is brazed at temperatures between 555 and 645 ºC


(1030 – 1195 ºF). Any strengthening, whether by heat treatment
or cold working, will be lost at these temperatures. Aluminum
poses particular brazing challenges since aluminum oxide is an
adherent and readily formed oxide, even at room temperatures.

1. Atmosphere Brazing Successful brazing relies on the proper control of oxygen con-
centration and dew point in the atmosphere. Studies [15] have
The aluminium strip used in making the heat exchangers is identified the relationship between oxygen concentration, dew
a compound material with a base alloy as the core and a thin point and flux load and Figure 35 graphically illustrates this re-
clad of a low melting alloy that serves as filler metal. Brazing lationship. An oxygen concentration level of 400 ppm (0.040
under controlled nitrogen atmosphere (CAB) produces a quality volume percent) inhibited effective brazing. With an oxygen

33
Figure 35. Relationship between brazability of aluminum and atmosphere
concentration of oxygen and dew point. [15]

Brazeability
Very Good Low oxygen concentration, < 50 ppm O2 High oxygen concentration, 400 ppm O2

Fluxload
3.2 g/m2
Poor Fluxload
Fluxload
1.5 g/m2 3.2 g/m2
Fluxload
1.1 g/m2
Fluxload 1.5 g/m2 and 1.1 g/m2
Bad

– 45 – 35 –30 – 45 – 35 –30
Dewpoint Dewpoint

concentration below 50 ppm (0.005 volume percent), a lowered zone the oxygen level was much lower. Thus it was clear that
dew point or an increased flux loading increased the braze joint oxygen was entering the furnace through the openings and the
quality. One conclusion from the study is that it is possible to atmosphere control system should eliminate or lower the effect
reduce the flux load and still have high quality brazements by of these disturbances. An atmosphere closed loop control sys-
lowering the dew point tem capable of keeping the oxygen concentration at the preset
level was developed. A block diagram of the system is shown in
The following real customer case illustrates the different steps Figure 36.
taken when designing a good atmosphere control system for
aluminium brazing. Oxygen analysis was first made at different The SOLDERFLEX® atmosphere control system is an active
positions in the customer’s CAB furnace when in production. flow rate control system based on the requirement that a certain
High oxygen concentrations were measured near the furnace set point for the oxygen concentration is maintained within the
inlet but also close to the outlet of the furnace. In the brazing brazing furnace. The nitrogen flow rate is always minimized to

Figure 36. Principle block diagram for the SOLDERFLEX® atmosphere control system

Process
computer

Gas
analyzer

Sample gas
Furnace scanner

Gas system

34
maintain this oxygen concentration set point. If the actual O2 2. Vacuum Brazing
concentration is higher than the set point then the nitrogen flow
rate is increased. If the actual O2 concentration is lower than the Vacuum brazing is made without a flux. No post cleaning is
set point then the nitrogen flow rate is decreased. Flow rate ad- therefore required. An additional benefit with the absence of
justments are continuous and step less by use of mass flow con- flux residues is that there is no corrosion associated with en-
trollers. Separate set points for the O2 concentration are used trapped flux. The aluminium parts to be brazed are clad with a
for idling and production respectively. A somewhat higher set high Mg concentration braze alloy, that acts as the filler metal.
point can be used for idling, which results in a lower nitrogen Mg in the clad alloy acts as an oxygen getter thereby improv-
consumption during that period. During idling, it is a require- ing wetting. An example of parts loading for vacuum brazing is
ment just to maintain good enough atmosphere conditions for shown in Figure 37.
enabling quick reconditioning time when starting production
again. The complete system is contained in one cabinet and con-
tains three major parts: Figure 37. Parts loaded on fixtures for vacuum brazing. The
vacuum furnace with diffusion pump to the left is seen in the
– Gas Flow Control System for the Nitrogen background. (Courtesy of Ipsen International GmbH)
– O2-Analyzing System (Dew point meter is an option)
– Control panel

The system in Figure 36 maintains the set point for the O2 at-
mosphere concentrations, of in the actual case 200 ppm, by
adapting the nitrogen flow rate. The nitrogen flow rate increases
initially during start up in order to get the oxygen concentration
down as fast as possible to the set point value, typically 200 ppm.
After a while, the flow is reduced to a minimum (=preset value)
as long as the oxygen level is below set point.

