CA2069363C - Thermal annealing of palladium alloys - Google Patents
Thermal annealing of palladium alloysInfo
- Publication number
- CA2069363C CA2069363C CA002069363A CA2069363A CA2069363C CA 2069363 C CA2069363 C CA 2069363C CA 002069363 A CA002069363 A CA 002069363A CA 2069363 A CA2069363 A CA 2069363A CA 2069363 C CA2069363 C CA 2069363C
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- Prior art keywords
- alloy
- nickel
- plated
- temperature
- palladium
- Prior art date
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R4/00—Electrically-conductive connections between two or more conductive members in direct contact, i.e. touching one another; Means for effecting or maintaining such contact; Electrically-conductive connections having two or more spaced connecting locations for conductors and using contact members penetrating insulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
Abstract
This invention is concerned with production of electrical devices comprising an electrodeposited conductive region free from cracking defects. In the production of a contact portion of the device from a metal strip electroplated with a conductive stripe of an alloy, the stripe exhibited, upon stamping and forrning operation, cracked areas. Typically, the stripe coating on the metal strip, such as a copper bronze material, includes a layer of nickel, a layer of palladium alloyed with nickel, cobalt, arsenic or silver, and a flash coating of hard gold. The cracking defects were eliminated by subjecting the plated strip to an annealing treatment prior to the stamping and forming operation. After the heat-treatment, the stripe was free from cracks and separations between the successive layers.
Description
, THERMAL ANNEALING OF PALLADIUM ALLOYS
Technical Field The invention is concerned with electroplated palla(lil1m alloys, especially electroplated as stripe-on-strip, for use in the fabrication of contacts in 5 electrical devices.
Back~round of the Invention Palladium and palladium alloys are used in a number of applir~tion~
because of their chemical inertness, hardness, excellent wearability, bright finish and high electrical conductivity. In addition, they do not form oxide surface coatings 10 that might increase surface contact resistance. Particularly attractive is the use of palladium alloys as electrical contact surfaces in the electrical arts such as in electrical connectors, relay contacts, switches, etc.
Electrical contact manufacture advantageously employs a "stripe-on-strip" processing. A metal strip, typically a copper bron~ material, is coated with a 15 stripe of a metal. To reduce an expense of precious metals the stripe is produced only on those portions of the strip which when subsequently formed into an electrical connector will be subjected to extended wear and requires superior electrical connection characteristics. Following the coating application, the metal strip is subjected to stamping and forming operations.
The process of coating the strip with a stripe of contact m~teri~l can be performed in several ways including an inlaying method and an electroplating method. The inlaying method calls for metal cladding of a metal substrate with an inlay of a noble metal or alloy. In the inlaying method a strip of a substrate metal is inlayed with a stripe of an alloy followed by capping with gold. For example, a strip of copper-bronze alloy is inlayed with 40/60 Ag/Pd alloy about 90 microinches thick followed by a 10 microinch thick Au capping. The inlayed strip is then stamped and formed into a connector. The alloy material is expensive and, unfortunately, theinlayed stripe wears out faster than is desirable. The electroplating method consists of electroplating a strip of the copper bronze substrate with a stripe of protective 30 coating, including electrodeposition of Pd alloyed with Ni or Co, followed by Au capping, typically in a reel-to-reel operation. A suitable process for electroplating palladium and palladium alloys from an aqueous solution is described in a number of U.S. patents granted to J. A. Abys and including U.S. Patent 4,468,296 issued on 2Q fi93~3 ' August 28, 1984; U.S. Patent No. 4,486,274 issued on December 4, 1984; and U.S.
Patent Nos.4,911,798 and 4,911,799, both issued on March 27,1990. The stripe-coated strip is then subjected to the stamping and forming operation. The total amount of precious metals deposited in the electroplating process is small and the process is less 5 costly than the inlaying process. Therefore, a device with an electrical contact produced with electroplated stripe would be less costly than with the inlayed stripe, even if being equal in other aspects.
Applicants have observed, however, that electrodeposits of alloys, for instance hard gold, palladium nickel or palladium cobalt alloy, exhibited undesirable 10 cracking defects when subjected to the forming operation as required in the production of such devices. Therefore, it is desirable to alleviate these undesirable characteristics of the electroplated palladium alloy stripe.
Summary of the Invention This invention is concerned with production of electrical devices 15 comprising an electrodeposited conductive region free from cracking defects. In the production of a contact portion of the device from a metal strip electroplated with a conductive stripe of an alloy, the stripe exhibited, upon stamping and forming operation, cracked areas. Typically, the stripe coating on the metal strip, such as a copper bronze material, includes a layer of nickel, a layer of palladium alloyed with nickel, cobalt, 20 arsenic or silver, and a flash coating of hard gold. The cracking defects were elimin~ted by subjecting the plated strip to an annealing treatment prior to the stamping and formign operation. After the heat-treatment, the stripe was free from cracks and separations between the successive layers.
According to one aspect of the invention there is provided the process 25 of fabricating an electrical device having at least one contact comprising a conductive region, which comprises, electroplating on at least a portion of a metal base a plated deposit layer comprising 20 mole percent to 80 mole percent palladium remainder being at least one metal selected from the group consisting of nickel, cobalt, arsenic, and silver, subjecting at least the plated portion to an annealing process, permitting the 30 annealed sample to cool to room temperature, and forming the plated base metal into a desired form, said annealing and cooling steps being conducted in an inert atmosphere, wherein the annealing step occurs prior to the forming step, and wherein the annealing process is a Rapid Thermal Anneal (RTA) heat treatment which comprises raising the plated portion from the plating temperature to a temperature above 380~C within a B
~ -2a- 2 ~ ~ g 3 ~ 3 period of time ranging from I second to 30 seconds and maintaining the plated portion at said holding temperature for a period of from l to 30 seconds, the total time of heat treatment being sufficient to anneal the plated deposit so as to elimin~te cracking of the deposit as a result of the forming step but insufficient to result in the loss of spring to S the metal base.
