U.S. patent number 3,929,516 [Application Number 05/501,990] was granted by the patent office on 1975-12-30 for process for producing cu-base alloys.
This patent grant is currently assigned to Olin Corporation. Invention is credited to Harvey P. Cheskis, Michael J. Pryor, Stanley Shapiro.
United States Patent |
3,929,516 |
Cheskis , et al. |
December 30, 1975 |
Process for producing Cu-base alloys
Abstract
A processing method for certain copper base alloys is described
which reduces or eliminates the tendency for blister formation
during annealing of alloy strip. The problem involves the formation
of internal voids and subsequent migration and expansion of
hydrogen within these voids, and the solution to the problem
includes annealing under carefully controlled conditions of
temperature and metal thickness so as to reduce the hydrogen level
followed by a controlled deformation which heals the internal
defects.
Inventors: |
Cheskis; Harvey P. (New Haven,
CT), Shapiro; Stanley (New Haven, CT), Pryor; Michael
J. (Woodbridge, CT) |
Assignee: |
Olin Corporation (New Haven,
CT)
|
Family
ID: |
23995852 |
Appl.
No.: |
05/501,990 |
Filed: |
August 30, 1974 |
Current U.S.
Class: |
148/681; 148/436;
148/687; 148/684 |
Current CPC
Class: |
C22F
1/08 (20130101) |
Current International
Class: |
C22F
1/08 (20060101); C22D 001/08 () |
Field of
Search: |
;148/11.5R ;75/162 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Stallard; W.
Attorney, Agent or Firm: Bachman; Robert H. Jackson; David
A.
Claims
What is claimed is:
1. A method for producing blister free copper alloy material using
as a starting material a copper alloy which has been hot worked at
least 50 percent to a thickness of from 0.200 to 0.750 inch
including the steps of:
A. annealing the copper alloy material at a temperature of from 40
to 70 percent of the absolute melting temperature of the alloy for
a time of from 1 to 24 hours; and
B. cold working the material at least 60 percent.
2. A method as in claim 1 wherein the starting material contains
from 2.5 to 3.1 percent aluminum, from 1.5 to 2.1 percent silicon,
from 0.25 to 0.55 percent cobalt, balance essentially copper.
3. A method as in claim 1 wherein the hot worked starting material
has been reduced in area by at least 75 percent during hot
working.
4. A method as in claim 1 wherein the thickness of the starting
material is from 0.300 to 0.500 inch.
5. A method as in claim 1 wherein Step A is performed in a
protective reducing atmosphere.
6. A method as in claim 1 wherein the deformation in Step B is at
least 75 percent.
7. A method for producing annealed blister free copper alloy
material using as a starting material a copper alloy which has been
hot worked at least 50 percent to a thickness from 0.200 to 0.750
inch including the steps of:
A. annealing the copper alloy material at a temperature of from 40
to 70 percent of the absolute melting temperature of the alloy for
a time of from 1 to 24 hours;
B. cold working the material at least 40 percent at a temperature
of less than the temperature used in Step A; and
C. annealing the material.
8. A method as in claim 7 wherein the starting material contains
from 2.5 to 3.1 percent aluminum, from 1.5 to 2.1 percent silicon,
from 0.25 to 0.55 percent cobalt, balance essentially copper.
9. A method as in claim 7 wherein the hot worked starting material
has been reduced in area by at least 75 percent during hot
working.
10. A method as in claim 7 wherein the thickness of the starting
material is from 0.300 to 0.500 inch.
11. A method as in claim 7 wherein Step A is performed in a
protective reducing atmosphere.
12. A method as in claim 7 wherein the deformation as in Step B is
at least 75 percent.
13. A method for producing blister free copper alloy material
including the steps of:
A. hot working the alloy at least 50 percent to a thickness of from
0.200 to 0.750 inch;
B. annealing the copper material at a temperature of from 40 to 70
percent of the absolute melting temperature of the alloy for a time
of from 1 to 24 hours; and
C. cold working the material at least 60 percent.
14. A method as in claim 13 wherein the starting material contains
from 2.5 to 3.1 percent aluminum, from 1.5 to 2.1 percent silicon,
from 0.25 to 0.55 percent cobalt, balance essentially copper.
15. A method as in claim 13 wherein the material is reduced at
least 75 percent during Step A.
16. A method as in claim 13 wherein the thickness of the copper
alloy material following Step A is from 0.300 to 0.500 inch.
17. A method as in claim 13 wherein the deformation in Step C is at
least 75 percent.