The brazing results when using the closed loop atmosphere con-
trol was the same as during normal production with constant ni-
trogen flow. No leaking radiators were produced and the overall
fault rate was zero percent. This specific mesh belt furnace was
originally running with a constant nitrogen flow of 40 m3/h, in-
dependent of the kind of radiator brazed. The flow distribution
is shown in Table 11, which also shows the flow distribution af-
ter installing the atmosphere control system. With the control
system in action during production, the average nitrogen flow D. Copper and Brass Brazing
was decreased to a level of 26 m3/h, corresponding to 35 % re-
duction. A constant oxygen concentration level at about 100 ppm Copper and Brasses encompass a large number of chemical
in the brazing zone was maintained during the whole cycle. An- compositions and most are readily brazed. Since coppers are
other result was that the personnel experienced a good overlook generally hardened by cold work, brazing temperatures often
of the atmosphere, being more aware of the quality of the total decrease the strength of the base metal. Braze alloys such as sil-
brazing production. ver and copper are commonly used and may be self-fluxing or
fluxless. The atmosphere is usually nitrogen based, often with
up to 15% hydrogen.

Table 11. Flow distribution before and after installation of One special consideration is that tough pitch (oxygen contain-
the SOLDERFLEX® atmosphere control system ing) coppers cannot be processed in hydrogen containing at-
mospheres due to the reaction between oxygen and hydrogen
Total Flow
Flow m3/h forming blisters or embrittlement.
Furnace
Zone Zone Zone Zone Volume
1 2 3 4 Copper is an alternative to aluminium in heat exchangers. High
thermal efficiency and strength are advantages for copper. The
Before 8 14 14 4 13.8
copper alloys used in the past have been adapted to soldering,
After 6 0 18 (Mean) 2 9.0 thus joining at a temperature below 450 °C (840 °F), and if used at
15-35 elevated temperature these alloys have softened. A development
(Regulating
of alloys that can be joined and still maintain their strength dur-
interval)
ing brazing above 450 °C (840 °F) have resulted in a new brazing

35
E. Brazing of reactive metals
Figure 38. Copper radiators brazed for automotive applications
(Courtesy of Seco Warwick Corporation) Metals such as titanium and zirconium that react readily with
oxygen, nitrogen or hydrogen are preferably brazed either in
dry and clean inert argon or helium atmosphere or in a vacu-
um. Vacuum brazing at a temperature in the range 900–950 °C
(1650–1740 °F) is increasingly preferred as the method, which
yields the best brazing result. The ease with which surface ox-
ides are formed in ambient air makes it necessary to perform
cleaning before brazing. Otherwise wetting will be poor. These
metals also have a tendency to form intermetallic brittle com-
pounds with commonly used filler metals like the silver-base
filler metals. Anyway silver based filler metals still are common
for brazing these metals. Alternative filler metals based on al-
loys from the elements Ti, Zr, Ni, Cu, and Be are used and still
developed.

As for steels it is important to select brazing temperature and


cycle to result in good base metal properties. Some titanium
alloys are heat treated for instance by solution annealing and ag-
ing (precipitation hardening). It may in certain cases be possi-
ble to combine the brazing and the heat treatment cycle.
process called CuproBraze®. The process results in stronger
joints and better high temperature performance of the base al-
loy. An alliance of companies with their own homepage [16] has F. Brazing of Ceramics and Glasses
been formed to market this technology. CuproBraze® is a lead
free brazing process for manufacturing of copper-brass automo- Ceramics and composites are difficult materials to form or ma-
tive and heavy-duty industrial heat exchangers, see Figure 38. chine into complex shapes, so joining expands the engineer’s
The brazing of radiators uses a non-toxic low temperature-melt- ability to design complex components. Brazing is the major
ing alloy, CuSnNiP (5%Ni, 15%Sn, 5%P) that works well in ni- method for joining ceramics, glasses, and metals. Especially
trogen based controlled atmosphere furnaces. The braze alloy in electronics production there are numerous examples of very
melts at 600 °C (1110 °F) and has a melting range of 10 °C. The advanced brazing applications for joining a great variety of ma-
core material is specially designed to withstand the high tem- terials. As an example, a variety of seals such as metal-metal,
perature. A normal solder joined radiator would be annealed at ceramic-metal and ceramic-ceramic are needed for solid oxide
this elevated temperature. fuel cells to enhance reliability and life of the cell stacks. These
seals are expected to function in the most severe environments
The paste, which has minimum 70% metal content, is applied with temperatures in the range 600–900°C and under thermal
to the tubes, headers and fins prior to brazing by spraying or gradients. Whether the desired application is to join ceramics
brushing. The parts are then brazed in an atmospheric continu- to ceramics, ceramic to metal, obtain a glass seal on ceramics
ous mesh belt furnace or in a backfilled vacuum furnace under or metals, or a combination of these joints in one assembly, the
nitrogen protection. Normal brazing temperature is 620 – 650 °C continuing advances in brazing technology make this possible.
(1150 – 1200 °F). The atmosphere conditions should be a dew Silicon carbides and silicon nitrides can be bonded to other
point less than –40 °C (–40 °F) and an oxygen concentration level components of similar or different compositions. Even diamond
less than 20 ppm. is brazed onto base metals for instance in some rock drills.