Brief Description of the Drawin~
FIG. 1 is a schematic representation of a connector and a mating pin in which mating contact surfaces are electroplated with a metal comprising palladium alloy;
FIG. 2 is a schematic representation of a connector pin, the inside of one end of which is coated with electroplated metal comprising palladium alloy;
FIG. 3 is a chart of PdNi plating crystallinity transition in terms of time in seconds on a log scale versus temperature in degrees centigrade for a 300 to 1000~C
zone;
B
i_ FIG. 4 is a chart of PdNi plating crystallinity transition in terms of time in seconds versus temperature in degrees centigrade for a 500-900 ~C zone;
FIG. S is a chart of an operating window in terms of ~ in degrees C versus time in seconds for a RTA of PdNi alloy at 600 ~C;
S FIG. 6 is a chart of an operating window in terms of te~ tul~ in degrees C versus time in seconds for a RTA of PdNi alloy at 625 ~C;
FIG. 7 is a chart of an operating window in terms of tell,pel~ture in degrees C versus time in seconds for a RTA of PdNi alloy at 650 ~C;
FIG. 8 is a chart of an operating window in terms of ~.~ c in 10 degrees C versus time in seconds for a RTA of PdNi alloy at 725 ~C;
FIG. 9 is a chart of an operating window in terms of ~ , in degrees C versus time in seconds for a RTA of PdNi alloy at 800 ~C.
Detailed Description In FIG. 1 is shown a schematic representation of an elec1ri~l connt~tor, 15 1, having a connector body, 2, and a mating pin, 3. Surfaces, 4, of the con~-f,clor body mating with the pin are electroplated with metal, comrri~ing a p~ m alloy and an overlay of hard gold.
In FIG. 2 is shown a schematic representation of a connector pin, 6, one portion of which is formed into a cylindrical configuration, 7, an inside surface of 20 end portion of which is coated with electroplated metal, 8, comprising a palladium alloy and an overlay of hard gold.
In the production of electrical connectors, a strip base metal, such as a copper-nickel-tin alloy No. 725 (88.2 Cu, 9.5 Ni, 2.3 Sn; ASTM Spec. No. B122) provided with a 50-70 micro-inch thick layer of nickel, typically electroplated from a 25 nickel sulfamate bath, is coated with a 20-30 micro-inch thick layer of p~ lmalloy followed by a 3-5 micro-inch thick flash coating of hard gold, such as a cobalt-hardened gold typically electroplated from a slightly acidic solution comprising gold cyanide, cobalt citride and a citric buffer. The palladium alloy is electroplated from the bath and under conditions described in the Abys patents 30 (supra.), especially U.S. Patent 4,911,799. Typically, palladium alloys for this use are made up from 20 to 80 mole percent palladium, rçm~inder being nickel, cobalt, arsenic or silver, with nickel and cobalt being a plerell~d and nickel being the most preferred alloying metal.
~W_ The palladium alloy plating bath may be plcpaled by adding to an aqueous solution of a complexing agent, a source of p~ m and of an alloying agent, e.g. PdCl2 and NiCl2, respectively, stirring, optionally he~ting, filt~rin~ and diluting the solution to a desired concentration. The palladium molar con~
5 in the bath typically may vary from 0.001 to saturation, with 0.01 to 1.0 being plGrGll~,d, and 0.1 to 0.5 being most preferred. To this solution buffer is added (e.g.
equal molar amounts of K3PO4 or NH4Cl) and the pH is adjusted up by the addition of KOH and down by the adtlitiQn of H3PO4 or HCl. Other buffer and pH-adjusting agents may be used as is well-known in the art. Typically, pH values 10 of the bath are between 5 and 14, with pH from 7 to 12 being more plGfe.lcd and 7.5 to 10 being most preferred. Plating at current densities as high as 200, 500 or even 2000 ASF for high-speed plating yield excellent results as do lower plating current densities of 0.01 to 50 or even 100 to 200 ASF typically used for low-speed plating.
Sources of pall~ m may be selected from PdCl2,PdBr2,PdI2,PdSO4, 15 Pd(NF3)2Cl2,Pd(NH3)2Br2, Pd(NH3)2I2, and tetrachlorop~ des (e.g.
K2PdC14), with PdC12 being preferred. The complexing agents may be selected form ammonia and alkyl ~ mines~ including aLkyl hydroxyamines with up to 50 carbon atoms, with up to 25 carbon atoms being plerGll~,d and up to 10 carbon atoms being most preferred. Alkyl hydroxyamines selected from bis-20 (hydroxymethyl)aminomethane, tris-(hydroxymethyl)~minomt th~ne, bis-(hydroxyethyl)~minomçthane and tris-(hydroxyethyl)~minometh~ne are among the most p~cfe~.,d aL~cyl hydroxyamines.
Normally, the electroplated deposits are well adhering and ductile.
However, it was discovered that under certain forming operation con~litiQn~ the 25 electroplated PdNi alloy coating unexpectedly exhibited cracks. The forming operation conditions include bending the electroplated strip such that the el~ng~tion of the electroplated coating on the outer surface of the contact, e.g. surface 4 (~;IG.
1), is in excess of 10% or such that the inside ~ m-oter of the formed contact portion (FIG. 2) is less than 2 mm.
This problem has been mitigated in accordance with the present invention by subjecting the electroplated strip, prior to the forming operation, to an ~nne~ling treatment, as described hereinbelow. During the ~nne~ling, the electroplated PdNi alloy undergoes a recryst~lli7~tion process. While crystallites in the coating as electroplated are of the order of 5-10 n~n~m~ters in size, the 35 crystallites in the thermally treated material increase to several mic.u~ el~ in si_e with resultant increase in the ductility of the electroplated material without any measurable deterioration in the hardness of the electrodeposit. The ~nn~l~ PdNi alloy-plated stripe, when subjected to the ~ pil1g and forming operation, lc;ll~aillS
free of cracking defects which develop in the thermally-untreated m~tPri~l The ~nnP~ling is con~lcted such that the plo?e.lies of the underlying substrate, such as 5 its spring characteristics, will not be affected by the anneal.
~ nne~ling may be a~complished in nu,ller~us ways. One could be by placing a reel or reels of the electroplated metal into an ~nnto~ling furnace for a time sufficient to anneal the stripe. However, in this procedure the ~nn~ling may not be effectively controlled since inner layers of the reel may take longer period to heat-up 10 to a desired temperature than the outer layers of the reel thus leading to a possible loss of spring in the substrate material in the outer layers. A more err~ way would be to advance the strip through a furnace in a reel-to-reel operation wLe-~
each portion would successively enter the furnace, the l~lllpel~lulc of the strip wouldbe raised to a desired annealing temperature, held there for a period of time s-~ffirient 15 to complete the ~nne~ling of the electroplated deposit and upon exiting the furnace, cooled down to the room temperature. More advantageously, thermal ~ n~el~t of the plated strip may be conducted in a furnace positioned at the exit from the plating line so that the plating and annealing steps are conducted in a con~inuo~ls f~hion An elongated tubular furnace with a heating zone several feet long, proportioned to20 enable the thermal processing of the plated strip during the p~s~ge of the strip through the furnace, could be used for this purpose. The speed of advance of thestrip through the furnace as well as the ~nn~ling process are progr~~ ed to coincide with the speed of advance of the strip through the plating operation. After the annealing step, the strip exits the furnace and is permitted to cool down to an 25 ambient temperature.
