US20040159379A1 - Silver containing copper alloy - Google Patents
Silver containing copper alloy Download PDFInfo
- Publication number
- US20040159379A1 US20040159379A1 US10/782,019 US78201904A US2004159379A1 US 20040159379 A1 US20040159379 A1 US 20040159379A1 US 78201904 A US78201904 A US 78201904A US 2004159379 A1 US2004159379 A1 US 2004159379A1
- Authority
- US
- United States
- Prior art keywords
- temperature
- copper alloy
- anneal
- alloy
- hours
- 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.)
- Abandoned
Links
Images
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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- This invention relates to a silver containing copper alloy. More particularly, the inclusion of a controlled amount of silver in a copper alloy that further contains chromium, titanium and silicon results in improved resistance to stress relaxation and improved isotropic bend properties without a detrimental effect on either yield strength or electrical conductivity.
- Copper alloys are formed into numerous products that take advantage of the high electrical conductivity and/or high thermal conductivity of the alloys.
- a partial list of such products includes electrical connectors, leadframes, wires, tubes, foils and powders that may be compacted into products.
- One type of electrical connector is a box-like structure formed by stamping a predefined shape from a copper alloy strip and then bending the stamped part to form the connector. It is necessary for the connector to have high strength and high electrical conductivity.
- the connector should have a minimal reduction in normal force as a function of time and temperature exposure, commonly referred to as resistance to stress relaxation.
- Properties important for an electrical connector include yield strength, bend formability, resistance to stress relaxation, modulus of elasticity, ultimate tensile strength and electrical conductivity.
- Target values for these properties and relative importance of the properties are dependent on the intended application of products manufactured from the subject copper alloys.
- the following property descriptions are generic for many intended applications, but the target values are specific for under the hood automotive applications.
- the yield strength is the stress at which a material exhibits a specified deviation, typically an offset of 0.2%, from proportionality of stress and strain. This is indicative of the stress at which plastic deformation becomes dominant with respect to elastic deformation. It is desirable for copper alloys utilized as connectors to have a yield strength on the order of 80 ksi, that is approximately 550 MPa.
- Copper based electrical connectors must maintain above a threshold contact force on a mating member for prolonged times for good electrical connection. Stress relaxation reduces the contact force to below the threshold leading to an open circuit. It is a target for a copper alloy for connector applications to maintain at least 90% of the initial stress when exposed to a temperature of 150° C. for 1000 hours and to maintain 85% of the initial stress when exposed to a temperature of 200° C. for 1000 hours.
- the modulus of elasticity also known as Young's modulus, is a measure of the rigidity or stiffness of a metal and is the ratio of stress to corresponding strain in the elastic region. Since the modulus of elasticity is a measure of the stiffness of a material, a high modulus, on the order of 150 GPa is desirable.
- MBR minimum bend radius
- Bend formability may be expressed as, MBR/t, where t is the thickness of the metal strip.
- MBR/t is a ratio of the minimum radius of curvature of a mandrel about which the metallic strip can be bent without failure.
- the “mandrel” test is specified in ASTM (American Society for Testing and Materials) designation E290-92, entitled Standard Test Method for Semi - Guided Bend Test for Ductility of Metallic Materials, and is incorporated by reference in its entirety herein.
- the MBR/t prefferably isotropic, a similar value in the “good way”, bend axis perpendicular to the rolling direction of the metallic strip, as well as the “bad way”, bend axis parallel to the rolling direction of the metallic strip. It is desirable for the MBR/t to be about 0.5 or less for a 90° bend and about 1 or less for a 180° bend.
- the bend formability for a 90° bend may be evaluated utilizing a block having a V-shaped recess and a punch with a working surface having a desired radius.
- a strip of the copper alloy in the temper to be tested is disposed between the block and the punch and when the punch is driven down into the recess, the desired bend is formed in the strip.
- V-block method related to the V-block method is the 180° “form punch” method in which a punch with a cylindrical working surface is used to shape a strip of copper alloy into a 180° bend.
- both methods give quantifiable bendability results and either method may be utilized to determine relative bendability.
- the ultimate tensile strength is a ratio of the maximum load a strip withstands until failure during a tensile test expressed as a ratio of the maximum load to the cross-sectional area of the strip. It is desirable for the ultimate tensile strength to be about 85-90 ksi, that is approximately 585-620 MPa.
- Electrical conductivity is expressed in % IACS (International Annealed Copper Standard) in which unalloyed copper is defined as having an electrical conductivity of 100% IACS at 20° C. It is desirable for copper alloys for high performance electrical connectors to have an electrical conductivity of at least 75% IACS. More preferably, the electrical conductivity is 80% IACS or higher.
- C18600 One copper alloy that approaches the desired properties is designated by the Copper Development Association, New York, N.Y., as C18600.
- C18600 is an iron containing copper-chromium-zirconium alloy and is disclosed in U.S. Pat. No. 5,370,840 to Caron, et al that is incorporated by reference in its entirety herein.
- C18600 has a nominal composition by weight of 0.3% chromium, 0.2% zirconium, 0.5% iron, 0.2% titanium and the balance copper and inevitable impurities.
- U.S. Pat. No. 4,678,637 to Duerrschnabel et al discloses a copper alloy containing additions of chromium, titanium and silicon and is incorporated by reference in its entirety herein.
- This alloy designated by the CDA as C18070, has a nominal composition of 0.28% chromium, 0.06% titanium, 0.04% silicon and the balance copper and unavoidable impurities.
- the alloy When processed by hot rolling, quench and cold rolling interspersed with one or two intermediate bell anneals, the alloy achieves as nominal properties: an electrical conductivity of 86% IACS; a yield strength of 72 ksi (496 MPa), a 90% MBR of 1.6 t in the good way and 2.6 t in the bad way; and a loss of 32% of the stress when subjected to 200° C. for 1000 hours.
- DE 196 00 864 C2 by Wieland-Werke A G discloses an alloy containing 0.1%-0.5% chromium, 0.01%-0.25% titanium, 0.01%-0.1% silicon, 0.02%-0.8% magnesium with the balance being copper and inevitable impurities.
- the magnesium addition is disclosed as improving the resistance of the alloy to stress relaxation.
- a small addition of silver on the order of up to 25 troy ounces per ton avoirdupois (0.085 weight percent), enables cold worked copper to maintain its strength at temperatures of up to about 400° C. as disclosed in Silver - Bearing Copper by Finlay, 1968.
- One silver-containing copper alloy is designated by the CDA as copper alloy C15500.
- C15500 contains 0.027-0.10% silver, 0.04-0.08% phosphorous, 0.08-0.13% magnesium and the balance is copper and unavoidable impurities.
- the alloy is reported in the ASM Handbook as having an electrical conductivity of 90% IACS in an annealed condition, a yield strength of 72 ksi (496 MPa) in the spring temper. Bend formability and resistance to stress relaxation are not reported.
- this copper base alloy contains chromium, titanium and silver.
- iron and tin may be added to promote grain refinement and increase strength.
- Still another feature of the invention is to maximize desired electrical and mechanical properties by processing of the alloy including the steps of solution anneal, quench, cold roll and age.
- Still a further feature of the invention is that a holistic approach to alloy properties is utilized to integrate multiple alloy properties by way of factors weighted by customer derived rankings for specific connector applications.
- the alloy of the invention may be processed to have a yield strength in excess of 80 ksi (550 MPa) and an electrical conductivity in excess of 80% IACS making the alloy particularly useful for forming into electrical connectors for both automotive and multimedia applications.
- a yield strength in excess of 80 ksi (550 MPa) and an electrical conductivity in excess of 80% IACS making the alloy particularly useful for forming into electrical connectors for both automotive and multimedia applications.
- the advantageous properties of the alloy of the invention are an enhanced resistance to stress relaxation at elevated temperatures of up to 200° C.
- a still further advantage is that a strip of metal formed from the alloy has substantially isotropic bend formability and excellent stampability making it particularly useful for forming into box-type connectors.
- a copper alloy that consists essentially of, by weight, from 0.15% to 0.7% of chromium, from 0.005% to 0.3% of silver, from 0.01% to 0.15% of titanium, from 0.01% to 0.10% of silicon, up to 0.2% of iron, up to 0.5% of tin, and the balance is copper and inevitable impurities.
- a process for forming a copper alloy having high electrical conductivity, good resistance to stress relaxation and isotropic bend properties includes the steps of casting a copper alloy that contains, by weight, from 0.15% to 0.7% of chromium, additional desired alloying additions, and the balance is copper and inevitable impurities.
- This copper alloy is formed into a strip that is solution annealed, by a strip anneal process, at a temperature of from 850° C. to 1030° C. for from 5 seconds to 10 minutes.
- a preferred strip anneal time is from 10 seconds to 5 minutes.
- the strip is then quenched from a temperature of at least 850° C. to a temperature of less than 500° C. in at most 10 seconds.
- the quenched strip is then cold rolled to a reduction of from 40% to 99% in thickness and then annealed at a temperature of between 350° C. and 550° C. for from one hour to 10 hours.
- FIG. 1 is a flow chart of processing steps for the manufacture of strip from the copper alloy of the invention.
- FIG. 2 is a flow chart of processing steps for the manufacture of wire or rod from the copper alloy of the invention.
- FIGS. 3 and 4 graphically illustrate recrystallized grain size for two related alloys of the invention as a function of solution annealing temperature and solution annealing time.
- the alloy of the invention is particularly suited for under the hood automotive applications where it may be subject to elevated ambient temperatures as well as relatively high electrical currents generating I 2 R heating.
- the alloy is useful for multimedia applications, such as computers or telephones, where the service temperature is lower, typically on the order of 100° C. maximum, and signals of relatively low electrical currents are carried.
- the alloy of the invention consists essentially of:
- the balance is copper and inevitable impurities.
- a more preferred alloy range is:
- the balance is copper and inevitable impurities.
- a most preferred alloy composition is:
- the balance is copper and inevitable impurities.
- the titanium content should be 0.05% or higher. If high electrical conductivity is of particularly high relative importance, then the titanium content should be 0.065% or less.
- Chromium Chromium particles precipitate during aging anneals thereby providing age-hardening and a concomitant conductivity increase. It is also believed that the chromium precipitate stabilizes the alloy microstructure by retarding grain growth through second phase pinning of grain boundaries. A minimum of 0.15%, by weight, of chromium is required to achieve these beneficial results.
- silver increases strength, particularly when the chromium content is at the low end, 0.3% or less, of the specified ranges.
- the silver addition improves resistance to elevated temperature stress relaxation.
- Titanium enhances stress relaxation resistance and increases the alloy strength. Below 0.01% titanium, these beneficial effects are not achieved. Excess titanium has a detrimental effect on electrical conductivity of the alloy, probably more so than any of the other alloying elements. To achieve an electrical conductivity of at least 80% IACS, the titanium content should be maintained at 0.065% or less. To achieve a high strength, the titanium content should be maintained at 0.05% or more.
- Iron—Iron is an optional addition that increases the strength of the alloy and also enhances grain refinement, in both the as-cast and as-processed condition.
- the grain refinement improves bend formability.
- an excess of iron unduly decreases electrical conductivity.
- An electrical conductivity of 80% IACS is a desirable consideration, and therefore the iron should be restricted to below 0.1% in accordance with the most preferred alloy composition.
- the iron to titanium ratio is preferably between 0.7:1 and 2.5:1, and more preferably between 0.9:1 and 1.7:1 and most preferably about 1.3:1.
- the iron to tin ratio is preferably between 0.9:1 and 1.1:1 and more preferably about 1:1.
- Tin—Tin is an optional addition that increases the strength of the alloy, but if present in an excessive amount reduces electrical conductivity and also appears to promote stress relaxation. Accordingly, there should be less than 0.5% by weight tin present in the alloy and preferably less than 0.05% tin in the alloy when an electrical conductivity of 80% IACS is required.
- alloy of the invention may be present in the alloy of the invention to achieve desired property enhancements without significantly reducing desirable properties such as bend formability, resistance to stress relaxation or electrical conductivity.
- the total content of these other elements is, for the most part, less than 1% and preferably less 0.5%. Exceptions to this generality are recited below.
- Cobalt may be added as a 1:1, by weight, substitute for iron.
- Magnesium may be added to improve solderability and solder adhesion. Magnesium is also effective to enhance cleaning of the alloy surface during processing. A preferred magnesium content is from about 0.05% to about 0.2%. Magnesium may also improve the stress relaxation characteristics of the alloy.