After brazing the copper-brass joint is significantly stronger than The greatest obstacles are getting the metal filler to wet the ce-
the solder metal. ramic substrate. Improving the wettability can be accomplished
in two ways:
The benefit with this process is that it makes it possible to man-
ufacture high performance products such as charge air coolers 1) By increasing the tendency of the ceramic surface to wet usu-
that are running under high pressure and elevated temperature. ally by surface modification techniques like metal coating.
New regulations regarding environmental emissions enhance
the use of heat exchangers with higher performance. Coppers 2) By changing the chemistry of the braze alloy so it wets the
higher thermal conductivity has a positive influence on the pro- surface. The most common method of accomplishing this
duction capacity, as the heat exchangers are reaching brazing is called “Active Metal Brazing”. When joining ceramics and
temperature faster. glasses, the braze alloys employed are still metallic. In ac-

36
tive metal brazing, a metal (usually titanium) is added to the G. Brazing of Cemented Carbides
braze alloy to promote reaction and wetting with a ceramic
substrate. The addition of the “active metal” results in in- There are numerous examples of brazed cemented carbide
creased reactivity and considerable improvement in wetting products such as cutting tools, drill tips, rock drill parts, dies,
behavior. The ceramic is wet by the formation of an inter- etc. Wetting is more difficult than for metals but better than
metallic interfacial reaction product which can then form a for ceramics, which makes brazing in hydrogen or vacuum the
joint with the braze alloy. Active metal brazing is normally preferred brazing methods. Silver base filler metals that contain
performed in an inert or vacuum atmosphere. The brazing nickel for improved wettability are preferred but also copper-base
temperature is typically 50 – 100 ºC (120–210 ºF) above the filler metals are used. Brazing is performed at a temperature of
braze alloy liquidus temperature. about 980°C (1800°F). Different thermal expansion between the
cemented carbide, the braze alloy and the alloy to be joined to
Another obstacle is the difference in thermal expansion between the cemented carbide causes thermal stresses that may have de-
dissimilar materials. Ductile interlayers, the use of a series of teriorating effect. By using a three-layer foil with copper at the
layers deposited upon the surfaces of the parts are used accom- centre surrounded by braze alloy it is possible to minimize these
modate the differences in thermal expansion between the com- thermal stresses. The soft copper will act to lower the stresses.
ponents and minimize the mismatch.

Examples of brazing conditions for different ceramic/metal


joints are shown in Table 12.

Table 12. Examples of ceramic/metal joints and corresponding brazing approach [17]

Process Ceramic/Metal Applications Specific Conditions Typical Strength (MPa)


Vacuum devices
W/Mo-Al2O3
Al2O3 (>97%) Electronic - 20-200 (bend)
MnO-SiO2
packaging
Al2O3, AlN, ZrO2, Vacuum devices,
Active metal brazing - 100-200 (bend)
SiC, Si3N4, Sialons automotive parts
Light sources,
Oxide meets from Al2O3, Sialons
automotive parts, - 50-200 (bend)
Al2O3-CaO-MgO-MnO—SiO system
recorder heads
Electronic
Metal-metal oxide eutectic Cu/CuO Al2O3, AlN, 50-150 (bend)
packaging
Ceramic frit joints Al2O3/Mo H2/N2, 1500 °C
- 150 (3-point bend)
(Al2O3-CaO-MgiO2 frit) (2730 °F), 2 min
Ceramic frit joints H2/N2, 1200 °C
Al2O3/Kovar - 150 (3-point bend)
(Al2O3-MnO-SiO2 frit) (2190 °F ), 2 min
Active metal brazing Vacuum, 900°C
316 steel/RBSN - < 45 (shear)
(Ag-13%Cu-18%Ti Filler alloy) (1650°F), 5 min
Vacuum (3mPa),
Active metal brazing 316 steel/PLS SiC
- 810°C (1490°F), < 50 (shear)
(Ag-13%Cu-1,5%Ti Filler alloy) (Ti-Mo interlayer)
10 min
W/Mn metallization Al2O3/Fe-Ni-Co
- - 80 (4-point bend)
(Ag-Cu filler alloys)
Active metal brazing (Ag-Cu-Ti) ZrO2/Steel - - 109-144 (shear)