The ~nne:~ling includes a preheating or rise step during which the ~elllp.,.~ture rises from the environment or plating bath tempe.ature to an op~imu annealing temperature level and a holding step during which the prehe~ted strip is held at the optimum annealing le~l~pel~ture level for a preselected period of time.
30 The ~nne~l~d is followed by a cooling step during which the ~nne~lçd sample is permitted to cool down to room lempel~ture. The ~nne~ling and the cooling are conducted in an inert gas atmosphere such as nitrogen, argon, helium. Of essence is the total time of the annealin, which consists of rise time to raise the lelllp~ ture of the plated deposit from an environment of platng bath lelllp~ ture to a hold 35 temperature, and hold time during which the article is held at the hold lelll~l~ture to complete the anneal of the deposit. Inadequate ~nne~ling shall result in stripe .
deposits which are insufficiently ductile and, thus, shall exhibit cracks after the stamping and forming operation. On the other hand, excessive anne~ling may lead to the loss of spring in the substrate. Therefore, the ~nnPaling should be conducted so as to fully anneal the stripe deposit while avoiding such anne~ling of the metal of 5 the substrate as to unfavorably affect its spring characteristics. Spring in the connector is needed to keep a tight contact with the other part of the connp~ctor couple, e.g. a contact between contact portion 4 and pin 3 (~;IG. 1).
In the preferred exemplary emb~limt nt, heat-tre~tment was ~.ro~ ed of stripe-on-strip coated material comprising a strip base metal of a copper-nickel-tin 10 alloy 725 (88.2 Cu, 9.5 Ni, 2.3 Sn, ASTM Spec. No. B122) having a 50-70 microinch thick layer of nickel, a 20-30 microinch thick layer of p~ m-nickel alloy (20-80 Pd, preferably 80 Pd, rem~inder Ni) and a 3-5 microinch flash coating of hard gold. Formation of electrical connectors from this m~teri~l leads to an elongation in the outer coatings of the device shown in FIG. 1 exceecling 10%;
15 however, PdNi alloy as plated typically can sustain elongation in the range of from 6 to 10% and cannot sustain elongations of 10% or more without cracking. Applicants have discovered that unexpectedly cracking defects in this material may be elimin~ted by annealing of the plated deposit at or above the lelllpe.alulc of 380 ~.
Differential calorimet-ry pelrol.ned at this temperature produces recrys~lli7~tion and 20 anne~ling which can be detected by its exothermal re~ction Here, the typical rate of temperature rise is 5 ~C per minute, thus amounting to a total anneal time of about 70 minutes. However, this rate of processing is not suitable for plating processes conducted at a plating velocity of typically 6-12 m/min. (0.1-0.2 mlsec.) Therefore, the ann~ling may be conclucted most expeditiously by a Rapid Thermal Anneal 25 (RTA) tre~tment in which a total heat treatment time, including rise and hold times, is typically limited to one minute or less. Utilizing this process, the optimum anne~ling temperature can be reached within a period of seconds, such as from 1 to 30 secon-l~ or more, depending on the rate at which the t~ e~alulc rises from the initial to the optimum annealing lelnp~"dture and holding of the deposit at that30 tell~l)el~ture for a period of from 1 to 30 seconds or more. The most effirient annealing of the coating is achieved if RTA is performed with a rapid rise lel"pc~ture, that is a rise in degrees per interval of time from the lel-lp~ lulc of the plated strip to the optimum annealing te~pe~dture. Typically, shorter rise timesinvolving sharp rise to the annealing lelnl)elature, are more successful in achieving 35 the appr~ iate annealing of PdNi coating than longer rise times.
Graphical presçnt~tiQn of the infonn~tion directed to time and telllpelature relation in the PdNi alloy thermal ~nne~ling is shown in FIGs. 3 and 4 of the drawings. The solid curve line represents a boundary between the fine crystallites of the PdNi electroplated alloy, as electroplated with ~10% elongation 5 capability, to the left of (or below) the boundary and enlarged cry~t~llinities with greater than 10%, e.g. 10-20%, elongation capabilities, to the right of (or above) the boundary. A PdNi alloy heat-treated at a selected lell~el~ture for total time of heat-tre~tmPnt represented by a point of intersection on the boundary defined by the curve, shall be crack free. Above this boundary the alloy shall remain crack free;
10 however, the material of the substrate when heated beyond the limits of te~ a~
and time representing an operating window for the material, may begin to loose its spring.
Below 500 ~C, the time needed to achieve any ~nne~ling of the PdNi alloy coating exceeds several minutes. While this time of processing could be 15 acceptable for batch operations, these conditions may be unacceptable for in-line plating and ~nne~ling of plated articles. The ~nne~ling involves rise from a room temperature to a hold temperature, e.g. 500 ~C and then holding the body at thattemperature. For example, the total time requirement at 500 ~C is about 120 seconds; if it takes 10 seconds to raise the temperature of the body to 500 ~C, then 20 another 110 seconds at that tempelature are needed to fully anneal the PdNi deposit.
It is seen that at 400 ~C, the total treatment time may add-up to about 3000 seconds before the plated deposit shall become crack-free.
Within a range of from 575 ~C up to 725 ~C lies a zone of exposure times (rise time and hold time combined) exceptionally well suited for the RTA. At 25 600 ~C the total exposure temperature time is between 25 to 30 seconds, while at higher temperatures it drops down to a few seconds at 725 deg C. At telllpel~tures above 725~ C the process becomes almost impractical due to the short time involved in processing. Thermal treatment at these higher le"lpel~tures may quickly lead to :~nnealing of both, the substrate and the coating, and may make the product 30 unacceptable due to the loss of spring in the substrate.