18. A method for producing blister free copper alloy material
including the steps of:
A. hot working the alloy at least 50 percent to a thickness of from
0.200 to 0.750 inch;
B. annealing the copper material at a temperature of from 40 to 70
percent of the absolute melting temperature of the alloy for a time
of from 1 to 24 hours;
C. cold working the material at least 40 percent; and
D. annealing the material.
19. A method as in claim 18 wherein the starting material contains
from .25 to 3.1 percent aluminum, from 1.5 to 2.1 percent silicon,
from 0.25 to 0.55 percent cobalt, balance essentially copper.
20. A method as in claim 18 wherein the material is reduced at
least 75 percent during Step A.
21. A method as in claim 18 wherein the thickness of the copper
alloy material following Step A is from 0.300 to 0.500 inch.
22. A method as in claim 18 wherein the deformation in Step C is at
least 75 percent.
Description
BACKGROUND OF THE INVENTION
Copper base alloys are widely used in industry and are
characterized by high formability, good conductivity and pleasing
appearance. A high percentage of all copper base alloys are
utilized in the form of strip or sheet. The method of producing
strip or sheet to final gauge usually involves alternate steps of
deformation and annealing. It is often found in certain alloys that
annealing after deformation, particularly at thinner gauges,
produces undesirable blistering. These blisters are gas filled
defects which become apparent when the alloy is heated. As the
temperature is raised, gas pressure inside the defect increases,
thus expanding and deforming the surrounding metal which has a low
yield strength because of the elevated temperature. This problem is
particularly common in CDA Alloy 638 which contains 2.5 to 3.1%
aluminum, 1.5 to 2.1% silicon, 0.25 to 0.55% cobalt, balance
essentiallly copper. Unless otherwise noted, all percentages in
this application are weight percentages.
SUMMARY OF THE INVENTION
The present invention comprises a process for the production of
copper strip which results in a blister free product. The process
is a comparatively simple one which can be applied using standard
equipment commonly available in a commercial copper alloy
production facility. The process of the present invention includes
a hot rolling step followed by a diffusion annealing step performed
under carefully controlled conditions. The diffusion anneal step
reduces the hydrogen content of the alloy without permitting
blister formation. Following the diffusion anneal the alloy is cold
worked according to a particular schedule. This cold working
operation welds shut the internal defects so that blistering will
not occur during subsequent annealing operations. The present
invention is broadly applicable to a wide range of copper alloys
but is particularly useful in connection with the production of CDA
Alloy 638.
It is an object of the present invention to provide a production
method for producing high quality copper alloy strip.
It is a further object of the present invention to provide a
processing technique which minimizes blister formation in copper
alloys.
Further objects will become apparent when the following description
of the preferred embodiments and claims are considered.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention provides a process for producing blister free
copper alloy sheet or strip through the use of a process which
includes the steps of casting, hot working, diffusion annealing,
cold rolling and optionally a further annealing step. The following
description will provide detailed parameters for each of the steps
in the process of the present invention.
The casting of the alloy may be performed using any process which
will produce a sound ingot. It is preferred, however, to use a
process in which a minimum surface area of molten metal is exposed
to the atmosphere during casting. For this reason it is preferred
to use D.C. casting.
Regardless of precautions taken, a certain amount of hydrogen will
be present within the metal if the casting operation is performed
in a normal atmosphere. Hydrogen pickup can occur from moisture or
dirt in the charge materials, moisture and impurities in the flux
or melt cover, moisture in the air and moisture or dirt in the
mold. As an approximation molten copper alloys can hold four times
as much hydrogen as solidified copper alloys at similar
temperatures. Thus, it is common that solidified copper alloys
contain more hydrogen than would be present under equilibrium
conditions.
The ingot is then hot worked, usually by rolling, using an
appropriate hot working temperature. In the case of CDA Alloy 638
which contains 2.5 to 3.5% aluminum, 1.5 to 2.1% silicon, 0.25 to
0.55% cobalt, balance essentially copper, an appropriate hot
working temperature is from 800.degree.to 920.degree.C, preferably
850.degree.to 900.degree.C. In general, the hot working temperature
will be from 0.7 to 0.95 T.sub.m where T.sub.m is the absolute
melting point of the alloy. During the initial stages of hot
working internal cracking occurs and it is to these internal cracks
which dissolved hydrogen may diffuse and subsequently cause
blisters. Hydrogen is present in the metal itself in dissociated or
atomic form. Hydrogen in internal defects will combine to form
molecular hydrogen, H.sub.2. Molecular hydrogen is essentially
insoluble in copper alloys and will not diffuse through copper
alloys. It is desirable to hot work more than 50 percent since
partial healing or bonding of these internal cracks occurs. As
increased deformation occurs, some of the defects heal as their
surfaces bond together. It is preferred that the hot working
reduction be from 75 to 95 percent since material made with
reductions of this order of magnitude has fewer internal defects
than material made with lower reduction. Complete healing of
internal cracks is not possible because of the presence of hydrogen
within the defect which interferes with the complete bonding of the
internal crack surfaces. The final gauge after hot working must be
from 0.200 to 0.750 inch and is preferably from 0.300 to 0.550
inch. The importance of this requirement will be made clear in a
subsequent paragraph.