37
VI. Safety Hazards and Precautions

Safety is a key concern whenever working with industrial proc- • Catalysers such as soot, sulphur-containing gases, finely
esses and any person working in the thermal treatment industry dispersed metal particles, chemical reactions between oxy-
should be aware of the hazards from processes and equipment. gen and fuel gases, electrostatic charging, and local over-
The European Committee for Standardisation, CEN, issues heating by soot fire.
safety standards in Europe and The National Fire Protection As- • Pilot burners and other open burners, lighted cigarettes, or
sociation, NFPA, issues standards in USA. The standards can flame curtains.
be purchased on the Internet at the homepages www.cenorm.be
and www.nfpa.org respectively. The following discusses the haz- 2. Flux/By-products
ards and the general safety concerns in relation to brazing fur-
naces. This section serves as additional information relevant to The by-products of brazing by any method may produce harm-
the codes and standards. Hazardous conditions during normal, ful fumes that should not be breathed.
emergency and maintenance operations are presented below.

A. Normal Operating Conditions B. Hazards Associated with Unexpected/Emergency Situations

1. Explosion/Flammability of Atmosphere – Fire Any commercially fabricated industrial furnace must meet the
industrial codes of the company where it will be installed. A
Some brazing atmospheres contain percentages of flammable number of emergency safety operations should be integrated
gases that may ignite when exposed to air. Explosions are likely into the furnace and they should be able to automatically and
to occur when these three items are present at the same time: safely shut down the furnace. Typical situations would include
furnace over-temperature or loss of heating, loss of atmosphere,
– Fuel electric system failure, and flame safety. The manufacturing
– Oxygen plant should also train their employees on proper procedures
– Ignition source for the unexpected or emergency situations that may arise.

The flammable gases commonly found in these atmospheres C. Hazards Associated with Maintenance Operations
are hydrogen, carbon monoxide, hydrocarbons, vaporized or dis-
sociated methanol (dissociation produces hydrogen and carbon 1. Confined Spaces and Oxygen Deficiency or Asphyxiation.
monoxide), and dissociated ammonia (forms hydrogen and ni-
trogen). Nitrogen is a natural part of the air we breathe. As a gas, it is not
hazardous until it displaces the oxygen component of air. If this
Exposing a flammable substance to fire (or ignition) in air will happens, a person could suffocate due to lack of oxygen while
result in fire or an explosion. Explosions may happen if the mix- still seeming to be able to breathe. Oxygen is about 21% of the
ture between air and fuel gas is within the lower and upper flam- air. If the level of oxygen drops to 15% or less, a person will be-
mability limits. The European safety standard EN-746-3 states: gin to feel faint or dizzy. If oxygen levels fall below 10%, fainting
“As a general rule, any gas mixture containing more than 5 vol- can occur without warning. Oxygen concentrations below that
ume percent combustibles (H2+CO+CH4) of which methane level or sustained exposure to low levels can have permanent or
(CH4) is not more than 1 volume percent where the remainder fatal consequences. A locality deficient in oxygen is considered
of the mixture is non-flammable, is considered to be flammable. a confined space. Until safety personnel have performed the
Any gas mixture that contains more than 1% volume percent appropriate air analysis and a working permit or confined space
CnHm or 2.5 volume percent ammonia (NH3) where the remain- entry permit issued, personnel must not enter spaces with inad-
der of the mixture is non-flammable is also considered flamma- equate ventilation.
ble. A flammable gas which contains 1 volume percent or less
oxygen cannot itself form an explosive or flammable mixture.” 2. Pressurized Piping and the Gas Expansion Hazard

When using combustible gases, it is important that the furnace The nitrogen supplied to the furnaces is under pressure. The
temperature be above the atmosphere’s ignition temperature, gas supply should be locked out from the furnace and the pres-
generally recognized as 750 ºC or 1400 ºF. sure in the lines released in a controlled manner prior to per-
forming maintenance on the system. Failure to do so can lead
Possible ignition sources are: to unexpected releases of energy or introduction of nitrogen into
• Surfaces with high temperature such as furnace inner walls, the furnace.
electric heating elements, and burners or burner tubes.
• Sparks caused by friction or impact for instance from fans
or electric insulators.