- Machinability without a significant decrease in electrical conductivity, can be enhanced by additions of sulfur, selenium, tellurium, lead or bismuth. These machinability enhancing additions form a separate phase within the alloy and do not reduce electrical conductivity. Preferred contents are up to 3% for lead, from about 0.2% to about 0.5% for sulfur and from about 0.4% to 0.7% for tellurium.
- De-oxidizers can be added in preferred amounts of from about 0.001% to about 0.1%.
- Suitable de-oxidizers include boron, lithium, beryllium, calcium and rare earth metals either individually or as mischmetal. Boron, that forms borides, is beneficial as it also increases the alloy strength. Magnesium, recited hereinabove, is also effective as a deoxidizer.
- Zirconium has a propensity to combine with silicon and form coarse particles of zirconium silicide. Therefore, it is preferred that the alloy be essentially zirconium free, that is zirconium in impurity amounts only.
- FIG. 1 illustrates in block diagram a sequence of processing steps to achieve the yield strength, bend formability, resistance to stress relaxation, modulus of elasticity, ultimate tensile strength and electrical conductivity desired for the subject copper alloy. These processing steps are believed beneficial for any chromium containing copper alloy.
- the alloy is initially cast 10 by any suitable process.
- cathode copper may be melted at a temperature of approximately 1200° C. in a crucible or a melt furnace with a charcoal cover.
- Chromium, and as desired, the other alloying elements of titanium, silicon, silver and iron are then added to the melt in the form of appropriate master alloys for a casting of a desired composition.
- the casting may be via a continuous process, such as strip casting or belt casting, in which the casting leaves the strip or belt at a thickness suitable for cold rolling 12 prior to solution annealing 14 . This casting thickness is preferably from about 0.4 inch to 1 inch and it is then cold rolled to a nominal thickness of about 0.045 inch.
- the alloy may be cast 10 ′ as a rectangular ingot and broken down into strip by hot rolling 16 .
- hot rolling will be at a temperature of between 750° C. and 1030° C. and used to reduce the thickness of the ingot to somewhat above the solution anneal thickness.
- Hot rolling may be in multiple passes and generally used to form a strip having a thickness greater than that desired for solution annealing.
- the copper alloys of the invention may also be formed into rods, wires or tubes in which instance, the working would more likely be in the form of drawing or extrusion.
- the strip is water quenched and then trimmed and milled to remove any oxide coatings.
- the strip is then cold rolled 12 to solution anneal 14 gauge.
- Cold rolling 12 may be in a single pass or multiple passes with intermediate anneals if necessary.
- the cold rolling step impart the strip with a degree of cold work, such as a 25% -90% reduction in thickness.
- the alloy is solution annealed 14 at a time and temperature effective to achieve full recrystallization without excessive grain growth.
- the maximum grain size is maintained at 20 microns or less. More preferably, the maximum grain size is 15 microns or less.
- the annealing time and temperature should further be selected to be effective to achieve microstructural homogeneity. Thus, if the annealing time or temperature is too low, hardness and microstructural deviations from one portion of the strip to the other are obtained leading to non-isotropic bend properties. Excessive annealing time or temperature leads to undue grain growth and poor bend formability.
- the solution anneal 14 should be a strip anneal at a temperature of from 850° C.
- the solution anneal 14 is at a temperature of from 900° C. to 1000° C. for from 15 seconds to ten minutes and most preferably from 930° C. to 980° C. for from 20 seconds to five minutes.
- FIG. 3 graphically illustrates the effect of solution annealing (SA) time and temperature on the recrystallization and grain growth for a copper alloy having 0.40% chromium.
- SA solution annealing
- FIG. 4 graphically illustrates the effect of solution annealing time to temperature when the alloy contains 0.54% chromium and demonstrates how increasing the chromium content broadens the acceptable range of annealing time and temperature. Recrystallization with a grain size of 10 to 15 microns is achievable in this instance at 950° C. with times of from about 7 seconds up to about 45 seconds. However, while grain size is very well controlled, undissolved chromium particles become larger degrading alloy properties.
- the solution annealed 14 alloy is next quenched 18 to retain microstructural homogeneity. Quenching should take the alloy temperature from the solution anneal temperature, minimum 850° C. and preferably in excess of 900° C., to below 500° C. in 20 seconds or less. More preferably, the quench rate is from 900° C. to less than 500° C. in 10 seconds or less.
- the alloy is cold rolled 20 to a 40% to 80%, by thickness, reduction for strip or sheet.
- a cold roll reduction in excess of 90%, or preferably up to 99%, in thickness is preferred.
- the strip or sheet cold rolled reduction is from 50% to 70%, by thickness, and effected with one or more passes through the rolling mill to generate a heavily cold worked strip.
- the alloy is next given an aging heat treatment 22 .
- the aging heat treatment 22 may be in one step, or preferably is in two steps. It has been found that step aging results in higher strength and electrical conductivity and it is believed that bend formability may also be improved by the step aging.
- the first aging step, and only aging step if done in a single step, is at a temperature of from about 350° C. to about 550° C. for from one to ten hours.
- this first aging step 22 is at a temperature of from 400° C. to 500° C. for from one to three hours.
- the second step anneal 24 is at a temperature of from about 300° C. to about 450° C. for from one to twenty hours leading to increased electrical conductivity without a loss in strength.
- the second step aging 24 is at a temperature of from about 350° C. to about 420° C. for from five to seven hours.
- the alloy may be used in the age annealed condition when enhanced resistance to stress relaxation is required, for example, in automotive applications. Following the aging anneal, the alloy has a yield strength of about 68 ksi (470 MPa) and an electrical conductivity of about 80% IACS. If still higher strengths are required, additional processing steps may follow the age anneal step 22 or 24 .
- the age annealed copper alloy strip is cold rolled 26 to a final gauge thickness, typically on the order of 0.25 mm to 0.35 mm, although it is a target for future connectors to have a thickness on the order of 0.15 mm (0.006 inch) or less.
- the thin strip material under about 0.006 inch, is also useful as a copper alloy foil product.
- the cold rolling 26 will be in one or more passes through a rolling mill with a reduction of between 10% and 50%, in thickness.
- a stress relief anneal 28 at a temperature of between 200° C. and 500° C. for from 10 seconds to 10 hours.
- the stress relief anneal 28 is at a temperature of between 250° C. and 350° C. for from 1 hour to 3 hours.
- FIG. 2 illustrates in block diagram a process flow particularly suited for the manufacture of wire and rod.
- the copper alloy of the invention is cast 30 by any suitable process and extruded 32 to form a rod with a desired cross-sectional shape, preferably the cross-sectional shape is circular.
- the hot extrusion is at a temperature of between 700° C. and 1030° C. and preferably at a temperature of between 930° C. and 1020° C.
- the extruded rod is quenched 34 and then cold drawn (or cold extruded) 36 to a reduction in diameter of up to 98%.
- the drawn rod is then annealed 38 at a temperature of from 350° C. to 900° C. for from 1 minute up to 6 hours.
- the sequence of cold draw 36 and anneal 38 may be repeated one or more additional times and then cold drawn (or cold extruded) 40 to final gauge.
- QFD Quality Function Deployment
- Table 1 recites a list of properties, ratings and ranges for a copper alloy intended for use in automotive applications while Table 2 recites similar properties, ratings and ranges for a copper alloy for use in a multimedia application.
- the “rating” is on a scale of 1 to 10 with 10 meaning the property value is of utmost value while 1 meaning the property value of minimal value.
- the copper alloys of the invention are capable of achieving a QFD value in excess of 50 (desirable) both for automotive and industrial applications and for multimedia applications indicating that a customer would find the subject copper alloy acceptable for both applications.
- the alloy and processing of the invention are equally suitable for forming into leadframes.
- Leadframes require good bend properties as the outer leads are bent at a 90° angle for insertion into a printed circuit board.
- the fine grain structure and absence of coarse particles makes the alloy amenable to uniform chemical etching, a process used in leadframe formation.
- the alloy and processing of the invention are equally suitable for forming rod, wire and sections for electrical applications.
- Prerequisite high stiffness is provided by the high Young's Modulus, around 140 GPa, of the alloy.
- Higher electrical conductivity and higher strength may be achieved, at the expense of bendability, by extending intermediate rolling or drawing to up to 98%, by thickness, and by adding one or more intermediate anneals at a temperature of from 350° C. to 900° C. for from 1 minute to 6 hours.
- a copper alloy having a nominal composition of 0.55% chromium, 0.10% silver, 0.09% iron, 0.06% titanium, 0.03% silicon, 0.03% tin and the balance copper and inevitable impurities was melted and cast into an ingot.
- the ingot was machined and hot rolled at 980° C., quenched and processed to a strip thickness of 1.1 mm.
- the strip was cut into a piece of about 300 mm in length, immersed into a molten salt bath at 950° C. for 20 seconds, and then quenched in water to room temperature (nominally 20° C.).
- the surfaces of the cut strip were milled to remove surface oxides and then cold rolled to an intermediate gauge of 0.45 mm and heat treated at 470° C. for 1 hour followed by heat treating at 390° C. for 6 hours. After that, the strip material was rolled to a final gauge of 0.3 mm and subjected to a stress relief anneal at 280° C. for two hours.
- This alloy had a QFD rating for automotive and industrial applications of 54, see Table 12 and for multimedia applications 64, see Table 11.
- the alloys were then cold rolled to a 60% reduction, by thickness, in a sequence of several passes to a thickness of 0.018′′ and then subjected to a double aging anneal consisting of a first static anneal at 470° C. for one hour followed by a second static anneal at 390° C. for six hours. This heat treatment hardened the alloys while increasing conductivity over the cold rolled values without recrystallizing the microstructure.
- the alloys were then cold rolled for a 33% reduction in thickness to 0.012′′ and given a relief anneal heat treatment of 280° C. for two hours.
- Alloys BT and BU were processed essentially the same way as alloys O and E except that the aging treatment consisted of two-stage anneal with a first stage of 470° C. for one hour and a second stage of 390° C. for six hours.
- the tensile strength and conductivity properties were measured in the as-aged condition and, as shown in Table 6, showed a decrease in stress relaxation (increase in stress relaxation resistance) with a silver addition at a 0.5% chromium level.
- TABLE 6 Amount (%) of Stress YS UTS Elong. Conductivity Relaxation at 1000 hours Alloy Ksi Ksi % % IACS 100° C. 150° C. 200° C. BT 70.1 74.8 9 79.1 2.4 4.8 10.9 BU 70.2 74.8 11 80.0 3.9 7.3 11.7
- Tables 7A and 7B show how both the composition and processing of the invention lead to improved bends.
- Table 7A when processed with a solution heat treatment (SHT) the alloy of the invention J310 had isotropic bends while the silver-free control alloy J306 had somewhat anisotropic bends.
- Control alloy K005 when processed with bell anneals (BA) with intervening cold rolling reductions, had anisotropic and poorer bends. Bend evaluation of alloys J306, J310 and K005 in Table 7A was by the mandrel method which has been found to give at least 0.5 higher bend values than by the V-block method.
- alloys K007 and K005 were processed by the steps of homogenization at between 850° C. and 1030° C. for from one to 24 hours, hot rolling at a temperature of between 600° C. and 1000° C. and then quenching at a cooling rate of between 50° C. and 1000° C. per minute. These steps were followed by cold rolling up to 99% with one or two intervening bell anneals at a temperature of 350° C. to 500° C. for up to 10 hours (conventional BA process).
- Table 7B shows that with the conventional BA process, the silver containing alloy K007 had better bends. Bend evaluation of the alloys reported in Table 7B was by the V-block method.
- Table 7B shows that better bends were obtained for alloys of the invention, K007 and K008, compared to commercial alloy K005 when both are processed either by a conventional bell anneal (BA) process or by a solution heat treatment (SHT) process. Better bend formability and isotropic values are obtained by the new process (SHT) relative to the conventional BA process.
- BA bell anneal
- SHT solution heat treatment
- the rating of the achievement should be low, e.g. 5%, at the disappointment limit. Close to the desirable property the rating should reach about 50% and should reveal a steep increase or decrease with small variations in the property measured. At the exaggeration limit the requirements are over-fulfilled. The rating should reach 95%. Further improvements can not improve customer satisfaction too much. Variations in property should only result in small variations of the rating.
- the constants c1 and c2 are calculated from the two ratings set by (x 1 ,f(x 1 )) and (x 2 ,f(x 2 )). These settings being made by decision about the suitable characteristic of the rating.
- w ( f ( x )) w ( f ( x min ))+( w ( f ( x max )) ⁇ w ( f ( x min ))) ⁇ ( f ( x ) ⁇ f ( x min ))/( f ( x max ) ⁇ f ( x min ))
- the overall rating of performance is given by a percentage with respect to a completely exaggerated 100% solution.
