Fig. 5.

Copper alloy after

bright annealing
(Photo courtesy of
Ebner-Industrieofenbau)

FEATURE | Industrial
Gases/Combustion

Bright Annealing Copper and its Alloys

Paul F. Stratton Linde Gas; Sheffield, U.K.
The annealing of the majority of copper-based alloys is not very demanding in
terms of protective atmospheres. However, the protective atmosphere used can be
critical to the apparent quality of the finished product.

igh-quality product usually requires a bright finish.

That finish can be obtained easily and consistently
using a high-quality atmosphere, but in addition to
the production engineers quality goals, minimizing
cost is also the objective. This optimization process will entail
closer tailoring of the atmosphere to material and furnace requirements.

the line the metal oxidized. The component requiring the most
reducing atmosphere must be considered the critical element. For
most practical purposes, however, elements with concentrations
below 1% can be ignored because they do not form continuous
oxide films.
As can be seen from Figure 1, for some alloying elements the
10+14

O2 + H2 H2O
From this equation we can see that the oxygen partial pressure is related to the H :H O ratio. The higher the ratio, the more

reducing the atmosphere. Thus, if the atmosphere composition is
above the line in Figure 1, the oxide would be reduced and below

Al
10+11
10+9
Hydrogen:water ratio

Basic Principles
The basic function of the furnace atmosphere in copper-basedalloy annealing is to protect the product from oxidation. To
achieve this, the oxygen partial pressure of the atmosphere must
be less than that necessary to form the oxide. Even high-purity
nitrogen contains one or two parts per million of oxygen, and furnace leaks are inevitable. Therefore, to reduce the oxygen, it is
reacted with an active gas, such as hydrogen, as follows:

Cr

10+5

Zn

10+2
Fe

Sn

10-1

Ni

10-4

Pb

Cu

10-7
10-10
0

200

400

600
800
Temperature, C

1000

1200

Fig. 1. The oxidation limits for various elements

IndustrialHeating.com - February 2010 51

FEATURE | Industrial
Gases/Combustion

H :H O ratio required to keep the alloy

bright rises as the temperature falls, making the cooling zone the most critical part
of a continuous furnace in these cases. If
the furnace atmosphere of such a furnace
is flammable and allowed to burn off at
the exit, oxidation of the product can occur as it passes through the flame front.
Such problems are best avoided either by
using a non-flammable atmosphere or ensuring that any flammable component is
diluted below the flammable limit before
the exit. These differing requirements, together with the need to minimize the total quantity of atmosphere gas used (and
hence minimize cost), are best achieved
using zoning technology. This technique
allows the use of different atmospheres in
different zones in a continuous furnace
and helps to minimize the overall atmosphere consumption.
Conclusions drawn from Figure 1 must
be regarded with caution, particularly
below about 300C (572F), since equilibrium conditions may not apply and reactions are slow. What happens is more related to reaction rates and availability. At
low temperatures, non-equilibrium oxides
of tin and copper may form, particularly
when the availability of oxygen is low. At

lower temperatures, the oxides formed on

alloys tend to reflect the most abundant
rather than the most active constituent.
Other reducing gases can be used to
prevent oxidation. Exothermically generated gas (exogas) is a partially combusted
natural gas mixture containing N2, CO,
CO2, H2 and H2O. It is sometimes used in
copper-alloy annealing. At typical annealing temperatures, the component gases
are at equilibrium, and it is sufficient to
examine the H2:H2O ratio to determine
its oxidizing tendencies. A point to note
about CO-bearing atmospheres, besides
their toxicity, is the possibility of forming carbon soot, particularly in the 400600C (752-1112F) range according to
the producer gas or Boudouard reaction:
2CO = CO2 + C
An additional role of the atmosphere is
to remove unwanted processing lubricants
from a furnace. This can be achieved either by physical flushing or by reacting
the lubricant with a component of the
atmosphere. In continuous furnaces it is
usually necessary to restrict the active atmosphere component to the entry areas
because they tend to be oxidizing to the
components at the annealing tempera-

Fig. 2. Copper tube annealed using a non-cryogenically generated nitrogen

and hydrogen atmosphere

52 February 2010 - IndustrialHeating.com

ture. The same is true of batch-furnace

operations where the process must be
completed well before the annealing temperature is reached. For some lubricants,
this can entail a dwell in the ramp-up to
annealing temperature at some intermediate temperature at which volatilization
or reaction is essentially complete.
Copper
Copper is difficult to oxidize and, as can be
seen from Figure 1, lies below most of the
common nonferrous metals. It is common
practice to anneal copper either in exogas
or in steam. The former contains some CO
which can decompose into soot and CO2,
and the latter is expensive. A cleaner, nontoxic alternative is high-purity nitrogen
with a small hydrogen addition (1-2% depending on furnace tightness). It should be
noted that tough pitch copper should be annealed in atmospheres containing no more
than 2% hydrogen to avoid embrittlement.
While high-purity nitrogen/hydrogen
will undoubtedly result in the highestquality finish, there are cheaper options
that, with the proper precautions, can
produce an equally good result (Fig. 2).
If the high-purity nitrogen is replaced by
lower-purity nitrogen from an ADSOSS

Fig. 3. ADSOSS-N nitrogen-generation plant

non-cryogenic nitrogen generator (Fig. 3),

costs can be reduced. The small amount
of oxygen present in the nitrogen will
react with some of the hydrogen to form
water vapor, which as stated previously is
not oxidizing to copper. Unfortunately,
however, the reaction is slow and steps
must be taken to ensure that it is complete before the gas mixture interacts
with the work. There are several ways of
achieving this, but perhaps the most effective is to pass the gas mixture over a
catalyst prior to its introduction into the
furnace. The hydrogen level must also be
adjusted to take into account that which

reacted with the oxygen.