FIGs. 5-9 are graphic representations of operating windows for the copper-nickel-tin alloy 725 substrate at 600, 625, 650, 725 and 800 ~C, respectively.
Upper limits of time in these charts suggest the permissible time of ~nn-~aling the device at these select temperatures beyond the boundary curve of FIG. 3, before the 35 onset of loss of spring in the substrate material. Similar windows may be developed for other lelllp~l~tures as well as for other substrate m~teri~l~ by simple trial-and-.,."
error technique.
In Table I, below, are shown some of the RTA tre~tmPnt effects on the performance of PdNi alloy (80 Pd-20Ni) electroplated deposit on the 725 copper alloy substrate.
TABLE I
RTA TREATMENT E~ CT ON PdNi PLATE PERFORMANOE
Temp. Rise Time Hold Time Cracks Spring % El.
(deg. C) (s) (s) yes/no OK/lost 500 10 20 yes OK
l 0 20 20 yes OK
yes OK
yes OK 5.1-9.3 600 10 20 no OK
no OK
625 1 10 yes/slight OK
yes/slight OK
no OK 10.7-16.9 yes OK
no OK
no OK
no OK
650 1 5 yes OK
yes/slight OK
no OK
1 20 no OK 12.7-20.2 yes OK
'~
g 10 yes/slight OK
no OK
700 1 5 no lost/slight no lost no lost 800 1 1 no lost/slight 2 no lost 3 no lost
Technical Field The invention is concerned with electroplated palla(lil1m alloys, especially electroplated as stripe-on-strip, for use in the fabrication of contacts in 5 electrical devices.
Back~round of the Invention Palladium and palladium alloys are used in a number of applir~tion~
because of their chemical inertness, hardness, excellent wearability, bright finish and high electrical conductivity. In addition, they do not form oxide surface coatings 10 that might increase surface contact resistance. Particularly attractive is the use of palladium alloys as electrical contact surfaces in the electrical arts such as in electrical connectors, relay contacts, switches, etc.
Electrical contact manufacture advantageously employs a "stripe-on-strip" processing. A metal strip, typically a copper bron~ material, is coated with a 15 stripe of a metal. To reduce an expense of precious metals the stripe is produced only on those portions of the strip which when subsequently formed into an electrical connector will be subjected to extended wear and requires superior electrical connection characteristics. Following the coating application, the metal strip is subjected to stamping and forming operations.
The process of coating the strip with a stripe of contact m~teri~l can be performed in several ways including an inlaying method and an electroplating method. The inlaying method calls for metal cladding of a metal substrate with an inlay of a noble metal or alloy. In the inlaying method a strip of a substrate metal is inlayed with a stripe of an alloy followed by capping with gold. For example, a strip of copper-bronze alloy is inlayed with 40/60 Ag/Pd alloy about 90 microinches thick followed by a 10 microinch thick Au capping. The inlayed strip is then stamped and formed into a connector. The alloy material is expensive and, unfortunately, theinlayed stripe wears out faster than is desirable. The electroplating method consists of electroplating a strip of the copper bronze substrate with a stripe of protective 30 coating, including electrodeposition of Pd alloyed with Ni or Co, followed by Au capping, typically in a reel-to-reel operation. A suitable process for electroplating palladium and palladium alloys from an aqueous solution is described in a number of U.S. patents granted to J. A. Abys and including U.S. Patent 4,468,296 issued on 2Q fi93~3 ' August 28, 1984; U.S. Patent No. 4,486,274 issued on December 4, 1984; and U.S.
Patent Nos.4,911,798 and 4,911,799, both issued on March 27,1990. The stripe-coated strip is then subjected to the stamping and forming operation. The total amount of precious metals deposited in the electroplating process is small and the process is less 5 costly than the inlaying process. Therefore, a device with an electrical contact produced with electroplated stripe would be less costly than with the inlayed stripe, even if being equal in other aspects.
Applicants have observed, however, that electrodeposits of alloys, for instance hard gold, palladium nickel or palladium cobalt alloy, exhibited undesirable 10 cracking defects when subjected to the forming operation as required in the production of such devices. Therefore, it is desirable to alleviate these undesirable characteristics of the electroplated palladium alloy stripe.
Summary of the Invention This invention is concerned with production of electrical devices 15 comprising an electrodeposited conductive region free from cracking defects. In the production of a contact portion of the device from a metal strip electroplated with a conductive stripe of an alloy, the stripe exhibited, upon stamping and forming operation, cracked areas. Typically, the stripe coating on the metal strip, such as a copper bronze material, includes a layer of nickel, a layer of palladium alloyed with nickel, cobalt, 20 arsenic or silver, and a flash coating of hard gold. The cracking defects were elimin~ted by subjecting the plated strip to an annealing treatment prior to the stamping and formign operation. After the heat-treatment, the stripe was free from cracks and separations between the successive layers.
According to one aspect of the invention there is provided the process 25 of fabricating an electrical device having at least one contact comprising a conductive region, which comprises, electroplating on at least a portion of a metal base a plated deposit layer comprising 20 mole percent to 80 mole percent palladium remainder being at least one metal selected from the group consisting of nickel, cobalt, arsenic, and silver, subjecting at least the plated portion to an annealing process, permitting the 30 annealed sample to cool to room temperature, and forming the plated base metal into a desired form, said annealing and cooling steps being conducted in an inert atmosphere, wherein the annealing step occurs prior to the forming step, and wherein the annealing process is a Rapid Thermal Anneal (RTA) heat treatment which comprises raising the plated portion from the plating temperature to a temperature above 380~C within a B
~ -2a- 2 ~ ~ g 3 ~ 3 period of time ranging from I second to 30 seconds and maintaining the plated portion at said holding temperature for a period of from l to 30 seconds, the total time of heat treatment being sufficient to anneal the plated deposit so as to elimin~te cracking of the deposit as a result of the forming step but insufficient to result in the loss of spring to S the metal base.