- the ideal solution (focus) will reveal a result of about 50%.
- the overall rating is a useful tool to compare alloys and tempers on a most objective basis. Values utilized for multimedia applications are recited in Table 8 and for automotive applications in Table 9.
- Table 10 illustrates that a copper alloy having the nominal desirable properties as recited in Table 2 has a QFD rating of 51.
- Table 11 illustrates that the copper alloy of Example 1 has a QFD value of 64 for multimedia applications and
- Table 12 illustrates the alloy has a QFD value of 54 for automotive and industrial applications.
Abstract
Description
- This patent application claims priority to U.S. Provisional Patent Application Serial No. 60/224,054 that was filed on Aug. 9, 2000. The subject matter of that provisional patent application is incorporated by reference in its entirety herein.
- 1. Field of the Invention
- This invention relates to a silver containing copper alloy. More particularly, the inclusion of a controlled amount of silver in a copper alloy that further contains chromium, titanium and silicon results in improved resistance to stress relaxation and improved isotropic bend properties without a detrimental effect on either yield strength or electrical conductivity.
- 2. Description of Related Art
- Copper alloys are formed into numerous products that take advantage of the high electrical conductivity and/or high thermal conductivity of the alloys. A partial list of such products includes electrical connectors, leadframes, wires, tubes, foils and powders that may be compacted into products. One type of electrical connector is a box-like structure formed by stamping a predefined shape from a copper alloy strip and then bending the stamped part to form the connector. It is necessary for the connector to have high strength and high electrical conductivity. In addition, the connector should have a minimal reduction in normal force as a function of time and temperature exposure, commonly referred to as resistance to stress relaxation.
- Properties important for an electrical connector include yield strength, bend formability, resistance to stress relaxation, modulus of elasticity, ultimate tensile strength and electrical conductivity.
- Target values for these properties and relative importance of the properties are dependent on the intended application of products manufactured from the subject copper alloys. The following property descriptions are generic for many intended applications, but the target values are specific for under the hood automotive applications.
- The yield strength is the stress at which a material exhibits a specified deviation, typically an offset of 0.2%, from proportionality of stress and strain. This is indicative of the stress at which plastic deformation becomes dominant with respect to elastic deformation. It is desirable for copper alloys utilized as connectors to have a yield strength on the order of 80 ksi, that is approximately 550 MPa.
- Stress relaxation becomes apparent when an external stress is applied to a metallic strip in service, such as when the strip is loaded after having been bent into a connector. The metal reacts by developing an equal and opposite internal stress. If the metal is held in a strained position, the internal stress will decrease as a function of both time and temperature. This phenomenon occurs because of the conversion of elastic strain in the metal to plastic, or permanent strain, by microplastic flow.
- Copper based electrical connectors must maintain above a threshold contact force on a mating member for prolonged times for good electrical connection. Stress relaxation reduces the contact force to below the threshold leading to an open circuit. It is a target for a copper alloy for connector applications to maintain at least 90% of the initial stress when exposed to a temperature of 150° C. for 1000 hours and to maintain 85% of the initial stress when exposed to a temperature of 200° C. for 1000 hours.
- The modulus of elasticity, also known as Young's modulus, is a measure of the rigidity or stiffness of a metal and is the ratio of stress to corresponding strain in the elastic region. Since the modulus of elasticity is a measure of the stiffness of a material, a high modulus, on the order of 150 GPa is desirable.
- Bendability determines the minimum bend radius (MBR) which identifies how severe a bend may be formed in a metallic strip without fracture along an outside radius of the bend. The MBR is an important property for connectors where different shapes are to be formed with bends at various angles.
- Bend formability may be expressed as, MBR/t, where t is the thickness of the metal strip. MBR/t is a ratio of the minimum radius of curvature of a mandrel about which the metallic strip can be bent without failure. The “mandrel” test is specified in ASTM (American Society for Testing and Materials) designation E290-92, entitledStandard Test Method for Semi-Guided Bend Test for Ductility of Metallic Materials, and is incorporated by reference in its entirety herein.
- It is desirable for the MBR/t to be substantially isotropic, a similar value in the “good way”, bend axis perpendicular to the rolling direction of the metallic strip, as well as the “bad way”, bend axis parallel to the rolling direction of the metallic strip. It is desirable for the MBR/t to be about 0.5 or less for a 90° bend and about 1 or less for a 180° bend.
- Alternatively, the bend formability for a 90° bend may be evaluated utilizing a block having a V-shaped recess and a punch with a working surface having a desired radius. In the “V-block” method, a strip of the copper alloy in the temper to be tested is disposed between the block and the punch and when the punch is driven down into the recess, the desired bend is formed in the strip.
- Related to the V-block method is the 180° “form punch” method in which a punch with a cylindrical working surface is used to shape a strip of copper alloy into a 180° bend.
- Both the V-block method and the form punch method are specified in ASTM designation B820-98, entitledStandard Test Method for Bend Test for Formability of Copper Alloy Spring Material, that is incorporated by reference in its entirety herein.
- For a given metal sample, both methods give quantifiable bendability results and either method may be utilized to determine relative bendability.
- The ultimate tensile strength is a ratio of the maximum load a strip withstands until failure during a tensile test expressed as a ratio of the maximum load to the cross-sectional area of the strip. It is desirable for the ultimate tensile strength to be about 85-90 ksi, that is approximately 585-620 MPa.
- Electrical conductivity is expressed in % IACS (International Annealed Copper Standard) in which unalloyed copper is defined as having an electrical conductivity of 100% IACS at 20° C. It is desirable for copper alloys for high performance electrical connectors to have an electrical conductivity of at least 75% IACS. More preferably, the electrical conductivity is 80% IACS or higher.
- One copper alloy that approaches the desired properties is designated by the Copper Development Association, New York, N.Y., as C18600. C18600 is an iron containing copper-chromium-zirconium alloy and is disclosed in U.S. Pat. No. 5,370,840 to Caron, et al that is incorporated by reference in its entirety herein. C18600 has a nominal composition by weight of 0.3% chromium, 0.2% zirconium, 0.5% iron, 0.2% titanium and the balance copper and inevitable impurities.
- Throughout this patent application, all percentages are expressed as weight percent unless otherwise noted.
- Mechanical and electrical properties of copper alloys are highly dependent on processing. If C18600 is subjected to an aging anneal, a 33% cold roll and a relief anneal, the alloy achieves as nominal properties: an electrical conductivity of 73% IACS; a yield strength of 90 ksi; a 90° MBR/t of 1.2 in the good way and 3.5 in the bad way utilizing the mandrel method(“roller bend” method); and a 20% loss in stress when subjected to 200° C. for 1000 hours.
- U.S. Pat. No. 4,678,637 to Duerrschnabel et al discloses a copper alloy containing additions of chromium, titanium and silicon and is incorporated by reference in its entirety herein. This alloy, designated by the CDA as C18070, has a nominal composition of 0.28% chromium, 0.06% titanium, 0.04% silicon and the balance copper and unavoidable impurities. When processed by hot rolling, quench and cold rolling interspersed with one or two intermediate bell anneals, the alloy achieves as nominal properties: an electrical conductivity of 86% IACS; a yield strength of 72 ksi (496 MPa), a 90% MBR of 1.6 t in the good way and 2.6 t in the bad way; and a loss of 32% of the stress when subjected to 200° C. for 1000 hours.
- DE 196 00 864 C2 by Wieland-Werke A G, discloses an alloy containing 0.1%-0.5% chromium, 0.01%-0.25% titanium, 0.01%-0.1% silicon, 0.02%-0.8% magnesium with the balance being copper and inevitable impurities. The magnesium addition is disclosed as improving the resistance of the alloy to stress relaxation.
- A small addition of silver, on the order of up to 25 troy ounces per ton avoirdupois (0.085 weight percent), enables cold worked copper to maintain its strength at temperatures of up to about 400° C. as disclosed inSilver-Bearing Copper by Finlay, 1968. One silver-containing copper alloy is designated by the CDA as copper alloy C15500. C15500 contains 0.027-0.10% silver, 0.04-0.08% phosphorous, 0.08-0.13% magnesium and the balance is copper and unavoidable impurities. The alloy is reported in the ASM Handbook as having an electrical conductivity of 90% IACS in an annealed condition, a yield strength of 72 ksi (496 MPa) in the spring temper. Bend formability and resistance to stress relaxation are not reported.
- While the copper alloys described above achieve some of the desired properties for connectors, there remains a need for an improved copper alloy that comes closer to the target requirements and further, there remains a need to characterize a copper alloy utilizing a holistic system that integrates multiple customer identified desired properties into a single performance indicator.
- Accordingly, it is an object of the invention to provide a copper base alloy that is particularly suited for electrical connector applications. It is a feature of the invention that this copper base alloy contains chromium, titanium and silver. Yet another feature of the invention is that iron and tin may be added to promote grain refinement and increase strength. Still another feature of the invention is to maximize desired electrical and mechanical properties by processing of the alloy including the steps of solution anneal, quench, cold roll and age. Still a further feature of the invention is that a holistic approach to alloy properties is utilized to integrate multiple alloy properties by way of factors weighted by customer derived rankings for specific connector applications.
- It is an advantage of the invention that the alloy of the invention may be processed to have a yield strength in excess of 80 ksi (550 MPa) and an electrical conductivity in excess of 80% IACS making the alloy particularly useful for forming into electrical connectors for both automotive and multimedia applications. Among the advantageous properties of the alloy of the invention are an enhanced resistance to stress relaxation at elevated temperatures of up to 200° C. A still further advantage is that a strip of metal formed from the alloy has substantially isotropic bend formability and excellent stampability making it particularly useful for forming into box-type connectors.
- In accordance with the invention, there is provided a copper alloy that consists essentially of, by weight, from 0.15% to 0.7% of chromium, from 0.005% to 0.3% of silver, from 0.01% to 0.15% of titanium, from 0.01% to 0.10% of silicon, up to 0.2% of iron, up to 0.5% of tin, and the balance is copper and inevitable impurities.
- In accordance with the invention there is provided a process for forming a copper alloy having high electrical conductivity, good resistance to stress relaxation and isotropic bend properties. This process includes the steps of casting a copper alloy that contains, by weight, from 0.15% to 0.7% of chromium, additional desired alloying additions, and the balance is copper and inevitable impurities. This copper alloy is formed into a strip that is solution annealed, by a strip anneal process, at a temperature of from 850° C. to 1030° C. for from 5 seconds to 10 minutes. A preferred strip anneal time is from 10 seconds to 5 minutes. The strip is then quenched from a temperature of at least 850° C. to a temperature of less than 500° C. in at most 10 seconds. The quenched strip is then cold rolled to a reduction of from 40% to 99% in thickness and then annealed at a temperature of between 350° C. and 550° C. for from one hour to 10 hours.
- The above stated objects, features and advantages will become more apparent from the specification and drawings that follow.
- FIG. 1 is a flow chart of processing steps for the manufacture of strip from the copper alloy of the invention.
- FIG. 2 is a flow chart of processing steps for the manufacture of wire or rod from the copper alloy of the invention.
- FIGS. 3 and 4 graphically illustrate recrystallized grain size for two related alloys of the invention as a function of solution annealing temperature and solution annealing time.
- The alloy of the invention is particularly suited for under the hood automotive applications where it may be subject to elevated ambient temperatures as well as relatively high electrical currents generating I2R heating. In addition, the alloy is useful for multimedia applications, such as computers or telephones, where the service temperature is lower, typically on the order of 100° C. maximum, and signals of relatively low electrical currents are carried.
- The alloy of the invention consists essentially of:
- from 0.15% to 0.7% chromium,
- from 0.005% to 0.3% silver,
- from 0.01% to 0.15% titanium,
- from 0.01% to 0.10% silicon,
- up to 0.2% iron,
- up to 0.5% tin, and
- the balance is copper and inevitable impurities.
- A more preferred alloy range is:
- from 0.25%-0.60% chromium,
- from 0.015%-0.2% silver,
- from 0.01%-0.10% titanium,
- from 0.01%-0.10% silicon,
- less than 0.1% iron,
- up to 0.25% tin, and
- the balance is copper and inevitable impurities.
- A most preferred alloy composition is:
- from 0.3%-0.55% chromium,
- from 0.08%-0.13% silver,
- from 0.02%-0.065% titanium,
- from 0.02%-0.08% silicon,
- 0.03%-0.09% iron,
- less than 0.05% tin, and
- the balance is copper and inevitable impurities.
