CA1045009A - Process for producing copper base alloys - Google Patents
Process for producing copper base alloysInfo
- Publication number
- CA1045009A CA1045009A CA232,192A CA232192A CA1045009A CA 1045009 A CA1045009 A CA 1045009A CA 232192 A CA232192 A CA 232192A CA 1045009 A CA1045009 A CA 1045009A
- Authority
- CA
- Canada
- Prior art keywords
- alloy
- copper
- temperature
- annealing
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Lead Frames For Integrated Circuits (AREA)
- Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
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.
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.
Description
. ~,.
BACKGROUND 0~ THE INVENTION
- . . __ .
Copper base alloys are widel~ 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 i creases, thus expanding and de~orming the surrounding metal whlch has a low yield strength because of the elevated temperature. This problem is particularly common in CDA Alloy 638 which contains
BACKGROUND 0~ THE INVENTION
- . . __ .
Copper base alloys are widel~ 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 i creases, thus expanding and de~orming the surrounding metal whlch 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% sillcon, .25 to .55% cohalt, balance essentially copper. Unless otherwise noted, all percentages in this application are weight percentages.
SUMMARY OF THE INVENTION
The present invention compri~es 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 a~ailable 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 permittlng blister formation. Following the diffusion anneal the alloy is cold worked according to a particular schedule. This cold working operation welds shut the i~ternal defects so that blistering will not occur during subsequent - 2 - ~ ~
~ :, i " , , ,", ", ;
-1~45C~0~ ~
- annealing operations. The present invention is broadly appli-cable 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 forma-tion in copper alloys.
It is an object of the present invention to provide , ; 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% to a thickness of from .200 to .750" including the i;
steps of:
A. annealing the copper alloy material at a .. ..
temperature of from 40 to 70% of the absolute melting temperature of the alloy for a time of from 1 to 2~ hours; and B. cold working the material at least 60%.
Further objects will become apparent when the follow-ing description of the preferred embodiments and claims are considered.
DESCRIPTION OF THE P
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.
,.. .
, . . .
~ - 3 _ . .
)450~9 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.
or 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 mater~
ials, 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 - .~ .
' .
- 3a -',' . ;''' ., '~ : so20-r~s 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, .25 to .55% cobalt, balance essentially copper, an appropriate hot working temperature is from 80oo to 920C, preferably 850 to 900C. In general, the hot working temperature will be from .7 to .95 Tm -where Tm 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 ccmbine to form molecular hydrogen, H2. Molecular hydrogen is essentially insoluble in copper alloys and will not diffuse through copper alloys. It is desirable to ho~ work more than 50% since partial healing or bonding of these internal ;- cracks occurs. As lncreased deformation occurs, some of the ~; 20 defects heal as ~heir surfaces bond together. It is preferred that the hot working reduction be from 75 to 95% since material made with reductions of this order of magnitude has fewer internal defects than material made with lower reduction. Complete healing Or 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 ~o 0.750" and is preferably from 0.300 to 0.550". The importance Or this requirement will be made clear in a subsequent paragraph.
me hot worked strip is then annealed under conditions which '" 5020-MB
)4~0Q9 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 ~s trapped in the defects to dissociate and diffuse out of the metal. It is ~ost surprising that at the temperatures employed the molecular hydrogen within the defects can dissociate to permit its diffuslon 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 .4 to .7 Tm where Tm is the absolute melting point of the alloy. In the case of CDA
Alloy 638 the temperature range is approximately 450 to 650C.
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 ~urther limited by the temperature of the treatment. In general, periods froim 1 to 24 hours are appropriate. Increasing the strip thickness requires longer diffusion times for the same temperature, and for strlps 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" since thin strips have less ability to resist the expansion of defects from increased lnternal 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.
_ 5020 MB
S(~09 These undesirable changes include changes in the amount and distribution of second phases, depletion of solute ~ements and/or undesirable increases in grain size.
The efficacy of this di~fusion annealing treatment ls lndependent 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 dlffuse into the alloy. Thus, either reducing~inert,or oxidizing environments are allowable. It is preferred to use conventional reducing atmos-pheres in order to minimize surface oxidation during this annealingstep.
After the diffusion annealing step the strip is cold rolled at least 60% and preferably at least 75%. This cold rolling operation serves to weld together the internal defects.
Reductions of less than 60% 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 carrled out at temperatures o~ from .4 to .9 Tm for times of from 5 seconds to 24 hours. Opt~onally, bonding may also be obtained if the rolling operation is performed at temperatures above room l -temperature.
Following the cold rolling operation the strip may optionally be annealed so as to obtain the desired mechanical properties such as strength and ductllity. This an~ealing operation is desirable in that lt 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 ls desired to have a ~inal product having mechanical properties which correspond to those which result from 10% cold work, it would be necessary :~ , l04saQs to anneal the material following the first cold rollin~ step and then cold roll to 10% since the first cold rolling step must lncorporate 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 inventlon 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.
o mis invention may be embodied in other forms~or carried out in other ways without departing from the spirit or essential characterlstics 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.
. . :-: . . . . .