Brief Description of the Drawin~
FIG. 1 is a schematic representation of a connector and a mating pin in which mating contact surfaces are electroplated with a metal comprising palladium alloy;
FIG. 2 is a schematic representation of a connector pin, the inside of one end of which is coated with electroplated metal comprising palladium alloy;
FIG. 3 is a chart of PdNi plating crystallinity transition in terms of time in seconds on a log scale versus temperature in degrees centigrade for a 300 to 1000~C
zone;
B
i_ FIG. 4 is a chart of PdNi plating crystallinity transition in terms of time in seconds versus temperature in degrees centigrade for a 500-900 ~C zone;
FIG. S is a chart of an operating window in terms of ~ in degrees C versus time in seconds for a RTA of PdNi alloy at 600 ~C;
S FIG. 6 is a chart of an operating window in terms of te~ tul~ in degrees C versus time in seconds for a RTA of PdNi alloy at 625 ~C;
FIG. 7 is a chart of an operating window in terms of tell,pel~ture in degrees C versus time in seconds for a RTA of PdNi alloy at 650 ~C;
FIG. 8 is a chart of an operating window in terms of ~.~ c in 10 degrees C versus time in seconds for a RTA of PdNi alloy at 725 ~C;
FIG. 9 is a chart of an operating window in terms of ~ , in degrees C versus time in seconds for a RTA of PdNi alloy at 800 ~C.
Detailed Description In FIG. 1 is shown a schematic representation of an elec1ri~l connt~tor, 15 1, having a connector body, 2, and a mating pin, 3. Surfaces, 4, of the con~-f,clor body mating with the pin are electroplated with metal, comrri~ing a p~ m alloy and an overlay of hard gold.
In FIG. 2 is shown a schematic representation of a connector pin, 6, one portion of which is formed into a cylindrical configuration, 7, an inside surface of 20 end portion of which is coated with electroplated metal, 8, comprising a palladium alloy and an overlay of hard gold.
In the production of electrical connectors, a strip base metal, such as a copper-nickel-tin alloy No. 725 (88.2 Cu, 9.5 Ni, 2.3 Sn; ASTM Spec. No. B122) provided with a 50-70 micro-inch thick layer of nickel, typically electroplated from a 25 nickel sulfamate bath, is coated with a 20-30 micro-inch thick layer of p~ lmalloy followed by a 3-5 micro-inch thick flash coating of hard gold, such as a cobalt-hardened gold typically electroplated from a slightly acidic solution comprising gold cyanide, cobalt citride and a citric buffer. The palladium alloy is electroplated from the bath and under conditions described in the Abys patents 30 (supra.), especially U.S. Patent 4,911,799. Typically, palladium alloys for this use are made up from 20 to 80 mole percent palladium, rçm~inder being nickel, cobalt, arsenic or silver, with nickel and cobalt being a plerell~d and nickel being the most preferred alloying metal.
~W_ The palladium alloy plating bath may be plcpaled by adding to an aqueous solution of a complexing agent, a source of p~ m and of an alloying agent, e.g. PdCl2 and NiCl2, respectively, stirring, optionally he~ting, filt~rin~ and diluting the solution to a desired concentration. The palladium molar con~
5 in the bath typically may vary from 0.001 to saturation, with 0.01 to 1.0 being plGrGll~,d, and 0.1 to 0.5 being most preferred. To this solution buffer is added (e.g.
equal molar amounts of K3PO4 or NH4Cl) and the pH is adjusted up by the addition of KOH and down by the adtlitiQn of H3PO4 or HCl. Other buffer and pH-adjusting agents may be used as is well-known in the art. Typically, pH values 10 of the bath are between 5 and 14, with pH from 7 to 12 being more plGfe.lcd and 7.5 to 10 being most preferred. Plating at current densities as high as 200, 500 or even 2000 ASF for high-speed plating yield excellent results as do lower plating current densities of 0.01 to 50 or even 100 to 200 ASF typically used for low-speed plating.
Sources of pall~ m may be selected from PdCl2,PdBr2,PdI2,PdSO4, 15 Pd(NF3)2Cl2,Pd(NH3)2Br2, Pd(NH3)2I2, and tetrachlorop~ des (e.g.
K2PdC14), with PdC12 being preferred. The complexing agents may be selected form ammonia and alkyl ~ mines~ including aLkyl hydroxyamines with up to 50 carbon atoms, with up to 25 carbon atoms being plerGll~,d and up to 10 carbon atoms being most preferred. Alkyl hydroxyamines selected from bis-20 (hydroxymethyl)aminomethane, tris-(hydroxymethyl)~minomt th~ne, bis-(hydroxyethyl)~minomçthane and tris-(hydroxyethyl)~minometh~ne are among the most p~cfe~.,d aL~cyl hydroxyamines.
Normally, the electroplated deposits are well adhering and ductile.
However, it was discovered that under certain forming operation con~litiQn~ the 25 electroplated PdNi alloy coating unexpectedly exhibited cracks. The forming operation conditions include bending the electroplated strip such that the el~ng~tion of the electroplated coating on the outer surface of the contact, e.g. surface 4 (~;IG.
1), is in excess of 10% or such that the inside ~ m-oter of the formed contact portion (FIG. 2) is less than 2 mm.
This problem has been mitigated in accordance with the present invention by subjecting the electroplated strip, prior to the forming operation, to an ~nne~ling treatment, as described hereinbelow. During the ~nne~ling, the electroplated PdNi alloy undergoes a recryst~lli7~tion process. While crystallites in the coating as electroplated are of the order of 5-10 n~n~m~ters in size, the 35 crystallites in the thermally treated material increase to several mic.u~ el~ in si_e with resultant increase in the ductility of the electroplated material without any measurable deterioration in the hardness of the electrodeposit. The ~nn~l~ PdNi alloy-plated stripe, when subjected to the ~ pil1g and forming operation, lc;ll~aillS
free of cracking defects which develop in the thermally-untreated m~tPri~l The ~nnP~ling is con~lcted such that the plo?e.lies of the underlying substrate, such as 5 its spring characteristics, will not be affected by the anneal.
~ nne~ling may be a~complished in nu,ller~us ways. One could be by placing a reel or reels of the electroplated metal into an ~nnto~ling furnace for a time sufficient to anneal the stripe. However, in this procedure the ~nn~ling may not be effectively controlled since inner layers of the reel may take longer period to heat-up 10 to a desired temperature than the outer layers of the reel thus leading to a possible loss of spring in the substrate material in the outer layers. A more err~ way would be to advance the strip through a furnace in a reel-to-reel operation wLe-~
each portion would successively enter the furnace, the l~lllpel~lulc of the strip wouldbe raised to a desired annealing temperature, held there for a period of time s-~ffirient 15 to complete the ~nne~ling of the electroplated deposit and upon exiting the furnace, cooled down to the room temperature. More advantageously, thermal ~ n~el~t of the plated strip may be conducted in a furnace positioned at the exit from the plating line so that the plating and annealing steps are conducted in a con~inuo~ls f~hion An elongated tubular furnace with a heating zone several feet long, proportioned to20 enable the thermal processing of the plated strip during the p~s~ge of the strip through the furnace, could be used for this purpose. The speed of advance of thestrip through the furnace as well as the ~nn~ling process are progr~~ ed to coincide with the speed of advance of the strip through the plating operation. After the annealing step, the strip exits the furnace and is permitted to cool down to an 25 ambient temperature.