- If high strength is of particularly high relative importance, then the titanium content should be 0.05% or higher. If high electrical conductivity is of particularly high relative importance, then the titanium content should be 0.065% or less.
- Chromium—Chromium particles precipitate during aging anneals thereby providing age-hardening and a concomitant conductivity increase. It is also believed that the chromium precipitate stabilizes the alloy microstructure by retarding grain growth through second phase pinning of grain boundaries. A minimum of 0.15%, by weight, of chromium is required to achieve these beneficial results.
- When the chromium content exceeds 0.7%, the maximum solid solubility limit of chromium in the copper alloy is approached and a coarse second phase precipitate develops. The coarse precipitate detrimentally affects both the surface quality and plating characteristics of the copper alloy without a further increase in the strength of the alloy. It is further believed that an excess of chromium detrimentally impacts recrystallization.
- Silver—Silver promotes isotropic bend properties thereby improving the utility of the alloy for electrical connector applications. In addition, silver increases strength, particularly when the chromium content is at the low end, 0.3% or less, of the specified ranges. When the alloy is in the aged condition, the silver addition improves resistance to elevated temperature stress relaxation.
- When the silver content is less than 0.005%, the beneficial effects are not fully realized. When the silver content exceeds 0.3%, the increased cost due to the presence of silver outweighs the benefits of its inclusion.
- Titanium—Titanium enhances stress relaxation resistance and increases the alloy strength. Below 0.01% titanium, these beneficial effects are not achieved. Excess titanium has a detrimental effect on electrical conductivity of the alloy, probably more so than any of the other alloying elements. To achieve an electrical conductivity of at least 80% IACS, the titanium content should be maintained at 0.065% or less. To achieve a high strength, the titanium content should be maintained at 0.05% or more.
- Silicon—Silicon enhances stress relaxation resistance and alloy strength. When the silicon content is less than 0.01%, the beneficial effect is not achieved. When the silicon content exceeds 0.1%, a loss in electrical conductivity outweighs any gain in stress relaxation resistance.
- Iron—Iron is an optional addition that increases the strength of the alloy and also enhances grain refinement, in both the as-cast and as-processed condition. The grain refinement improves bend formability. However, an excess of iron unduly decreases electrical conductivity. An electrical conductivity of 80% IACS is a desirable consideration, and therefore the iron should be restricted to below 0.1% in accordance with the most preferred alloy composition.
- When present, the iron to titanium ratio, by weight, is preferably between 0.7:1 and 2.5:1, and more preferably between 0.9:1 and 1.7:1 and most preferably about 1.3:1. For some embodiments, the iron to tin ratio, by weight, is preferably between 0.9:1 and 1.1:1 and more preferably about 1:1.
- Tin—Tin is an optional addition that increases the strength of the alloy, but if present in an excessive amount reduces electrical conductivity and also appears to promote stress relaxation. Accordingly, there should be less than 0.5% by weight tin present in the alloy and preferably less than 0.05% tin in the alloy when an electrical conductivity of 80% IACS is required.
- Other additions—Other elements may be present in the alloy of the invention to achieve desired property enhancements without significantly reducing desirable properties such as bend formability, resistance to stress relaxation or electrical conductivity. The total content of these other elements is, for the most part, less than 1% and preferably less 0.5%. Exceptions to this generality are recited below.
- Cobalt may be added as a 1:1, by weight, substitute for iron.
- Magnesium may be added to improve solderability and solder adhesion. Magnesium is also effective to enhance cleaning of the alloy surface during processing. A preferred magnesium content is from about 0.05% to about 0.2%. Magnesium may also improve the stress relaxation characteristics of the alloy.
- Machinability, without a significant decrease in electrical conductivity, can be enhanced by additions of sulfur, selenium, tellurium, lead or bismuth. These machinability enhancing additions form a separate phase within the alloy and do not reduce electrical conductivity. Preferred contents are up to 3% for lead, from about 0.2% to about 0.5% for sulfur and from about 0.4% to 0.7% for tellurium.
- De-oxidizers can be added in preferred amounts of from about 0.001% to about 0.1%. Suitable de-oxidizers include boron, lithium, beryllium, calcium and rare earth metals either individually or as mischmetal. Boron, that forms borides, is beneficial as it also increases the alloy strength. Magnesium, recited hereinabove, is also effective as a deoxidizer.
- Additions which increase strength, with a reduction in electrical conductivity, including aluminum and nickel, should be present in amounts of less than 0.1%.
- Zirconium has a propensity to combine with silicon and form coarse particles of zirconium silicide. Therefore, it is preferred that the alloy be essentially zirconium free, that is zirconium in impurity amounts only.
- The processing of the alloy of the invention has a significant impact on the finished gauge alloy properties. FIG. 1 illustrates in block diagram a sequence of processing steps to achieve the yield strength, bend formability, resistance to stress relaxation, modulus of elasticity, ultimate tensile strength and electrical conductivity desired for the subject copper alloy. These processing steps are believed beneficial for any chromium containing copper alloy.
- The alloy is initially cast 10 by any suitable process. For example, cathode copper may be melted at a temperature of approximately 1200° C. in a crucible or a melt furnace with a charcoal cover. Chromium, and as desired, the other alloying elements of titanium, silicon, silver and iron are then added to the melt in the form of appropriate master alloys for a casting of a desired composition. The casting may be via a continuous process, such as strip casting or belt casting, in which the casting leaves the strip or belt at a thickness suitable for
cold rolling 12 prior tosolution annealing 14. This casting thickness is preferably from about 0.4 inch to 1 inch and it is then cold rolled to a nominal thickness of about 0.045 inch. - Alternatively, the alloy may be cast10′ as a rectangular ingot and broken down into strip by hot rolling 16. Typically, hot rolling will be at a temperature of between 750° C. and 1030° C. and used to reduce the thickness of the ingot to somewhat above the solution anneal thickness. Hot rolling may be in multiple passes and generally used to form a strip having a thickness greater than that desired for solution annealing.
- While processing is described in terms of a copper alloy strip with working by hot and cold rolling, the copper alloys of the invention may also be formed into rods, wires or tubes in which instance, the working would more likely be in the form of drawing or extrusion.
- Following hot rolling16, the strip is water quenched and then trimmed and milled to remove any oxide coatings. The strip is then cold rolled 12 to solution anneal 14 gauge. Cold rolling 12 may be in a single pass or multiple passes with intermediate anneals if necessary. An intermediate anneal at a temperature of from about 400° C. to 550° C. for from about four hours to eight hours yielded, at the end of the process, a higher strength alloy with fine grains, on the order of 10 microns, and a homogenous structure. If the intermediate anneal temperature approaches full homogenization, the alloy at the end of the process has lower strength and coarse grain stringers. Omitting the intermediate anneal results in an alloy at the end of processing with a grain size in the 25 micron to 30 micron range. To enhance the recrystallized grain structure, it is preferred that the cold rolling step impart the strip with a degree of cold work, such as a 25% -90% reduction in thickness.
- The alloy is solution annealed14 at a time and temperature effective to achieve full recrystallization without excessive grain growth. Preferably, the maximum grain size is maintained at 20 microns or less. More preferably, the maximum grain size is 15 microns or less. The annealing time and temperature should further be selected to be effective to achieve microstructural homogeneity. Thus, if the annealing time or temperature is too low, hardness and microstructural deviations from one portion of the strip to the other are obtained leading to non-isotropic bend properties. Excessive annealing time or temperature leads to undue grain growth and poor bend formability. As a broad range, the
solution anneal 14 should be a strip anneal at a temperature of from 850° C. to 1030° C. for from 10 seconds to 15 minutes. More preferably, thesolution anneal 14 is at a temperature of from 900° C. to 1000° C. for from 15 seconds to ten minutes and most preferably from 930° C. to 980° C. for from 20 seconds to five minutes. - FIG. 3 graphically illustrates the effect of solution annealing (SA) time and temperature on the recrystallization and grain growth for a copper alloy having 0.40% chromium. The reported values, such as 10-15 μm, are grain size. At a temperature of 950° C., recrystallization without undue grain growth is achieved at an annealing time of from about 17 seconds to about 35 seconds. At less than 17 seconds there is limited recrystallization. In excess of 35 seconds, the alloy is fully recrystallized but grain sizes of between 20 and 25 microns are formed and when the time exceeds about 40 seconds, rapid grain growth with grains in the 30 micron up to 100 micron range are obtained.
- FIG. 4 graphically illustrates the effect of solution annealing time to temperature when the alloy contains 0.54% chromium and demonstrates how increasing the chromium content broadens the acceptable range of annealing time and temperature. Recrystallization with a grain size of 10 to 15 microns is achievable in this instance at 950° C. with times of from about 7 seconds up to about 45 seconds. However, while grain size is very well controlled, undissolved chromium particles become larger degrading alloy properties.
- Referring back to FIG. 1, the solution annealed14 alloy is next quenched 18 to retain microstructural homogeneity. Quenching should take the alloy temperature from the solution anneal temperature, minimum 850° C. and preferably in excess of 900° C., to below 500° C. in 20 seconds or less. More preferably, the quench rate is from 900° C. to less than 500° C. in 10 seconds or less.
- While multiple solutionization anneals14 effective for recrystallization may be utilized, it is preferred that there is a single solution anneal effective for recrystallization.
- Following quenching18, the alloy is cold rolled 20 to a 40% to 80%, by thickness, reduction for strip or sheet. For foil, a cold roll reduction in excess of 90%, or preferably up to 99%, in thickness, is preferred. Preferably, the strip or sheet cold rolled reduction is from 50% to 70%, by thickness, and effected with one or more passes through the rolling mill to generate a heavily cold worked strip.
- The alloy is next given an aging
heat treatment 22. The agingheat treatment 22 may be in one step, or preferably is in two steps. It has been found that step aging results in higher strength and electrical conductivity and it is believed that bend formability may also be improved by the step aging. The first aging step, and only aging step if done in a single step, is at a temperature of from about 350° C. to about 550° C. for from one to ten hours. Preferably, this first agingstep 22 is at a temperature of from 400° C. to 500° C. for from one to three hours. - If the age anneal is done in multiple steps, the
second step anneal 24 is at a temperature of from about 300° C. to about 450° C. for from one to twenty hours leading to increased electrical conductivity without a loss in strength. Preferably, the second step aging 24 is at a temperature of from about 350° C. to about 420° C. for from five to seven hours. - The alloy may be used in the age annealed condition when enhanced resistance to stress relaxation is required, for example, in automotive applications. Following the aging anneal, the alloy has a yield strength of about 68 ksi (470 MPa) and an electrical conductivity of about 80% IACS. If still higher strengths are required, additional processing steps may follow the
age anneal step - The age annealed copper alloy strip is cold rolled26 to a final gauge thickness, typically on the order of 0.25 mm to 0.35 mm, although it is a target for future connectors to have a thickness on the order of 0.15 mm (0.006 inch) or less. The thin strip material, under about 0.006 inch, is also useful as a copper alloy foil product. Generally, the
cold rolling 26 will be in one or more passes through a rolling mill with a reduction of between 10% and 50%, in thickness. - Following
cold roll 26, there may be astress relief anneal 28 at a temperature of between 200° C. and 500° C. for from 10 seconds to 10 hours. Preferably, thestress relief anneal 28 is at a temperature of between 250° C. and 350° C. for from 1 hour to 3 hours. - FIG. 2 illustrates in block diagram a process flow particularly suited for the manufacture of wire and rod. The copper alloy of the invention is cast30 by any suitable process and extruded 32 to form a rod with a desired cross-sectional shape, preferably the cross-sectional shape is circular. The hot extrusion is at a temperature of between 700° C. and 1030° C. and preferably at a temperature of between 930° C. and 1020° C.
- The extruded rod is quenched34 and then cold drawn (or cold extruded) 36 to a reduction in diameter of up to 98%. The drawn rod is then annealed 38 at a temperature of from 350° C. to 900° C. for from 1 minute up to 6 hours. The sequence of cold draw 36 and
anneal 38 may be repeated one or more additional times and then cold drawn (or cold extruded) 40 to final gauge. - While individual properties such as yield strength, resistance to stress relaxation and electrical conductivity are individually important to characterizing a copper alloy suitable for use as an electrical connector, a holistic value integrating multiple relevant properties is more useful. This holistic approach may utilize Quality Function Deployment, QFD. QFD is a methodology for developing a design quality aimed at satisfying the customer and then translating the customer's demand into design targets to be used throughout the production phase. The customer is surveyed to identify those properties most important to the customer's application and to rank the relative importance of each of those properties. The customer also identifies a range of values for each of the desired properties from a “disappointing” minimally acceptable value to “desirable” up to “exaggerated”. QFD is more fully described in two articles by Edwin B. Dean,Quality Function Deployment from the Perspective of Competitive Advantage, 1994 and Comprehensive QFD from the Perspective of Competitive Advantage, 1995. Both articles are downloadable at http://mijuno.larc.nasa.gov/dfc/qfd/cqfd.html and incorporated by reference in their entireties herein.