, : , .;-~
SUMMARY OF THE INVENTION
The present invention compri~es 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 a~ailable 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 permittlng blister formation. Following the diffusion anneal the alloy is cold worked according to a particular schedule. This cold working operation welds shut the i~ternal defects so that blistering will not occur during subsequent - 2 - ~ ~
~ :, i " , , ,", ", ;
-1~45C~0~ ~
- annealing operations. The present invention is broadly appli-cable 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 forma-tion in copper alloys.
It is an object of the present invention to provide , ; 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% to a thickness of from .200 to .750" including the i;
steps of:
A. annealing the copper alloy material at a .. ..
temperature of from 40 to 70% of the absolute melting temperature of the alloy for a time of from 1 to 2~ hours; and B. cold working the material at least 60%.
Further objects will become apparent when the follow-ing description of the preferred embodiments and claims are considered.
DESCRIPTION OF THE P
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.
,.. .
, . . .
~ - 3 _ . .
)450~9 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.
or 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 mater~
ials, 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 - .~ .
' .
- 3a -',' . ;''' ., '~ : so20-r~s 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, .25 to .55% cobalt, balance essentially copper, an appropriate hot working temperature is from 80oo to 920C, preferably 850 to 900C. In general, the hot working temperature will be from .7 to .95 Tm -where Tm 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 ccmbine to form molecular hydrogen, H2. Molecular hydrogen is essentially insoluble in copper alloys and will not diffuse through copper alloys. It is desirable to ho~ work more than 50% since partial healing or bonding of these internal ;- cracks occurs. As lncreased deformation occurs, some of the ~; 20 defects heal as ~heir surfaces bond together. It is preferred that the hot working reduction be from 75 to 95% since material made with reductions of this order of magnitude has fewer internal defects than material made with lower reduction. Complete healing Or 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 ~o 0.750" and is preferably from 0.300 to 0.550". The importance Or this requirement will be made clear in a subsequent paragraph.
me hot worked strip is then annealed under conditions which '" 5020-MB
)4~0Q9 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 ~s trapped in the defects to dissociate and diffuse out of the metal. It is ~ost surprising that at the temperatures employed the molecular hydrogen within the defects can dissociate to permit its diffuslon 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 .4 to .7 Tm where Tm is the absolute melting point of the alloy. In the case of CDA
Alloy 638 the temperature range is approximately 450 to 650C.
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 ~urther limited by the temperature of the treatment. In general, periods froim 1 to 24 hours are appropriate. Increasing the strip thickness requires longer diffusion times for the same temperature, and for strlps 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" since thin strips have less ability to resist the expansion of defects from increased lnternal 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.
_ 5020 MB
S(~09 These undesirable changes include changes in the amount and distribution of second phases, depletion of solute ~ements and/or undesirable increases in grain size.
The efficacy of this di~fusion annealing treatment ls lndependent 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 dlffuse into the alloy. Thus, either reducing~inert,or oxidizing environments are allowable. It is preferred to use conventional reducing atmos-pheres in order to minimize surface oxidation during this annealingstep.
After the diffusion annealing step the strip is cold rolled at least 60% and preferably at least 75%. This cold rolling operation serves to weld together the internal defects.
Reductions of less than 60% 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 carrled out at temperatures o~ from .4 to .9 Tm for times of from 5 seconds to 24 hours. Opt~onally, bonding may also be obtained if the rolling operation is performed at temperatures above room l -temperature.
Following the cold rolling operation the strip may optionally be annealed so as to obtain the desired mechanical properties such as strength and ductllity. This an~ealing operation is desirable in that lt 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 ls desired to have a ~inal product having mechanical properties which correspond to those which result from 10% cold work, it would be necessary :~ , l04saQs to anneal the material following the first cold rollin~ step and then cold roll to 10% since the first cold rolling step must lncorporate 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 inventlon 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.
o mis invention may be embodied in other forms~or carried out in other ways without departing from the spirit or essential characterlstics 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.
. . :-: . . . . .
, : , .;-~
Claims (22)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
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% to a thickness of from .200 to .750" including the steps of:
A. annealing the copper alloy material at a temperature of from 40 to 70% 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%.
A. annealing the copper alloy material at a temperature of from 40 to 70% 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%.
2. A method as in Claim 1 wherein the starting material contains from 2.5 to 3.1% aluminum, from 1.5 to 2.1% silicon, from .25 to .55% 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% during hot working.
4. A method as in Claim 1 wherein the thickness of the starting material is from .300 to .500".
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%.
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% to a thickness from .200 to .750' including the steps of:
A. annealing the copper alloy material at a temperature of from 40 to 70% 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% at a temperature of less than the temperature used in Step A; and C. annealing the material.
A. annealing the copper alloy material at a temperature of from 40 to 70% 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% 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% aluminum, from 1.5 to 2.1% silicon, from .25 to .55% 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% during hot working.
10. A method as in Claim 7 wherein the thickness of the starting material is from .300 to .500".
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%.
13. A method for producing blister free copper alloy material including the steps of:
A. hot working the alloy at least 50% to a thickness of from .200 to .750";
B. annealing the copper material at a temperature of from 40 to 70% 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%.