The ~nne:~ling includes a preheating or rise step during which the ~elllp.,.~ture rises from the environment or plating bath tempe.ature to an op~imu annealing temperature level and a holding step during which the prehe~ted strip is held at the optimum annealing le~l~pel~ture level for a preselected period of time.
30 The ~nne~l~d is followed by a cooling step during which the ~nne~lçd sample is permitted to cool down to room lempel~ture. The ~nne~ling and the cooling are conducted in an inert gas atmosphere such as nitrogen, argon, helium. Of essence is the total time of the annealin, which consists of rise time to raise the lelllp~ ture of the plated deposit from an environment of platng bath lelllp~ ture to a hold 35 temperature, and hold time during which the article is held at the hold lelll~l~ture to complete the anneal of the deposit. Inadequate ~nne~ling shall result in stripe .
deposits which are insufficiently ductile and, thus, shall exhibit cracks after the stamping and forming operation. On the other hand, excessive anne~ling may lead to the loss of spring in the substrate. Therefore, the ~nnPaling should be conducted so as to fully anneal the stripe deposit while avoiding such anne~ling of the metal of 5 the substrate as to unfavorably affect its spring characteristics. Spring in the connector is needed to keep a tight contact with the other part of the connp~ctor couple, e.g. a contact between contact portion 4 and pin 3 (~;IG. 1).
In the preferred exemplary emb~limt nt, heat-tre~tment was ~.ro~ ed of stripe-on-strip coated material comprising a strip base metal of a copper-nickel-tin 10 alloy 725 (88.2 Cu, 9.5 Ni, 2.3 Sn, ASTM Spec. No. B122) having a 50-70 microinch thick layer of nickel, a 20-30 microinch thick layer of p~ m-nickel alloy (20-80 Pd, preferably 80 Pd, rem~inder Ni) and a 3-5 microinch flash coating of hard gold. Formation of electrical connectors from this m~teri~l leads to an elongation in the outer coatings of the device shown in FIG. 1 exceecling 10%;
15 however, PdNi alloy as plated typically can sustain elongation in the range of from 6 to 10% and cannot sustain elongations of 10% or more without cracking. Applicants have discovered that unexpectedly cracking defects in this material may be elimin~ted by annealing of the plated deposit at or above the lelllpe.alulc of 380 ~.
Differential calorimet-ry pelrol.ned at this temperature produces recrys~lli7~tion and 20 anne~ling which can be detected by its exothermal re~ction Here, the typical rate of temperature rise is 5 ~C per minute, thus amounting to a total anneal time of about 70 minutes. However, this rate of processing is not suitable for plating processes conducted at a plating velocity of typically 6-12 m/min. (0.1-0.2 mlsec.) Therefore, the ann~ling may be conclucted most expeditiously by a Rapid Thermal Anneal 25 (RTA) tre~tment in which a total heat treatment time, including rise and hold times, is typically limited to one minute or less. Utilizing this process, the optimum anne~ling temperature can be reached within a period of seconds, such as from 1 to 30 secon-l~ or more, depending on the rate at which the t~ e~alulc rises from the initial to the optimum annealing lelnp~"dture and holding of the deposit at that30 tell~l)el~ture for a period of from 1 to 30 seconds or more. The most effirient annealing of the coating is achieved if RTA is performed with a rapid rise lel"pc~ture, that is a rise in degrees per interval of time from the lel-lp~ lulc of the plated strip to the optimum annealing te~pe~dture. Typically, shorter rise timesinvolving sharp rise to the annealing lelnl)elature, are more successful in achieving 35 the appr~ iate annealing of PdNi coating than longer rise times.
Graphical presçnt~tiQn of the infonn~tion directed to time and telllpelature relation in the PdNi alloy thermal ~nne~ling is shown in FIGs. 3 and 4 of the drawings. The solid curve line represents a boundary between the fine crystallites of the PdNi electroplated alloy, as electroplated with ~10% elongation 5 capability, to the left of (or below) the boundary and enlarged cry~t~llinities with greater than 10%, e.g. 10-20%, elongation capabilities, to the right of (or above) the boundary. A PdNi alloy heat-treated at a selected lell~el~ture for total time of heat-tre~tmPnt represented by a point of intersection on the boundary defined by the curve, shall be crack free. Above this boundary the alloy shall remain crack free;
10 however, the material of the substrate when heated beyond the limits of te~ a~
and time representing an operating window for the material, may begin to loose its spring.
Below 500 ~C, the time needed to achieve any ~nne~ling of the PdNi alloy coating exceeds several minutes. While this time of processing could be 15 acceptable for batch operations, these conditions may be unacceptable for in-line plating and ~nne~ling of plated articles. The ~nne~ling involves rise from a room temperature to a hold temperature, e.g. 500 ~C and then holding the body at thattemperature. For example, the total time requirement at 500 ~C is about 120 seconds; if it takes 10 seconds to raise the temperature of the body to 500 ~C, then 20 another 110 seconds at that tempelature are needed to fully anneal the PdNi deposit.
It is seen that at 400 ~C, the total treatment time may add-up to about 3000 seconds before the plated deposit shall become crack-free.
Within a range of from 575 ~C up to 725 ~C lies a zone of exposure times (rise time and hold time combined) exceptionally well suited for the RTA. At 25 600 ~C the total exposure temperature time is between 25 to 30 seconds, while at higher temperatures it drops down to a few seconds at 725 deg C. At telllpel~tures above 725~ C the process becomes almost impractical due to the short time involved in processing. Thermal treatment at these higher le"lpel~tures may quickly lead to :~nnealing of both, the substrate and the coating, and may make the product 30 unacceptable due to the loss of spring in the substrate.
FIGs. 5-9 are graphic representations of operating windows for the copper-nickel-tin alloy 725 substrate at 600, 625, 650, 725 and 800 ~C, respectively.