- Table 1 recites a list of properties, ratings and ranges for a copper alloy intended for use in automotive applications while Table 2 recites similar properties, ratings and ranges for a copper alloy for use in a multimedia application. The “rating” is on a scale of 1 to 10 with 10 meaning the property value is of utmost value while 1 meaning the property value of minimal value.
TABLE 1 AUTOMOTIVE AND INDUSTRIAL CONNECTOR Relative Disappointing Desirable Exaggerated Properties Importance Eu (5) Ei (50) Eo (95) Yield Strength 1.0 300 MPa 550 MPa 800 MPa Stress Relaxation .82 150°/1000 h .55 30% 10% 5% 200°/1000 h .27 40% 15% 5% Modulus of Elasticity .66 100 GPa 150 GPa 200 GPa Bendability .65 90°-Bend .325 1 × t 0.5 × t 0 × t with coining prior to bending 180°-Bend .325 2 × t 1 × t 0 × t Ultimate Tensile Strength .59 420 MPa 680 MPa 950 MPa Conductivity .46 40% IACS 75% IACS 90% IACS Tolerance of .46 140 MPa 50 MPa 30 MPa Yield Strength -
TABLE 2 MULTIMEDIA CONNECTORS Relative Disappointing Desirable Exaggerated Properties Importance Eu (5) Ei (50) Eo (95) Yield Strength 1.0 400 MPa 600 MPa 800 MPa Modulus of .8 90 GPa 130 GPa 180 GPa Elasticity Bendability .65 90°-Bend .325 4 × t 1 × t 0 × t 180°-Bend .325 5 × t 2 × t 0 × t Ultimate .6 500 MPa 700 MPa 950 MPa Tensile Strength Stress .5 40% 15% 5% Relaxation 100° C./1000 h Conductivity .4 3 % IACS 30% IACS 60% IACS Tolerance of .3 140 MPa 60 MPa 30 MPa Yield Strength - The copper alloys of the invention are capable of achieving a QFD value in excess of 50 (desirable) both for automotive and industrial applications and for multimedia applications indicating that a customer would find the subject copper alloy acceptable for both applications.
- While described above in terms of copper alloy strip formed into electrical connectors, the alloy and processing of the invention are equally suitable for forming into leadframes. Leadframes require good bend properties as the outer leads are bent at a 90° angle for insertion into a printed circuit board. The fine grain structure and absence of coarse particles makes the alloy amenable to uniform chemical etching, a process used in leadframe formation.
- While described above in terms of a copper alloy formed into a strip, the alloy and processing of the invention are equally suitable for forming rod, wire and sections for electrical applications. Prerequisite high stiffness is provided by the high Young's Modulus, around 140 GPa, of the alloy. Higher electrical conductivity and higher strength may be achieved, at the expense of bendability, by extending intermediate rolling or drawing to up to 98%, by thickness, and by adding one or more intermediate anneals at a temperature of from 350° C. to 900° C. for from 1 minute to 6 hours.
- The advantages of the copper alloy of the invention will become more apparent from the examples that follow.
- A copper alloy having a nominal composition of 0.55% chromium, 0.10% silver, 0.09% iron, 0.06% titanium, 0.03% silicon, 0.03% tin and the balance copper and inevitable impurities was melted and cast into an ingot. The ingot was machined and hot rolled at 980° C., quenched and processed to a strip thickness of 1.1 mm. The strip was cut into a piece of about 300 mm in length, immersed into a molten salt bath at 950° C. for 20 seconds, and then quenched in water to room temperature (nominally 20° C.). The surfaces of the cut strip were milled to remove surface oxides and then cold rolled to an intermediate gauge of 0.45 mm and heat treated at 470° C. for 1 hour followed by heat treating at 390° C. for 6 hours. After that, the strip material was rolled to a final gauge of 0.3 mm and subjected to a stress relief anneal at 280° C. for two hours.
- The final product showed the following properties:
- Yield strength=84 ksi (580 MPa);
- Modulus of elasticity=145 GPa;
- 90°
bending radius 0×t (V-block method, micrographic inspection revealed no cracks); - 180° bending radii 0.8×t (form punch method micrographic inspection revealed no cracks);
- Stress relaxation
- 6% loss of stress following 100° C. exposure for 1000 hours,
- 13% drop in stress following exposure to 150° C. for 1000 hours, and
- 22% loss of stress following 200° C. exposure for 1000 hours;
- Ultimate tensile strength 86 ksi (593 MPa); and
- Electrical conductivity 79% IACS.
- This alloy had a QFD rating for automotive and industrial applications of 54, see Table 12 and for multimedia applications 64, see Table 11.
- Seven copper alloys having the compositions identified in Table 3 were melted and cast as 10 pound ingots into steel molds. After gating, the ingots had a size of 4″×4″×1.75″. The cast ingots were heat-soaked at 950° C. for two hours and then hot rolled in six passes to a thickness of 0.50″ and water quenched. Following trimming and milling to remove oxide coating, the alloys were cold rolled to a nominal thickness of 0.045″ and solution heat-treated at 950° C. for 20 seconds in a fluidized bed furnace followed by a water quench.
- The alloys were then cold rolled to a 60% reduction, by thickness, in a sequence of several passes to a thickness of 0.018″ and then subjected to a double aging anneal consisting of a first static anneal at 470° C. for one hour followed by a second static anneal at 390° C. for six hours. This heat treatment hardened the alloys while increasing conductivity over the cold rolled values without recrystallizing the microstructure. The alloys were then cold rolled for a 33% reduction in thickness to 0.012″ and given a relief anneal heat treatment of 280° C. for two hours. As shown in Table 4, the nominal commercially favorable combination of 80 ksi yield strength and 80% IACS electrical conductivity was approached with the alloys of the invention.
TABLE 3 Cr Ti Si Ag Fe Sn J306 0.32 0.060 0.020 X X X J308 0.50 0.048 0.020 0.046 X X J310 0.53 0.057 0.015 0.10 X X O 0.3 0.06 0.03 0.1 X X E 0.3 0.06 0.03 X X X BT 0.50 0.06 0.03 0.1 0.06 0.10 BU 0.50 0.06 0.03 X 0.06 0.10 K005 0.30 0.06 0.03 X X X K007 0.40 0.05 0.04 0.10 0.07 0.04 K008 0.54 0.06 0.03 0.1 0.01 X -
TABLE 4 YS UTS Elong. Conductivity Alloy Condition Ksi Ksi % % IACS Cold Roll 62 64 2 44.7 J308 Aged 72 76 9 84.3 Relief Anneal 79 81 2 83.2 Cold Roll 62 64 2 41.8 J310 Aged 72 76 8 79.7 Relief Anneal 81 82 3 77.3 -
Alloys 0 and E were processed essentially the same way as alloys J308 and J310 except that the hot rolling began after a 1000° C. for 12 hour homogenization anneal, the solution heat treatment was 900° C. for 90 seconds in a salt bath followed by a water quench and the aging treatment was 500° C. for one hour. The tensile and conductivity properties were obtained in the as-aged condition at both 0.2 mm gauge (Process A) and at 0.3 mm gauge (Process B) and shows (Table 5) the increase in strength provided by the silver addition at a 0.3% chromium level.TABLE 5 YS UTS Elong. Conductivity Alloy Process Ksi Ksi % % IACS O A 67.6 72.1 12 78.6 E A 63.2 68.3 8 80.3 O B 66.7 71.5 11 78.1 E B 64.4 69.3 12 80.3 - Alloys BT and BU were processed essentially the same way as alloys O and E except that the aging treatment consisted of two-stage anneal with a first stage of 470° C. for one hour and a second stage of 390° C. for six hours. The tensile strength and conductivity properties were measured in the as-aged condition and, as shown in Table 6, showed a decrease in stress relaxation (increase in stress relaxation resistance) with a silver addition at a 0.5% chromium level.
TABLE 6 Amount (%) of Stress YS UTS Elong. Conductivity Relaxation at 1000 hours Alloy Ksi Ksi % % IACS 100° C. 150° C. 200° C. BT 70.1 74.8 9 79.1 2.4 4.8 10.9 BU 70.2 74.8 11 80.0 3.9 7.3 11.7 - Tables 7A and 7B show how both the composition and processing of the invention lead to improved bends. As shown in Table 7A, when processed with a solution heat treatment (SHT) the alloy of the invention J310 had isotropic bends while the silver-free control alloy J306 had somewhat anisotropic bends. Control alloy K005 when processed with bell anneals (BA) with intervening cold rolling reductions, had anisotropic and poorer bends. Bend evaluation of alloys J306, J310 and K005 in Table 7A was by the mandrel method which has been found to give at least 0.5 higher bend values than by the V-block method.
- When alloys K007 and K005 were processed by the steps of homogenization at between 850° C. and 1030° C. for from one to 24 hours, hot rolling at a temperature of between 600° C. and 1000° C. and then quenching at a cooling rate of between 50° C. and 1000° C. per minute. These steps were followed by cold rolling up to 99% with one or two intervening bell anneals at a temperature of 350° C. to 500° C. for up to 10 hours (conventional BA process). Table 7B shows that with the conventional BA process, the silver containing alloy K007 had better bends. Bend evaluation of the alloys reported in Table 7B was by the V-block method.
- Table 7B shows that better bends were obtained for alloys of the invention, K007 and K008, compared to commercial alloy K005 when both are processed either by a conventional bell anneal (BA) process or by a solution heat treatment (SHT) process. Better bend formability and isotropic values are obtained by the new process (SHT) relative to the conventional BA process.
TABLE 7A % SR YS UTS Cond. 90° MBR/ 150° C./ Alloy Process Ksi Ksi Elong. % % IACS tGW/BW 1000 h J310 SHT 81 82 3 77.3 1.2/1.2 14 J306 SHT 78 80 3 78.2 1.2/0.8 Not tested K005 BA 72 81 10 86.6 1.6/2.6 30 -
TABLE 7B % SR YS UTS Cond. 90° MBR/ 150° C./ Alloy Process Ksi Ksi Elong. % % IACS tGW/BW 1000 h K005 BA 78 84 10 84.5 1.7/4.0 Not Tested K007 BA 78 82 10 80.2 0.5/2 Not Tested K005 SHT 74 78 8 81.4 0.5/0.5 12 K008 SHT 78 81 8 81.9 0/0 15 - Calculations supporting the rating as a function of the measured value illustrate that the achievement of the requirements by different alloys or tempers should be measurable.
- For this purpose s-shaped mathematical functions can be used. The rating of the achievement should be low, e.g. 5%, at the disappointment limit. Close to the desirable property the rating should reach about 50% and should reveal a steep increase or decrease with small variations in the property measured. At the exaggeration limit the requirements are over-fulfilled. The rating should reach 95%. Further improvements can not improve customer satisfaction too much. Variations in property should only result in small variations of the rating.
- We use a scaled arc tan-function w(f(x)) for this purpose. The function is bound to a lowest (xmin) and highest value (xmax) of the property of interest. Here the ratings w(f(x)) are set to zero or 100% respectively. Between these values for the rating f(x) two points given will shape the s-function.
- f(x)=50+(100/B)·arc tan(c1·(x+c2))
- The constants c1 and c2 are calculated from the two ratings set by (x1,f(x1)) and (x2,f(x2)). These settings being made by decision about the suitable characteristic of the rating.
- w(f(x))=w(f(x min))+(w(f(x max))−w(f(x min)))·(f(x)−f(x min))/(f(x max)−f(x min))
- Where x is the actual value of the property under scrutiny. w(f(x)) gives the rating for this property.
- Holistic ratings for the entirety of properties are achieved by multiplying ratings of each property of interest with the designated value given by the QFD of its relative importance. These results are summed up and divided by the sum of all values of relative importance.
- By this, the overall rating of performance is given by a percentage with respect to a completely exaggerated 100% solution. The ideal solution (focus) will reveal a result of about 50%. The overall rating is a useful tool to compare alloys and tempers on a most objective basis. Values utilized for multimedia applications are recited in Table 8 and for automotive applications in Table 9.