If the exposure time of the copper to
the annealing atmosphere is short (as, for
example, in the continuous annealing of
wire for electrical cable), then increasing
amounts of free oxygen can be tolerated
with increasing speed. For annealing of
heavier cables in tube furnaces, highpurity nitrogen alone with 1 or 2 ppm of
free oxygen will suffice. Where speeds are
higher in the induction annealing of fine
wires, oxygen levels of up to 3% can be
used, allowing non-cryogenically generated nitrogen to be employed directly as
the protective atmosphere.

Fig. 4. Brass wire after annealing in 100% hydrogen in a high-integrity HICON/H2 bell
furnace (Photo courtesy of Ebner-Industrieofenbau)

Brass
Brass is a very different problem than copper. Zinc is much more oxidizable than copper. To make matters worse, both zinc and
its oxide volatilize at high temperatures.
Zinc can volatilize from coils of brass strip
and oxidize to form white discoloration at
the edges of coils. If zinc oxide forms at
high temperatures, it also volatilizes and
reprecipitates in the cooler parts of the
furnace, including the cooling work, forming an unsightly white bloom. None of the
atmospheres generated from the partial
combustion of hydrocarbon fuel gases are
suitable for the bright annealing of brass,
although endothermically generated atmospheres are sometimes employed. Once
again, however, the Boudouard reaction
must be considered as such atmospheres
contain CO, which will break down to
soot and discolor the components.
In most furnaces a mixture of highpurity nitrogen with 40% hydrogen is suitable, although many operators use 100%
hydrogen in high-integrity bell furnaces
for the highest-quality product (Fig. 4).
It is recommended that the dew point is
maintained at less that -40C. A HYDROFLEX control system can be used
to ensure optimum atmosphere conditions
at all times in continuous furnaces. It may
be possible to use slightly less hydrogen if
the furnace is very tight (for example, for
hump-back continuous furnaces or where a
less than fully bright finish is acceptable).
Cracked ammonia can also be used but
with the caveats given below for bronzes.
Bronze
Tin, as well as being less easily oxidized
than zinc, forms a stable protective oxide
at annealing temperatures. This makes
bronzes easier to protect during the process. Although a rich exogas can be employed, it contains even more CO than
the lean gas used for copper annealing.
Hence, the toxicity and propensity to
soot are increased. The non-toxic alternative is nitrogen/hydrogen. One solution
to the provision of nitrogen/hydrogen
mixtures is cracked ammonia. As in this
case, however, where the proportion of
IndustrialHeating.com - February 2010 53

FEATURE | Industrial
Gases/Combustion

hydrogen required is well below the 75%

level produced, the economics are often
poor. They can be improved by diluting
the cracked ammonia with high-purity
nitrogen. If cracking equipment is not
well-maintained, ammonia carryover can
occur, resulting in corrosive attack on
copper-based alloys.
The optimum solution is, therefore, to
use a mixture of high-purity nitrogen and
high-purity hydrogen. The proportion
of hydrogen actually required is dependent upon the tightness of the furnace
used. If possible, the proportion should
be kept below 4.9%, which is the lower
explosive limit. In the majority of wellsealed furnaces this is not a problem, and
hydrogen levels as low as 2% have been
successfully employed.
Other Alloys
Other copper-based alloys contain active alloying elements such as aluminum,

beryllium and zinc, but in relatively low

amounts. These alloys can be annealed in
protective atmospheres based on exothermically generated gas, as described above.
However, nitrogen/hydrogen mixtures are
preferable because of the ease of adjusting
the reducing potential as well as considerations of toxicity and soot (Fig. 5 lead
photo). Monel 400 (66% Ni, 0.12% C,
0.90% Mn, 1.35% Fe, 0.15% Si, 31.5% Cu)
and similar alloys remain bright and free
of discoloration when heat treated in a reducing atmosphere.
Summary
Although the basic requirements of the
atmosphere to keep any given alloy bright
during annealing are fixed, the techniques
available for meeting those requirements
are numerous. The optimum method of
supply in terms of cost, performance and
environmental considerations depends
on a number of factors, including furnace

THE

SCIENCE

www.tmvacuum.com

54IH11084TM.indd
February 2010
- IndustrialHeating.com
1

For more information: Contact Dr. Paul

Stratton, CEng CSci FIMMM, heat-treatment
and electronic-packaging application development, Linde AG BOC, Rother Valley Way,
Holbrook, Sheffield, S20 3RP, UK; tel: +44 1484
328736; e-mail: heat-treatment@linde-gas.
com; web: www.linde-gas.com

Additional related information may be

found by searching for these (and other)
key words/terms via BNP Media SEARCH
at www.industrialheating.com: reducing
atmosphere, exothermically generated
atmosphere, bright annealing, induction
annealing

OF VACUUM
> Manufacturing vacuum furnaces
and ovens in our New Jersey
facility since 1965
> Unsurpassed temperature
uniformity, precision control
and data logging
> Easier AMS2750D and NADCAP
conformance
> Offering a range of sizes and
options to fit your budget

T-M Vacuum Products, Inc.

1-856-829-2000

type and size. Several sources of advice are

available, including the Copper Development Association (helpline@copperdev.
co.uk), industrial gas suppliers such as
Linde Gas (heat-treatment@linde-gas.
com) or specialist furnace manufacturers like Ebner-Industrieofenbau (sales@
ebner.cc). IH

info@tmvacuum.com

Cinnaminson, NJ USA
10/20/08 1:24:04 PM