38
VII. Troubleshooting Common Problems

Outlined below are some of the more common brazing problems


and possible solutions.

Table 13. Common Brazing Problems and Possible Solutions

Problem or Symptoms Possible Cause


Furnace brazed parts exit furnace gold
Parts are exiting the furnace at too high a temperature. Parts temperature
or straw in color, generally uniform in
should be less than 150 ºC when exiting.
appearance. Braze joint is good.
Furnace brazed steel parts exit furnace
Parts may be exiting the furnace at too high a temperature. Also, check for
with blue or black coloration, either
air leaks in high temperature zone possibly at muffle flanges or water leak in
uniform or not uniform. Braze joint
the cooling jackets
may or may not be good.
Air infiltration in the backfill gas and/or contamination from an external
or internal source. Check to make sure that the parts have been thoroughly
Vacuum brazed parts are discolored with
cleaned and dried prior to processing, Leak check the backfill lines to the
or without poor braze joint quality.
furnace. If the base material contains nitrogen as a strengthening agent, it
will not braze well using filler metals with boron, even if the furnace is clean.

Strength of base metal may be too high. If possible, use metal in annealed
Common brazing defects: Cracking condition.
Modify joint design to avoid stress concentration points.
Common brazing defects: Porosity in Porosity occurs when gases become trapped, particularly in blind joints.
braze joint Modify design or assembly so gases may vent properly.
• Check joint design. Cross-sections should be similar in size and part
Common brazing defects: Disbonding thicknesses must be comparable.
• Verify parts are not shifting during heat-up with resultant oversize gap.
The most common causes:
• Improper pre-braze cleaning
• Cleaning residue left from aqueous cleaning system
Common brazing defects: Discoloration
• The presence of oxygen at too high a temperature in the heating or cooling
portion of the cycle.
• Residual lubricants or machining fluids
• Contaminated quenching gases or too high a vacuum level in vacuum
furnace
Common brazing defects: Discoloration • Furnace opened before parts were cooled below 150 ºC (300 ºF)
from Vacuum furnace • Water leak from heat exchanger
• Faulty door seal
• Out-gassing of parts
• Insufficient hydrogen percentage
Common brazing defects: Discoloration
• Verify quality of furnace atmosphere (dew point and oxygen level)
from pusher, belt or humpback furnaces
• Air infiltration from entrance or exit.

39
VIII. Terminology

Braze alloy: Flow:


An alternative term for the brazing filler metal. The ability of molten filler metal to spread over a surface.
Base metal: Flow through:
The name for the original pieces. The objective in brazing A term used to describe the motion of parts moving in a
is to not melt the base metal. continuous furnace.
Brazing: Gap:
Joining of materials by allowing a filler metal to flow into Another term for joint clearance.
a close space, or gap, between them via capillary action. Heat Affected Zone (HAZ):
Bonding results from the intimate contact produced by That portion of the base metal whose mechanical proper-
dissolution of a small amount of base metal into the mol- ties or microstructure have been altered by the heat cre-
ten filler metal, without melting of the base metal. The ated by brazing.
term brazing is used when the filler metal has a liquidus Hydrogen Bake Out:
temperature of 450 ºC (840 ºF) or higher. Brazing is ame- A procedure used to remove hydrogen from inside a com-
nable for metals, ceramics, composites and glass. ponent by heating to 95ºC - 205ºC (200ºF - 400ºF) and
Capillary action: soaking for an extended period until the material ductility
The physical phenomena where a liquid gets drawn into is regained.
a tight space, gap, crevice or joint due to the reduction in Jig:
surface energy. Alignment of a braze joint or the fixturing to assure that
Diffusion: a joint will maintain the desired orientation and spacing
The degree to which the brazing filler metal penetrates during the braze process.
the alloys with the base metal during brazing. Joint:
Eutectic: The area associated with joining of pieces either along an
Term indicating the point where an alloy has a liquidus edge or at a junction. The term joint can be used for braz-
and solidus occurring at the same temperature. ing, welding or soldering.
Filler metal: Liquidus:
The material used that becomes molten during the heat- The lowest temperature at which a metal or alloy is com-
ing process and either 1.) is drawn into the gap between pletely liquid on heating.
the base metal parts by capillary action or 2. was inserted Preform:
into the gap as a preform, where it melts and stays. When The physical shape of the filler metal if it is not applied in
the filler metal solidifies, the joint is considered brazed. paste form.
The melting point of the filler metal is always lower than Setting the Braze:
that of the base material. A term used to describe an intermediate cooling step
Fillet: whereby the filler metal is allowed to cool to a semi-stable
A region of brazing filler metal where the various parts of (liquid/solid) phase prior to the onset of rapid cooling.
the assembly are joined. Skull:
Flash: An unmelted residue of filler metal.
A brazing defect where excess filler metal exits the joint. Solidus:
Excessive flash may need to be removed in subsequent The highest temperature at which a metal or alloy is com-
processing steps for quality or cosmetic reasons. pletely solid.
Freezing: Spacer:
Solidification of the filler metal during cooling. Small spheres made of stainless steel or nickel that help
Flux: fill the gap and allow the filler metal to bridge larger gaps
A chemical compound applied to the surface of a compo- or fill spaces that it would not normally fill.
nent to be brazed for the purpose of hindering or prevent-
ing the formation of oxides and other undesirable sub-
stances; used so as to allow the brazing filler metal and
base metal surface to remain relatively clean while being
heated to brazing temperature.

40
IX. References

1. Schwartz M., Brazing, 2nd Edition, ASM International, 10. Skogsmo JU., Nordänger S., Hydrogen embrittlement, IVF
Materials Park, 2003. 97823, 1997

2. ASM Handbook 6, Welding Brazing and Soldering, ASM 11. Herring D.H., “What is Vacuum?” Hot Topics in Heat
International, Materials Park, 1993. Treatment and Metallurgy, January 2004.

3. Gundel P., personal communication 12. Oliver J., Lille C., Pettersson R., Nylén M., Evaluation of Ni-
brazed prototypes in stainless & tool steels (VAMP-13), Swed-
4. Hermanek F.J., An introduction to brazing, brochure, Alloy ish Institute for Metals Research Report IM-2002-549
Metals, Inc.
13. Lille C., Chèse I., Pettersson R.F.A., “Corrosion of Brazed
5. Brazing Handbook, 4th edition, American Welding Society, Joints in Stainless and Tool Steels (VAMP 13)”, Swedish
Miami, 199 Institute for Metals Research Report IM-2001-535.

6. Humpston G., Jacobson D.M., Principles of Soldering and 14. Alfa Laval press release, AlfaNova – a revolution in heat
Brazing, ASM, Materials Park, 1993 transfer technology, September, 2003

7. Edenhofer B., Steel Treatment Handbook, edited by G.Totten 15. Claesson E., Engström H., Holm T., Schölin K., “Nitrogen
& M.Howes, Marcel Dekker, Inc., New York, 1997 Flow Optimization System for CAB (NOCOLOK) Furnaces”,
VTMS Conference, England, May 1995.
8. Holm T., Wiberg S., Mahlo T., Andersson R., Furnace At-
mospheres for Tube Annealing, Linde Gas Special Edition, 16. http://www.cuprobraze.com/
2004.
17. do Nascimento R. M., Martinelli A. E., A. BuschinelliJ. A.,
9. Engström A., Thermo-Calc, http://www.thermocalc.se/ Review Article: Recent advances in metal-ceramic brazing,
Cerâmica 49 (2003) 178-198

41
Appendix

Pressure conversions
Pa (=1N/m2) Bar Torr Atm
–5 –3
1 Pa (=1N/m2) 1 10 7,50 × 10 0,987 × 10 –5

1 Bar 105 1 750 0,987


2 –3
1 Torr 1,33 × 10 1,33 ×10 1 1,32 × 10 –3

1 Atm 1,01 ×105 1,013 760 1

Prefixes:
k = thousand = 103; Example: 1 kPa = 1000 Pa
m = millionth = 10 –6; Example: 1 mbar = 0,000001 bar
M = million = 10 6; Example: 1 Mbar = 1000000 bar

42
43
Spec-Edit.BrazingMetals.US.05.05 30.05.2005 8:47 Uhr Seite 4

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