TABLE 8 QFD-Calculus for Multimedia-Applications Adjusted Settings Calculated Result f f w w Constants w Property x1 (x1) X2 (x2) xmin xmax (f xmin) (f xmax) c1 c2 x (f(x)) Yield Strength 400 5 600 50 150 1000 0 100 0.03157 −600 600 50.15 (MPa) Modulus Elasticity 90 5 130 50.0001 90 220 0 100 0.1578 −130 130 48.51 (GPa) Bendability I (1) 4 5 1 50.0001 0 5 100 0 −2.105 −1 1 56.31 Bendabillty II (1) 5 5 2 50.0001 0 6 100 0 −2.105 −2 2 52.06 Ultimate Tensile 500 5 700 50.0001 300 1200 0 100 0.03157 −700 700 49.74 Strength (MPa) Stress relaxation 40 5 15 50.0001 2 70 100 0 −0.2526 −15 30 48.95 (%) Tolerance of 140 5 60 50.0001 10 100 100 0 −0.07892 −60 60 52.82 Yield Strength (MPa) Conductivity 3 5 30 50.0001 1 80 0 100 0.2338 −30 30 48.95 (% IACS) -
TABLE 9 QFD-Calculus for Automotive and Industrial Applications: Parameter Adjusted Settings Calculated Result f f w w Constants w Property x1 (x1) X2 (x2) xmin xmax (f xmin) (f xmax) c1 c2 x (f(x)) Yield Strength 300 5 550 50 150 1000 0 100 0.02526 −550 550 49.82 (MPa) Stress 10 50.0001 40 5 2 70 100 0 −0.2105 −10 10 59.04 elaxation 1 (%) Stress 15 50.0001 30 5 2 70 100 0 −0.4209 −15 15 52.36 relaxation 2 (%) Modulus of 100 5 200 95 90 220 0 100 0.1263 −150 150 49.68 Elasticity (GPa) Bendability I (1) 0 95 1 5 0 5 100 0 −12.63 −0.5 0.5 52.35 Bendablllty II (1) 2 5 0 95 0 5 100 0 −6.314 −1 1 52.0 Ultimate Tensile 420 5 680 50.0001 250 1200 0 100 0.02428 −680 680 49.72 Strength (MPa) Conductivity 40 5 75 50.0001 5 100 0 100 0.1804 −75 75 52.45 (% IACS) Tolerance of 140 5 50 50 10 200 100 0 −0.07015 −50 50 54.58 Yield Strength (MPa) - Table 10 illustrates that a copper alloy having the nominal desirable properties as recited in Table 2 has a QFD rating of 51. Table 11 illustrates that the copper alloy of Example 1 has a QFD value of 64 for multimedia applications and Table 12 illustrates the alloy has a QFD value of 54 for automotive and industrial applications.
- It is apparent that there has been provided in accordance with this invention a copper alloy characterized by high strength and high electrical conductivity that is particularly suited for electrical connector applications that fully satisfies the objects, means and advantages set forth hereinbefore. While the invention has been described in combination with specific embodiments and examples thereof, it is evident that many alternatives, modifications and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, it is intended to embrace all such alternatives, modifications and variations as fall within the spirit and broad scope of the appended claims.
TABLE 10 ACHIEVEMENT EVALUATION - MULTIMEDIA APPLICATIONS Measured Relative Perfor- Property Parameter Value Rating Importance mance Y.S. MPa 600.00 50.15 1.0 50.15 M. of E. GPa 130.00 48.51 0.8 38.81 Bend I MBR/t 1.00 56.31 0.325 18.30 Bend II MBR/t 2.00 52.06 0.325 16.92 U.T.S. MPa 700.00 49.74 0.6 29.84 S.R. % Loss at 15.00 54.03 0.5 27.02 100° C./ 1000 hour Conduct % IACS 30.00 48.95 0.4 19.58 Y.S. Tolerance MPa 60.00 52.82 0.3 15.85 Overall Performance 216.46 Maximum 425.00 Overall Rating 51 -
TABLE 11 EXAMPLE 1 ALLOY EVALUATION- MULTIMEDIA APPLICATIONS Measured Relative Property Parameter Value Rating Importance Performance Y.S. MPa 580.00 31.33 1.0 31.33 M. of E. GPa 145.00 88.70 0.8 70.96 Bend I MBR/t 0.00 100.00 0.325 32.50 Bend II MBR/t 0.80 94.85 0.325 30.83 U.T.S. MPa 593.00 6.96 0.6 4.18 S.R. % Loss at 6.00 95.72 0.5 47.86 100° C./ 1000 hour Conduct % IACS 79.00 99.94 0.4 39.98 Y.S. MPa 60.00 52.82 0.3 15.85 Tolerance Overall 273.47 Performance Maximum 425.00 Overall 64 Rating -
TABLE 12 EXAMPLE 1 ALLOY EVALUATION - AUTOMOTIVE APPLICATIONS Measured Relative Perfor- Property Parameter Value Rating Importance mance Y.S. MPa 580.00 71.76 1.0 50.15 S.R. I % Loss 13.00 36.75 0.55 38.81 150°/1000 h S.R. II % Loss 22.00 9.73 0.27 18.30 200°/1000 h M.E. GPa 145.00 49.68 0.66 16.92 Bend I MBR/t 0.00 100.00 0.325 29.84 Bend II MBR/t 0.80 82.59 0.325 27.02 U.T.S MPa 593.00 11.68 0.59 19.58 Conduct. % IACS 79.00 74.42 0.46 15.85 Y.S. MPa 50.00 54.58 0.46 25.11 Tolerance Overall 251.94 Performance Maximum 462.70 Overall Rating 54
Claims (54)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/782,019 US20040159379A1 (en) | 2000-08-09 | 2004-02-19 | Silver containing copper alloy |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US22405400P | 2000-08-09 | 2000-08-09 | |
US09/923,137 US6749699B2 (en) | 2000-08-09 | 2001-08-06 | Silver containing copper alloy |
US10/782,019 US20040159379A1 (en) | 2000-08-09 | 2004-02-19 | Silver containing copper alloy |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/923,137 Division US6749699B2 (en) | 2000-08-09 | 2001-08-06 | Silver containing copper alloy |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040159379A1 true US20040159379A1 (en) | 2004-08-19 |
Family
ID=22839111
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/923,137 Expired - Lifetime US6749699B2 (en) | 2000-08-09 | 2001-08-06 | Silver containing copper alloy |
US10/782,019 Abandoned US20040159379A1 (en) | 2000-08-09 | 2004-02-19 | Silver containing copper alloy |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/923,137 Expired - Lifetime US6749699B2 (en) | 2000-08-09 | 2001-08-06 | Silver containing copper alloy |
Country Status (16)
Country | Link |
---|---|
US (2) | US6749699B2 (en) |
EP (1) | EP1179606B1 (en) |
JP (2) | JP2002180159A (en) |
KR (1) | KR100842726B1 (en) |
CN (2) | CN101012519A (en) |
AT (1) | ATE252651T1 (en) |
AU (1) | AU2001284756A1 (en) |
CA (1) | CA2416574C (en) |
DE (1) | DE60101026T2 (en) |
ES (1) | ES2204790T3 (en) |
HK (1) | HK1042732B (en) |
HU (2) | HU227988B1 (en) |
MX (1) | MXPA03000958A (en) |
PL (1) | PL196643B1 (en) |
TW (1) | TWI237665B (en) |
WO (1) | WO2002012583A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1649950A2 (en) * | 2004-10-22 | 2006-04-26 | Outokumpu Copper Products Oy | Method for manufacturing copper alloys |
US20130224070A1 (en) * | 2012-02-24 | 2013-08-29 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Copper alloy |
CN104561487A (en) * | 2015-01-23 | 2015-04-29 | 海安县恒昌金属压延有限公司 | Thermomechanical treatment process for rare earth zinc-copper-titanium alloy strip |
Families Citing this family (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6835655B1 (en) | 2001-11-26 | 2004-12-28 | Advanced Micro Devices, Inc. | Method of implanting copper barrier material to improve electrical performance |
US6703307B2 (en) | 2001-11-26 | 2004-03-09 | Advanced Micro Devices, Inc. | Method of implantation after copper seed deposition |
US6703308B1 (en) | 2001-11-26 | 2004-03-09 | Advanced Micro Devices, Inc. | Method of inserting alloy elements to reduce copper diffusion and bulk diffusion |
US7696092B2 (en) * | 2001-11-26 | 2010-04-13 | Globalfoundries Inc. | Method of using ternary copper alloy to obtain a low resistance and large grain size interconnect |
US6861349B1 (en) | 2002-05-15 | 2005-03-01 | Advanced Micro Devices, Inc. | Method of forming an adhesion layer with an element reactive with a barrier layer |
AU2003272276A1 (en) * | 2002-09-13 | 2004-04-30 | Olin Corporation | Age-hardening copper-base alloy and processing |
JP2004353011A (en) * | 2003-05-27 | 2004-12-16 | Ykk Corp | Electrode material and manufacturing method therefor |
US7169706B2 (en) * | 2003-10-16 | 2007-01-30 | Advanced Micro Devices, Inc. | Method of using an adhesion precursor layer for chemical vapor deposition (CVD) copper deposition |
CN1293212C (en) * | 2004-02-23 | 2007-01-03 | 西安交通大学 | Alloy of copper |
JP4524471B2 (en) * | 2004-08-30 | 2010-08-18 | Dowaメタルテック株式会社 | Copper alloy foil and manufacturing method thereof |
DE102007001525A1 (en) * | 2007-01-10 | 2008-07-17 | Gustav Klauke Gmbh | Cable lug, has pipe section-outer surface with point angle that amounts to preset degree, where lug is made of copper material, which exhibits chromium, silver, iron, and titanium as alloy element, and is nickel-plated |
KR100797682B1 (en) * | 2007-02-07 | 2008-01-23 | 삼성전기주식회사 | Method for manufacturing printed circuit board |
WO2009057697A1 (en) * | 2007-11-01 | 2009-05-07 | The Furukawa Electric Co., Ltd. | Conductor material for electronic device and electric wire for wiring using the same |
WO2011024909A1 (en) * | 2009-08-28 | 2011-03-03 | 古河電気工業株式会社 | Copper material for use in a sputtering target, and manufacturing method therefor |
CN102482768B (en) * | 2009-09-18 | 2014-03-12 | 古河电气工业株式会社 | Copper material for use as sputtering target and process for producing same |
US20110123643A1 (en) * | 2009-11-24 | 2011-05-26 | Biersteker Robert A | Copper alloy enclosures |
CN101724798B (en) * | 2009-12-22 | 2011-04-20 | 浙江大学 | Multiplex heat treatment method for Cu-12 percent Fe alloy |
KR101185548B1 (en) * | 2010-02-24 | 2012-09-24 | 주식회사 풍산 | Copper alloy having high strength and high conductivity, and method for manufacture the same |
CN101812651A (en) * | 2010-04-15 | 2010-08-25 | 中南大学 | Method for refining grains of precipitation- or dispersion-strengthened copper alloy plate strip |
US8821655B1 (en) * | 2010-12-02 | 2014-09-02 | Fisk Alloy Inc. | High strength, high conductivity copper alloys and electrical conductors made therefrom |
JP5818724B2 (en) * | 2011-03-29 | 2015-11-18 | 株式会社神戸製鋼所 | Copper alloy material for electric and electronic parts, copper alloy material for plated electric and electronic parts |
KR101914322B1 (en) * | 2011-08-29 | 2018-11-01 | 후루카와 덴키 고교 가부시키가이샤 | Copper alloy material and manufacturing method thereof |
CN102383078B (en) * | 2011-11-10 | 2013-07-24 | 中色(宁夏)东方集团有限公司 | Preparation method of high-strength and high-conductivity beryllium copper alloy |
JP6265582B2 (en) * | 2011-12-22 | 2018-01-24 | 古河電気工業株式会社 | Copper alloy material and method for producing the same |
JP5840235B2 (en) * | 2012-07-02 | 2016-01-06 | 古河電気工業株式会社 | Copper alloy wire and method for producing the same |
JP5470483B1 (en) * | 2012-10-22 | 2014-04-16 | Jx日鉱日石金属株式会社 | Copper alloy sheet with excellent conductivity and stress relaxation properties |
JP5525101B2 (en) * | 2012-10-22 | 2014-06-18 | Jx日鉱日石金属株式会社 | Copper alloy sheet with excellent conductivity and stress relaxation properties |
JP5718426B2 (en) * | 2012-10-31 | 2015-05-13 | 古河電気工業株式会社 | Copper foil, negative electrode for non-aqueous electrolyte secondary battery, and non-aqueous electrolyte secondary battery |
JP5952726B2 (en) * | 2012-12-10 | 2016-07-13 | 株式会社神戸製鋼所 | Copper alloy |
CN103805802A (en) * | 2014-01-09 | 2014-05-21 | 东莞市共民实业有限公司 | Copper-silver alloy for ultra-fine copper enameled wire and production process thereof |