Upper limits of time in these charts suggest the permissible time of ~nn-~aling the device at these select temperatures beyond the boundary curve of FIG. 3, before the 35 onset of loss of spring in the substrate material. Similar windows may be developed for other lelllp~l~tures as well as for other substrate m~teri~l~ by simple trial-and-.,."
error technique.
In Table I, below, are shown some of the RTA tre~tmPnt effects on the performance of PdNi alloy (80 Pd-20Ni) electroplated deposit on the 725 copper alloy substrate.
TABLE I
RTA TREATMENT E~ CT ON PdNi PLATE PERFORMANOE
Temp. Rise Time Hold Time Cracks Spring % El.
(deg. C) (s) (s) yes/no OK/lost 500 10 20 yes OK
l 0 20 20 yes OK
yes OK
yes OK 5.1-9.3 600 10 20 no OK
no OK
625 1 10 yes/slight OK
yes/slight OK
no OK 10.7-16.9 yes OK
no OK
no OK
no OK
650 1 5 yes OK
yes/slight OK
no OK
1 20 no OK 12.7-20.2 yes OK
'~
g 10 yes/slight OK
no OK
700 1 5 no lost/slight no lost no lost 800 1 1 no lost/slight 2 no lost 3 no lost
Claims (11)
1. The process of fabricating an electrical device having at least one contact comprising a conductive region, which comprises, electroplating on at least a portion of a metal base a plated deposit layer comprising 20 mole percent to 80 mole percent palladium remainder being at least one metal selected from the group consisting of nickel, cobalt, arsenic, and silver,subjecting at least the plated portion to an annealing process, permitting the annealed sample to cool to room temperature, and forming the plated base metal into a desired form, said annealing and cooling steps being conducted in an inert atmosphere, wherein the annealing step occurs prior to the forming step, and wherein the annealing process is a Rapid Thermal Anneal (RTA) heat treatment which comprises raising the plated portion from the plating temperature to a temperature above 380°C within a period of time ranging from 1 second to 30 seconds and maintaining the plated portion at said holding temperature for a period of from 1 to 30 seconds, the total time of heat treatment being sufficient to anneal the plated deposit so as to eliminate cracking of the deposit as a result of the forming step but insufficient to result in the loss of spring to the metal base.
2. The process of claim 1 in which the alloy is a palladium nickel alloy.
3. The process of claim 2 in which said annealing temperature is within a range of from 380 to 1000°C.
4. The process of claim 2 in which said palladium nickel alloy is plated on a surface of a layer of nickel on the metal base.
5. The process of claim 2 in which the conductive region comprises, sequentially from the metal base, a layer of nickel, a layer of palladium alloy and a flash coating comprising gold.
6. The process of claim S in which said metal base is of copper-nickel-tin alloy, said nickel layer is 50-70 micro-inch thick, said palladium nickel alloy layer is 20-30 micro-inch thick, and said flash coating comprising gold is 3-5 micro-inch thick.
7. The process of claim 2 in which said annealing is a Rapid Thermal Anneal (RTA) heat treatment which comprises raising the plating portion from theplating temperature to a temperature within a range from 575-800°C within a period of time ranging from 1 second to 30 seconds, maintaining the plated portion at saidholding temperature for a period of from 1 to 30 seconds, and permitting the annealed body to cool to an ambient temperature.
8. The process of claim 1 in which the metal base comprises a copper-nickel-tin alloy.
9. The process of claim 1 in which said forming includes bending of the plated portion of the metal base so as to result in an elongation of the palladium alloy deposit of at least ten percent.
10. The process of claim 1 in which said forming includes rolling of the plated portion about a mandrel with a diameter of less than 2 mm, the plated palladium alloy being on the inside of the rolled portion.
11. The process of claim 1 in which said atmosphere comprises at least one gas selected from the group consisting of nitrogen, argon, helium and xenon.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/733,492 US5180482A (en) | 1991-07-22 | 1991-07-22 | Thermal annealing of palladium alloys |
| US733,492 | 1991-07-22 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2069363A1 CA2069363A1 (en) | 1993-01-23 |
| CA2069363C true CA2069363C (en) | 1999-05-18 |
Family
ID=24947830
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002069363A Expired - Fee Related CA2069363C (en) | 1991-07-22 | 1992-05-25 | Thermal annealing of palladium alloys |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5180482A (en) |
| EP (1) | EP0524760B1 (en) |
| JP (1) | JP2607002B2 (en) |
| KR (1) | KR950004992B1 (en) |
| CA (1) | CA2069363C (en) |
| DE (1) | DE69210704T2 (en) |
| HK (1) | HK179096A (en) |
| SG (1) | SG43778A1 (en) |
| TW (1) | TW208046B (en) |
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| US7200930B2 (en) * | 1994-11-15 | 2007-04-10 | Formfactor, Inc. | Probe for semiconductor devices |
| US5665639A (en) * | 1994-02-23 | 1997-09-09 | Cypress Semiconductor Corp. | Process for manufacturing a semiconductor device bump electrode using a rapid thermal anneal |
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| KR960039315A (en) * | 1995-04-06 | 1996-11-25 | 이대원 | Lead frame manufacturing method |
| FR2766396B1 (en) * | 1997-07-25 | 1999-10-01 | Radiall Sa | PROCESS FOR COATING A METAL PART TO BE BRAZED, COATING USED FOR THIS PURPOSE AND PART THUS COATED |
| US6807734B2 (en) * | 1998-02-13 | 2004-10-26 | Formfactor, Inc. | Microelectronic contact structures, and methods of making same |
| US6255126B1 (en) * | 1998-12-02 | 2001-07-03 | Formfactor, Inc. | Lithographic contact elements |