A. hot working the alloy at least 50% to a thickness of from .200 to .750";
B. annealing the copper material at a temperature of from 40 to 70% 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%.
14. A method as in Claim 13 wherein the starting material contains from 2.5 to 3.1% aluminum, from 1.5 to 2.1% silicon, from .25 to .55% cobalt, balance essentially copper.
15. A method as in Claim 13 wherein the material is reduced at least 75% during Step A.
16. A method as in Claim 13 wherein the thickness of the copper alloy material following Step A is from .300 to .500".
17. A method as in Claim 13 wherein the deformation in Step C is at least 75%.
18. A method for producing blister free copper alloy material including the steps of:
A. hot working the alloy at least 50% to a thickness of from .200 to .750";
B. annealing the copper material at a temperature of from 40 to 70% 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%; and D. annealing the material.
A. hot working the alloy at least 50% to a thickness of from .200 to .750";
B. annealing the copper material at a temperature of from 40 to 70% 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%; and D. annealing the material.
19. A method as in Claim 18 wherein the starting material contains from .25 to 3.1% aluminum, from 1.5 to 2.1% silicon, from .25 to .55% cobalt, balance essentially copper.
20. A method as in Claim 18 wherein the material is reduced at least 75% during Step A.
21. A method as in Claim 18 wherein the thickness of the copper alloy material following Step A is from ,300 to .500".
22. A method as in Claim 18 wherein the deformation in Step C is at least 75%.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US501990A US3929516A (en) | 1974-08-30 | 1974-08-30 | Process for producing Cu-base alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1045009A true CA1045009A (en) | 1978-12-26 |
Family
ID=23995852
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA232,192A Expired CA1045009A (en) | 1974-08-30 | 1975-07-24 | Process for producing copper base alloys |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US3929516A (en) |
| JP (1) | JPS5143314A (en) |
| AU (1) | AU502316B2 (en) |
| CA (1) | CA1045009A (en) |
| DE (1) | DE2536167B2 (en) |
| FR (1) | FR2283239A1 (en) |
| GB (1) | GB1507227A (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2490116A1 (en) * | 1980-09-12 | 1982-03-19 | Gp Konstruk | Prodn. of brass pipes - by cold working a tubular blank and then annealing in a protective atmos. |
| KR890003966B1 (en) * | 1984-05-23 | 1989-10-14 | 스미또모 덴끼 고오교 가부시기가이샤 | Wire electrode for wire electro-discharge machine |
| US4728372A (en) * | 1985-04-26 | 1988-03-01 | Olin Corporation | Multipurpose copper alloys and processing therefor with moderate conductivity and high strength |
| US8746008B1 (en) * | 2009-03-29 | 2014-06-10 | Montana Instruments Corporation | Low vibration cryocooled system for low temperature microscopy and spectroscopy applications |
| US11125663B1 (en) | 2016-03-11 | 2021-09-21 | Montana Instruments Corporation | Cryogenic systems and methods |
| US10775285B1 (en) | 2016-03-11 | 2020-09-15 | Montana Intruments Corporation | Instrumental analysis systems and methods |
| US10451529B2 (en) | 2016-03-11 | 2019-10-22 | Montana Instruments Corporation | Cryogenic systems and methods |
| WO2020076988A1 (en) | 2018-10-09 | 2020-04-16 | Montana Instruments Corporation | Cryocooler assemblies and methods |
| US11956924B1 (en) | 2020-08-10 | 2024-04-09 | Montana Instruments Corporation | Quantum processing circuitry cooling systems and methods |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3259491A (en) * | 1963-05-21 | 1966-07-05 | Olin Mathieson | Copper base alloys and process for preparing same |
| US3788902A (en) * | 1972-11-24 | 1974-01-29 | Olin Corp | Process for improving the elongation of grain refined copper base alloys |
| US3841921A (en) * | 1973-03-02 | 1974-10-15 | Olin Corp | Process for treating copper alloys to improve creep resistance |
-
1974
- 1974-08-30 US US501990A patent/US3929516A/en not_active Expired - Lifetime
-
1975
- 1975-07-24 CA CA232,192A patent/CA1045009A/en not_active Expired
- 1975-07-24 GB GB31013/75A patent/GB1507227A/en not_active Expired
- 1975-07-28 AU AU83432/75A patent/AU502316B2/en not_active Expired
- 1975-08-05 FR FR7524414A patent/FR2283239A1/en active Granted
- 1975-08-07 JP JP50096275A patent/JPS5143314A/ja active Pending
- 1975-08-13 DE DE2536167A patent/DE2536167B2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US3929516A (en) | 1975-12-30 |
| AU8343275A (en) | 1977-02-03 |
| DE2536167A1 (en) | 1976-03-11 |
| DE2536167B2 (en) | 1979-02-08 |
| JPS5143314A (en) | 1976-04-14 |
| AU502316B2 (en) | 1979-07-19 |
| GB1507227A (en) | 1978-04-12 |
| FR2283239B1 (en) | 1978-10-13 |
| FR2283239A1 (en) | 1976-03-26 |
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