DE102014018061A1 (en) * | 2014-12-05 | 2016-06-09 | Wieland-Werke Ag | Metallic composite and manufacturing process |
CN104502166A (en) * | 2014-12-15 | 2015-04-08 | 首钢总公司 | Method of preparing sample wafer capable of representing grain sliding of steel and iron materials |
JP6611222B2 (en) * | 2015-02-24 | 2019-11-27 | 株式会社神戸製鋼所 | Copper alloy plate for electric and electronic parts having high strength, high conductivity and excellent stress relaxation characteristics, and method for producing the same |
JP6359758B2 (en) | 2015-03-23 | 2018-07-18 | 株式会社東芝 | Permanent magnets, motors, and generators |
JP2016211054A (en) * | 2015-05-12 | 2016-12-15 | 株式会社神戸製鋼所 | Copper alloy |
CN105349819B (en) * | 2015-11-26 | 2017-11-28 | 山西春雷铜材有限责任公司 | A kind of preparation method of copper alloy with high strength and high conductivity strip |
CN107716885B (en) * | 2016-08-12 | 2019-09-10 | 北京科技大学 | A kind of copper alloy with high strength and high conductivity band short-flow production method |
KR102075199B1 (en) * | 2017-03-31 | 2020-02-07 | 주식회사 솔루에타 | Method for Manufacturing Copper Alloy and Ultra Thin Foil Using the Same |
CN107377657A (en) * | 2017-06-14 | 2017-11-24 | 绍兴市力博电气有限公司 | A kind of pole coil copper material and its production method |
KR102437192B1 (en) | 2017-08-10 | 2022-08-26 | 다나카 기킨조쿠 고교 가부시키가이샤 | High-strength and high-conductivity copper alloy plate and its manufacturing method |
CN107755451B (en) * | 2017-09-30 | 2019-02-12 | 重庆鸽牌电线电缆有限公司 | The preparation method of large capacity phase modifier argentiferous copper bar |
CN107739878B (en) * | 2017-11-23 | 2019-10-18 | 全南晶环科技有限责任公司 | A kind of anti-softening copper alloy of high-strength highly-conductive and preparation method thereof |
CN109226323A (en) * | 2018-09-11 | 2019-01-18 | 安徽楚江科技新材料股份有限公司 | A kind of cold rolling heat treatment process of tab copper strips |
EP3699958A1 (en) * | 2019-02-20 | 2020-08-26 | Infineon Technologies AG | Electronic chip reliably mounted with compressive strain |
EP3953495A4 (en) * | 2019-04-12 | 2022-12-21 | Materion Corporation | Copper alloys with high strength and high conductivity, and processes for making such copper alloys |
CN111014286B (en) * | 2019-12-12 | 2022-04-26 | 西安圣泰金属材料有限公司 | Preparation method of titanium alloy wire with high torsion performance based on texture regulation |
CN111118335B (en) * | 2020-01-17 | 2022-04-08 | 河北中泊防爆工具集团股份有限公司 | Titanium bronze alloy material and preparation method and application thereof |
CN111690838B (en) * | 2020-06-22 | 2021-10-15 | 宁波金田铜业(集团)股份有限公司 | Easily-wound transformer-used red copper strip and preparation method thereof |
CN111996411B (en) * | 2020-07-15 | 2021-11-30 | 宁波博威合金板带有限公司 | High-strength high-conductivity copper alloy material and preparation method and application thereof |
CN112322917A (en) * | 2020-10-16 | 2021-02-05 | 山西春雷铜材有限责任公司 | Preparation method of Cu-Cr-Si-Ti copper alloy plate strip |
CN112680623A (en) * | 2021-01-08 | 2021-04-20 | 北京中超伟业信息安全技术股份有限公司 | Low-radiation high-strength high-conductivity copper alloy wire and preparation method and application thereof |
CN113913642B (en) * | 2021-09-26 | 2022-07-05 | 宁波博威合金板带有限公司 | Copper alloy strip and preparation method thereof |
CN114507830A (en) * | 2022-01-20 | 2022-05-17 | 浙江力博实业股份有限公司 | Manufacturing method of high-strength high-conductivity copper-chromium-silver alloy |
CN115125413B (en) * | 2022-06-30 | 2023-08-01 | 宁波金田铜业(集团)股份有限公司 | Copper alloy strip with excellent comprehensive performance and preparation method thereof |
CN115171973B (en) * | 2022-06-30 | 2023-03-03 | 上海超导科技股份有限公司 | Copper-silver alloy reinforced superconducting tape, reinforcing method and superconducting coil |
Citations (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2033709A (en) * | 1935-02-08 | 1936-03-10 | Westinghouse Electric & Mfg Co | Copper alloys |
US2127596A (en) * | 1937-06-15 | 1938-08-23 | Mallory & Co Inc P R | Alloy |
US3677745A (en) * | 1969-02-24 | 1972-07-18 | Cooper Range Co | Copper base composition |
US3778318A (en) * | 1969-02-24 | 1973-12-11 | Cooper Range Co | Copper base composition |
US4362579A (en) * | 1979-12-25 | 1982-12-07 | Nihon Kogyo Kabushiki Kaisha | High-strength-conductivity copper alloy |
US4605532A (en) * | 1984-08-31 | 1986-08-12 | Olin Corporation | Copper alloys having an improved combination of strength and conductivity |
US4612166A (en) * | 1985-10-15 | 1986-09-16 | Olin Corporation | Copper-silicon-tin alloys having improved cleanability |
US4678637A (en) * | 1985-07-31 | 1987-07-07 | Weiland-Werke Ag | Copper-chromium-titanium-silicon alloy and application thereof |
US4810468A (en) * | 1986-10-17 | 1989-03-07 | Wieland-Werke Ag | Copper-chromium-titanium-silicon-alloy |
US4886641A (en) * | 1987-04-28 | 1989-12-12 | Mitsubishi Kinzoku Kabushiki Kaisha | Electrical contact spring material made of copper base alloy of high strength and toughness with reduced anisotropy in characteristics |
US5004520A (en) * | 1987-03-04 | 1991-04-02 | Nippon Mining Co., Ltd. | Method of manufacturing film carrier |
US5024814A (en) * | 1989-02-21 | 1991-06-18 | Mitsubishi Shindoh Co., Ltd. | Copper alloy having excellent hot rollability and excellent adhesion strength of plated surface thereof when heated |
US5032358A (en) * | 1989-05-09 | 1991-07-16 | Outokumpu Oy | Resistance welding electrode of chalcogene bearing copper alloy |
US5147469A (en) * | 1990-11-15 | 1992-09-15 | Dowa Mining Co. Ltd. | Process for producing copper-based alloys having high strength and high electric conductivity |
US5306465A (en) * | 1992-11-04 | 1994-04-26 | Olin Corporation | Copper alloy having high strength and high electrical conductivity |
US5315152A (en) * | 1990-05-31 | 1994-05-24 | Kabushiki Kaisha Toshiba | Lead frame with improved adhesiveness property against plastic and plastic sealing type semiconductor packaging using said lead frame |
US5370840A (en) * | 1992-11-04 | 1994-12-06 | Olin Corporation | Copper alloy having high strength and high electrical conductivity |
US5486244A (en) * | 1992-11-04 | 1996-01-23 | Olin Corporation | Process for improving the bend formability of copper alloys |
US5833920A (en) * | 1996-02-20 | 1998-11-10 | Mitsubishi Denki Kabushiki Kaisha | Copper alloy for electronic parts, lead-frame, semiconductor device and connector |
Family Cites Families (34)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5751253A (en) | 1980-09-11 | 1982-03-26 | Kobe Steel Ltd | Manufacture of copper alloy with high electric conductivity |
JPS59193233A (en) | 1983-04-15 | 1984-11-01 | Toshiba Corp | Copper alloy |
JPS60218440A (en) | 1984-04-13 | 1985-11-01 | Furukawa Electric Co Ltd:The | Copper alloy for lead frame |
JPS61183426A (en) | 1985-02-06 | 1986-08-16 | Furukawa Electric Co Ltd:The | High strength, highly conductive heat resisting copper alloy |
JPS6250426A (en) | 1985-08-29 | 1987-03-05 | Furukawa Electric Co Ltd:The | Copper alloy for electronic appliance |
JPS62133050A (en) | 1985-12-03 | 1987-06-16 | Nippon Mining Co Ltd | Manufacture of high strength and high conductivity copper-base alloy |
JPS62182240A (en) | 1986-02-06 | 1987-08-10 | Furukawa Electric Co Ltd:The | Conductive high-tensile copper alloy |
JPH0768597B2 (en) | 1986-02-28 | 1995-07-26 | 株式会社東芝 | Non-magnetic spring material and manufacturing method thereof |
JPS6338561A (en) | 1986-08-05 | 1988-02-19 | Furukawa Electric Co Ltd:The | Manufacture of copper alloy for lead of electronic appliance |
JPS63130739A (en) | 1986-11-20 | 1988-06-02 | Nippon Mining Co Ltd | High strength and high conductivity copper alloy for semiconductor device lead material or conductive spring material |
JPH07109016B2 (en) | 1987-06-10 | 1995-11-22 | 古河電気工業株式会社 | Copper alloy for flexible printing |
JPH0830234B2 (en) | 1987-07-24 | 1996-03-27 | 古河電気工業株式会社 | High strength and high conductivity copper alloy |
JPH01198439A (en) | 1988-02-01 | 1989-08-10 | Furukawa Electric Co Ltd:The | Lead material for plastic-pin-grid-array ic |
JPH02163331A (en) | 1988-12-15 | 1990-06-22 | Nippon Mining Co Ltd | High strength and high conductivity copper alloy having excellent adhesion for oxidized film |
JPH0372045A (en) | 1989-08-14 | 1991-03-27 | Nippon Mining Co Ltd | High strength and high conductivity copper alloy having excellent adhesion for oxidized film |
JPH03188247A (en) | 1989-12-14 | 1991-08-16 | Nippon Mining Co Ltd | Production of high strength and high conductivity copper alloy excellent in bendability |
JPH0463864A (en) * | 1990-07-03 | 1992-02-28 | Unitika Ltd | Resin composition |
JPH04221031A (en) | 1990-12-21 | 1992-08-11 | Nikko Kyodo Co Ltd | High strength and high thermal conductivity copper alloy for die for plastic molding and its manufacture |
JPH07258775A (en) * | 1994-03-22 | 1995-10-09 | Nikko Kinzoku Kk | High tensile strength and high conductivity copper alloy for electronic equipment |
JP3467711B2 (en) | 1995-07-06 | 2003-11-17 | 同和鉱業株式会社 | Copper based alloy casting method |
DE19600864C2 (en) | 1996-01-12 | 2000-02-10 | Wieland Werke Ag | Use of a copper-chrome-titanium-silicon-magnesium alloy |
JPH09263864A (en) | 1996-03-26 | 1997-10-07 | Kobe Steel Ltd | Copper alloy excellent in electric-discharge wear resistance |
JP3769695B2 (en) * | 1996-05-23 | 2006-04-26 | 同和鉱業株式会社 | Copper alloy for lead frame and manufacturing method thereof |
US5820701A (en) * | 1996-11-07 | 1998-10-13 | Waterbury Rolling Mills, Inc. | Copper alloy and process for obtaining same |
JPH1180863A (en) | 1997-09-10 | 1999-03-26 | Kobe Steel Ltd | Copper alloy excellent in stress relaxation resistance and spring property |
JPH11199954A (en) * | 1998-01-20 | 1999-07-27 | Kobe Steel Ltd | Copper alloy for electrical and electronic part |
JP3748709B2 (en) | 1998-04-13 | 2006-02-22 | 株式会社神戸製鋼所 | Copper alloy sheet excellent in stress relaxation resistance and method for producing the same |
JP3733548B2 (en) | 1998-05-19 | 2006-01-11 | 同和鉱業株式会社 | Method for producing a copper-based alloy having excellent stress relaxation resistance |
JP3807475B2 (en) * | 1998-07-08 | 2006-08-09 | 株式会社神戸製鋼所 | Copper alloy plate for terminal and connector and manufacturing method thereof |
JP3846664B2 (en) * | 1998-08-21 | 2006-11-15 | 株式会社神戸製鋼所 | Copper alloy plate for contact parts where ON / OFF of electric circuit is repeated |
JP3800279B2 (en) | 1998-08-31 | 2006-07-26 | 株式会社神戸製鋼所 | Copper alloy sheet with excellent press punchability |