The hot worked strip is then annealed under conditions which will
permit the diffusion of hydrogen from within the strip to the
surface of the strip and then to the surrounding environment. The
temperature and metal thickness required are interrelated such that
the metal will not yield under the action of the internal gas
pressure, but rather will permit the hydrogen which is trapped in
the defects to dissociate the diffuse out of the metal. It is most
surprising that at the temperatures employed the molecular hydrogen
within the defects can dissociate to permit its diffusion out of
the void through the metal and to the surrounding environment. This
is particularly unusual since at the temperatures involved,
hydrogen in the surrounding atmosphere will not dissociate and thus
cannot enter the metal. The annealing temperature should fall
within the range of 0.4 to 0.7 T.sub.m where T.sub.m is the
absolute melting point of the alloy. In the case of CDA Alloy 638
the temperature range is approximately 450.degree. to 650.degree.C.
Naturally, the time of the treatment must be selected so as to
permit the diffusion of the hydrogen out of the metal. The time
limitation is affected by the thickness of the strip which controls
the average diffusion distance for the hydrogen. It is further
limited by the temperature of the treatment. In general, periods
from 1 to 24 hours are appropriate. Increasing the strip thickness
requires longer diffusion times for the same temperature, and for
strips of the same thickness longer times are required at lower
temperatures. It is important for the temperature range
contemplated that the strip be no thinner than 0.200 inch since
thin strips have less ability to resist the expansion of defects
from increased internal hydrogen pressure than do thick strips. It
is also important that the length of the diffusion anneal treatment
not be any longer than necessary since undesirable changes to the
metallurgical microstructure and properties of the alloy may occur.
These undesirable changes include changes in the amount and
distribution of second phases, depletion of solute elements and/or
undesirable increases in grain size.
The efficacy of this diffusion annealing treatment is independent
of the furnace atmosphere employed since the atomic hydrogen will
recombine at the free surface of the metal and since the molecular
hydrogen in the atmosphere cannot diffuse into the alloy. Thus,
either reducing, inert, or oxidizing environments are allowable. It
is preferred to use conventional reducing atmospheres in order to
minimize surface oxidation during this annealing step.
After the diffusion annealing step the strip is cold rolled at
least 60 percent and preferably at least 75 percent. This cold
rolling operation serves to weld together the internal defects.
Reductions of less than 60 percent do not provide adequate bonding
of internal defect surfaces. However, if the strip is to be
annealed subsequent to this cold rolling step reductions as low as
40% may be satisfactory. Such optional annealing may be carried out
at temperatures of from 0.4 to 0.9 T.sub.m for times of from 5
seconds to 24 hours. Optionally, bonding may also be obtained if
the rolling operation is performed at temperatures above room
temperature.
Following the cold rolling operation the strip may optionally be
annealed so as to obtain the desired mechanical properties such as
strength and ductility. This annealing operation is desirable in
that it will help to remove any vestige of the prior internal
defects. Following the optional annealing step, further operations
may be performed. If for example it is desired to have a final
product having mechanical properties which correspond to those
which result from 10 percent cold work, it would be necessary to
anneal the material following the first cold rolling step and then
cold roll to 10 percent since the first cold rolling step must
incorporate a higher amount of deformation.
Although the preceding discussion has been in terms of the
production of copper strip or sheet it will be appreciated that the
process of the present invention is equally applicable to other
material forms such as rod and wire. The process of the present
invention is applicable to all copper alloys in which blistering
occurs as a result of entrapped hydrogen.
This invention may be embodied in other forms or carried out in
other ways without departing from the spirit or essential
characteristics thereof. The present embodiment is therefore to be
considered as in all respects illustrative and not restrictive, the
scope of the invention being indicated by the appended claims and
all changes which come within the meaning and range of equivalency
are intended to be embraced therein.
* * * * *