JP2000080428A (en) | 1998-08-31 | 2000-03-21 | Kobe Steel Ltd | Copper alloy sheet excellent in bendability |
US6471792B1 (en) | 1998-11-16 | 2002-10-29 | Olin Corporation | Stress relaxation resistant brass |
US6241831B1 (en) | 1999-06-07 | 2001-06-05 | Waterbury Rolling Mills, Inc. | Copper alloy |
-
2001
- 2001-08-06 US US09/923,137 patent/US6749699B2/en not_active Expired - Lifetime
- 2001-08-07 HU HU0300498A patent/HU227988B1/en unknown
- 2001-08-07 AU AU2001284756A patent/AU2001284756A1/en not_active Abandoned
- 2001-08-07 CN CNA2007100054340A patent/CN101012519A/en active Pending
- 2001-08-07 MX MXPA03000958A patent/MXPA03000958A/en active IP Right Grant
- 2001-08-07 CA CA2416574A patent/CA2416574C/en not_active Expired - Lifetime
- 2001-08-07 CN CNB018130291A patent/CN1302145C/en not_active Expired - Lifetime
- 2001-08-07 PL PL365670A patent/PL196643B1/en unknown
- 2001-08-07 HU HU0600421A patent/HU228707B1/en unknown
- 2001-08-07 KR KR1020037001373A patent/KR100842726B1/en active IP Right Grant
- 2001-08-07 WO PCT/US2001/024854 patent/WO2002012583A1/en active Application Filing
- 2001-08-08 AT AT01119160T patent/ATE252651T1/en not_active IP Right Cessation
- 2001-08-08 DE DE60101026T patent/DE60101026T2/en not_active Expired - Lifetime
- 2001-08-08 JP JP2001275764A patent/JP2002180159A/en active Pending
- 2001-08-08 EP EP01119160A patent/EP1179606B1/en not_active Expired - Lifetime
- 2001-08-08 TW TW090119333A patent/TWI237665B/en not_active IP Right Cessation
- 2001-08-08 ES ES01119160T patent/ES2204790T3/en not_active Expired - Lifetime
-
2002
- 2002-06-17 HK HK02104488.9A patent/HK1042732B/en not_active IP Right Cessation
-
2004
- 2004-02-19 US US10/782,019 patent/US20040159379A1/en not_active Abandoned
-
2007
- 2007-10-15 JP JP2007268003A patent/JP5847987B2/en not_active Expired - Lifetime
Patent Citations (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2033709A (en) * | 1935-02-08 | 1936-03-10 | Westinghouse Electric & Mfg Co | Copper alloys |
US2127596A (en) * | 1937-06-15 | 1938-08-23 | Mallory & Co Inc P R | Alloy |
US3677745A (en) * | 1969-02-24 | 1972-07-18 | Cooper Range Co | Copper base composition |
US3778318A (en) * | 1969-02-24 | 1973-12-11 | Cooper Range Co | Copper base composition |
US4362579A (en) * | 1979-12-25 | 1982-12-07 | Nihon Kogyo Kabushiki Kaisha | High-strength-conductivity copper alloy |
US4605532A (en) * | 1984-08-31 | 1986-08-12 | Olin Corporation | Copper alloys having an improved combination of strength and conductivity |
US4678637A (en) * | 1985-07-31 | 1987-07-07 | Weiland-Werke Ag | Copper-chromium-titanium-silicon alloy and application thereof |
US4612166A (en) * | 1985-10-15 | 1986-09-16 | Olin Corporation | Copper-silicon-tin alloys having improved cleanability |
US4810468A (en) * | 1986-10-17 | 1989-03-07 | Wieland-Werke Ag | Copper-chromium-titanium-silicon-alloy |
US5004520A (en) * | 1987-03-04 | 1991-04-02 | Nippon Mining Co., Ltd. | Method of manufacturing film carrier |
US4886641A (en) * | 1987-04-28 | 1989-12-12 | Mitsubishi Kinzoku Kabushiki Kaisha | Electrical contact spring material made of copper base alloy of high strength and toughness with reduced anisotropy in characteristics |
US5024814A (en) * | 1989-02-21 | 1991-06-18 | Mitsubishi Shindoh Co., Ltd. | Copper alloy having excellent hot rollability and excellent adhesion strength of plated surface thereof when heated |
US5032358A (en) * | 1989-05-09 | 1991-07-16 | Outokumpu Oy | Resistance welding electrode of chalcogene bearing copper alloy |
US5315152A (en) * | 1990-05-31 | 1994-05-24 | Kabushiki Kaisha Toshiba | Lead frame with improved adhesiveness property against plastic and plastic sealing type semiconductor packaging using said lead frame |
US5147469A (en) * | 1990-11-15 | 1992-09-15 | Dowa Mining Co. Ltd. | Process for producing copper-based alloys having high strength and high electric conductivity |
US5306465A (en) * | 1992-11-04 | 1994-04-26 | Olin Corporation | Copper alloy having high strength and high electrical conductivity |
US5370840A (en) * | 1992-11-04 | 1994-12-06 | Olin Corporation | Copper alloy having high strength and high electrical conductivity |
US5486244A (en) * | 1992-11-04 | 1996-01-23 | Olin Corporation | Process for improving the bend formability of copper alloys |
US5565045A (en) * | 1992-11-04 | 1996-10-15 | Olin Corporation | Copper base alloys having improved bend formability |
US5601665A (en) * | 1992-11-04 | 1997-02-11 | Olin Corporation | Process for improving the bend formability of copper alloys |
US5833920A (en) * | 1996-02-20 | 1998-11-10 | Mitsubishi Denki Kabushiki Kaisha | Copper alloy for electronic parts, lead-frame, semiconductor device and connector |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1649950A2 (en) * | 2004-10-22 | 2006-04-26 | Outokumpu Copper Products Oy | Method for manufacturing copper alloys |
EP1649950A3 (en) * | 2004-10-22 | 2008-02-27 | Luvata Oy | Method for manufacturing copper alloys |
US20130224070A1 (en) * | 2012-02-24 | 2013-08-29 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Copper alloy |
US9121084B2 (en) * | 2012-02-24 | 2015-09-01 | Kobe Steel, Ltd. | Copper alloy |
CN104561487A (en) * | 2015-01-23 | 2015-04-29 | 海安县恒昌金属压延有限公司 | Thermomechanical treatment process for rare earth zinc-copper-titanium alloy strip |
Also Published As
Publication number | Publication date |
---|---|
HK1042732A1 (en) | 2002-08-23 |
JP2008057046A (en) | 2008-03-13 |
ATE252651T1 (en) | 2003-11-15 |
EP1179606A2 (en) | 2002-02-13 |
WO2002012583A1 (en) | 2002-02-14 |
EP1179606A3 (en) | 2002-08-14 |
CN1455823A (en) | 2003-11-12 |
MXPA03000958A (en) | 2004-08-02 |
CA2416574A1 (en) | 2002-02-14 |
US20020039542A1 (en) | 2002-04-04 |
HU0600421D0 (en) | 2006-07-28 |
AU2001284756A1 (en) | 2002-02-18 |
HU228707B1 (en) | 2013-05-28 |
PL196643B1 (en) | 2008-01-31 |
DE60101026D1 (en) | 2003-11-27 |
KR100842726B1 (en) | 2008-07-01 |
PL365670A1 (en) | 2005-01-10 |
CA2416574C (en) | 2011-05-31 |
DE60101026T2 (en) | 2004-04-22 |
HU227988B1 (en) | 2012-07-30 |
EP1179606B1 (en) | 2003-10-22 |
ES2204790T3 (en) | 2004-05-01 |
HUP0300498A3 (en) | 2005-04-28 |
HK1042732B (en) | 2004-04-23 |
TWI237665B (en) | 2005-08-11 |
HUP0300498A2 (en) | 2003-09-29 |
CN1302145C (en) | 2007-02-28 |
KR20030031139A (en) | 2003-04-18 |
CN101012519A (en) | 2007-08-08 |
JP2002180159A (en) | 2002-06-26 |
JP5847987B2 (en) | 2016-01-27 |
US6749699B2 (en) | 2004-06-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6749699B2 (en) | Silver containing copper alloy | |
US7182823B2 (en) | Copper alloy containing cobalt, nickel and silicon | |
US20040166017A1 (en) | Age-hardening copper-base alloy and processing | |
KR101211984B1 (en) | Cu-ni-si-based alloy for electronic material | |
EP0175183A1 (en) | Copper alloys having an improved combination of strength and conductivity | |
JP3962751B2 (en) | Copper alloy sheet for electric and electronic parts with bending workability | |
JP2002180165A (en) | Copper based alloy having excellent press blanking property and its production method | |
JP2008081846A (en) | High-conductivity, stress relaxation-resistant beryllium-nickel-copper lean-alloy | |
JP3797882B2 (en) | Copper alloy sheet with excellent bending workability | |
US6241831B1 (en) | Copper alloy | |
US5853505A (en) | Iron modified tin brass | |
US5882442A (en) | Iron modified phosphor-bronze | |
JP2001032029A (en) | Copper alloy excellent in stress relaxation resistance, and its manufacture | |
JP7374904B2 (en) | copper-zinc alloy | |
KR20150034078A (en) | Copper alloy plate, and electronic component for high current and electronic component for radiating heat each having the same | |
US20030029532A1 (en) | Nickel containing high copper alloy | |
JPH09143597A (en) | Copper alloy for lead frame and its production | |
JPS6141751A (en) | Manufacture of copper alloy material for lead frame |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: GLOBAL METALS, LLC, ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OLIN CORPORATION;REEL/FRAME:020125/0985 Effective date: 20071119 Owner name: GLOBAL METALS, LLC,ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:OLIN CORPORATION;REEL/FRAME:020125/0985 Effective date: 20071119 |
|
AS | Assignment |
Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:GLOBAL MARKET;REEL/FRAME:020143/0178 Effective date: 20071119 Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:GLOBAL MARKET;REEL/FRAME:020143/0178 Effective date: 20071119 |
|
AS | Assignment |
Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION, NEW YORK Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE CONVEYING PARTY NAME FROM GLOBAL MARKET, LLC TO GLOBAL METALS, LLC PREVIOUSLY RECORDED ON REEL 020143 FRAME 0178;ASSIGNOR:GLOBAL METALS, LLC;REEL/FRAME:020156/0265 Effective date: 20071119 Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION,NEW YORK Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE CONVEYING PARTY NAME FROM GLOBAL MARKET, LLC TO GLOBAL METALS, LLC PREVIOUSLY RECORDED ON REEL 020143 FRAME 0178. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT;ASSIGNOR:GLOBAL METALS, LLC;REEL/FRAME:020156/0265 Effective date: 20071119 Owner name: WACHOVIA BANK, NATIONAL ASSOCIATION, NEW YORK Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE CONVEYING PARTY NAME FROM GLOBAL MARKET, LLC TO GLOBAL METALS, LLC PREVIOUSLY RECORDED ON REEL 020143 FRAME 0178. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY AGREEMENT;ASSIGNOR:GLOBAL METALS, LLC;REEL/FRAME:020156/0265 Effective date: 20071119 Owner name: KPS CAPITAL FINANCE MANAGEMENT, LLC, NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:GLOBAL METALS, LLC;REEL/FRAME:020196/0073 Effective date: 20071119 Owner name: KPS CAPITAL FINANCE MANAGEMENT, LLC,NEW YORK Free format text: SECURITY AGREEMENT;ASSIGNOR:GLOBAL METALS, LLC;REEL/FRAME:020196/0073 Effective date: 20071119 |
|
AS | Assignment |
Owner name: GBC METALS, LLC, ILLINOIS Free format text: CHANGE OF NAME;ASSIGNOR:GLOBAL METALS, LLC;REEL/FRAME:020741/0549 Effective date: 20071213 Owner name: GBC METALS, LLC,ILLINOIS Free format text: CHANGE OF NAME;ASSIGNOR:GLOBAL METALS, LLC;REEL/FRAME:020741/0549 Effective date: 20071213 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |
|
AS | Assignment |
Owner name: GLOBAL METALS, LLC, ILLINOIS Free format text: RELEASE OF SECURITY INTEREST RECORDED AT REEL/FRAME 20143/0178;ASSIGNOR:WELLS FARGO BANK, NATIONAL ASSOCIATION, AS AGENT, SUCCESSOR BY MERGER TO WACHOVIA BANK, NATIONAL ASSOCIATION, AS AGENT;REEL/FRAME:039394/0201 Effective date: 20160718 |