| US6235177B1 (en) * | 1999-09-09 | 2001-05-22 | Aerogen, Inc. | Method for the construction of an aperture plate for dispensing liquid droplets |
| US6335107B1 (en) * | 1999-09-23 | 2002-01-01 | Lucent Technologies Inc. | Metal article coated with multilayer surface finish for porosity reduction |
| MXPA02010884A (en) * | 2000-05-05 | 2003-03-27 | Aerogen Ireland Ltd | Apparatus and methods for the delivery of medicaments to the respiratory system. |
| US8336545B2 (en) * | 2000-05-05 | 2012-12-25 | Novartis Pharma Ag | Methods and systems for operating an aerosol generator |
| US6948491B2 (en) * | 2001-03-20 | 2005-09-27 | Aerogen, Inc. | Convertible fluid feed system with comformable reservoir and methods |
| US7600511B2 (en) * | 2001-11-01 | 2009-10-13 | Novartis Pharma Ag | Apparatus and methods for delivery of medicament to a respiratory system |
| US7971588B2 (en) * | 2000-05-05 | 2011-07-05 | Novartis Ag | Methods and systems for operating an aerosol generator |
| US7100600B2 (en) * | 2001-03-20 | 2006-09-05 | Aerogen, Inc. | Fluid filled ampoules and methods for their use in aerosolizers |
| US6546927B2 (en) | 2001-03-13 | 2003-04-15 | Aerogen, Inc. | Methods and apparatus for controlling piezoelectric vibration |
| US6732944B2 (en) * | 2001-05-02 | 2004-05-11 | Aerogen, Inc. | Base isolated nebulizing device and methods |
| US20050205089A1 (en) * | 2002-01-07 | 2005-09-22 | Aerogen, Inc. | Methods and devices for aerosolizing medicament |
| CA2472644C (en) | 2002-01-07 | 2013-11-05 | Aerogen, Inc. | Devices and methods for nebulizing fluids for inhalation |
| US7677467B2 (en) * | 2002-01-07 | 2010-03-16 | Novartis Pharma Ag | Methods and devices for aerosolizing medicament |
| ES2603067T3 (en) | 2002-01-15 | 2017-02-23 | Novartis Ag | Methods and systems for operating an aerosol generator |
| US7109111B2 (en) * | 2002-02-11 | 2006-09-19 | Applied Materials, Inc. | Method of annealing metal layers |
| US20070044792A1 (en) * | 2005-08-30 | 2007-03-01 | Aerogen, Inc. | Aerosol generators with enhanced corrosion resistance |
| EP1509259B1 (en) * | 2002-05-20 | 2016-04-20 | Novartis AG | Apparatus for providing aerosol for medical treatment and methods |
| US8616195B2 (en) * | 2003-07-18 | 2013-12-31 | Novartis Ag | Nebuliser for the production of aerosolized medication |
| US7267121B2 (en) * | 2004-04-20 | 2007-09-11 | Aerogen, Inc. | Aerosol delivery apparatus and method for pressure-assisted breathing systems |
| BRPI0509991A (en) * | 2004-04-20 | 2007-10-16 | Aerogen Inc | aerosol delivery apparatus, methods and compositions for pressure-assisted breathing systems |
| US7290541B2 (en) * | 2004-04-20 | 2007-11-06 | Aerogen, Inc. | Aerosol delivery apparatus and method for pressure-assisted breathing systems |
| US7946291B2 (en) | 2004-04-20 | 2011-05-24 | Novartis Ag | Ventilation systems and methods employing aerosol generators |
| JP5064383B2 (en) * | 2005-05-25 | 2012-10-31 | エアロジェン，インコーポレイテッド | Vibration system and method |
| JP4828884B2 (en) * | 2005-07-26 | 2011-11-30 | 株式会社東芝 | Printed circuit wiring board and electronic device |
| CN100388572C (en) * | 2006-03-15 | 2008-05-14 | 上海坤链电子产品有限公司 | Partial electric plating method for box type structure jack contact of electric connector |
| JP5318375B2 (en) * | 2007-06-25 | 2013-10-16 | 株式会社サンユー | Palladium-cobalt alloy plating solution, method for forming palladium-cobalt alloy coating, and method for producing palladium-cobalt alloy hard coating |
| JP4846740B2 (en) * | 2008-01-23 | 2011-12-28 | 旭鍍金株式会社 | Plating product manufacturing method and electroplating method |
| US7842170B1 (en) * | 2009-03-09 | 2010-11-30 | Von Detten Volker | Device for selective plating of electrical contacts for connectors |
| BR112013016671B1 (en) | 2010-12-28 | 2020-12-15 | Stamford Devices Ltd | PLATE WITH NEBULIZING OPENING, VIBRATING MESH OF THE NEBULIZING TYPE AND METHOD FOR THE MANUFACTURING OF THAT PLATE |
| BR112014027624B1 (en) | 2012-06-11 | 2021-01-19 | Stamford Devices Ltd | method of making an aerosol forming orifice plate blade, orifice plate, aerosol forming device and orifice plate blade |
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|---|---|---|---|---|
| US3925170A (en) * | 1974-01-23 | 1975-12-09 | American Chem & Refining Co | Method and composition for producing bright palladium electrodepositions |
| GB1495910A (en) * | 1975-10-30 | 1977-12-21 | Ibm | Method and bath for electroplating palladium on an articl |
| US4066517A (en) * | 1976-03-11 | 1978-01-03 | Oxy Metal Industries Corporation | Electrodeposition of palladium |
| JPS569387A (en) * | 1979-07-04 | 1981-01-30 | Seiko Instr & Electronics Ltd | Plating method of decorative article |
| JPS6019630B2 (en) * | 1979-07-18 | 1985-05-17 | 日本鉱業株式会社 | contact |
| US4319967A (en) * | 1979-11-01 | 1982-03-16 | Bell Telephone Laboratories, Incorporated | Fabrication of palladium anode for X-ray lithography |
| JPS5772284A (en) * | 1980-10-21 | 1982-05-06 | Fujitsu Ltd | Method of producing electric contactor |
| US4486274A (en) * | 1981-02-27 | 1984-12-04 | At&T Bell Laboratories | Palladium plating prodedure |
| US4468296A (en) * | 1982-12-10 | 1984-08-28 | At&T Bell Laboratories | Process for electroplating palladium |
| JPH0244106B2 (en) * | 1985-06-17 | 1990-10-02 | Yazaki Corp | DENKYOSETSUTEN |
| JPS6353872A (en) * | 1986-08-22 | 1988-03-08 | 三菱電機株式会社 | Contactor material |
| US4911798A (en) * | 1988-12-20 | 1990-03-27 | At&T Bell Laboratories | Palladium alloy plating process |
| US4911799A (en) * | 1989-08-29 | 1990-03-27 | At&T Bell Laboratories | Electrodeposition of palladium films |
-
1991
- 1991-07-22 US US07/733,492 patent/US5180482A/en not_active Expired - Lifetime
-
1992
- 1992-05-20 TW TW081103936A patent/TW208046B/zh active
- 1992-05-25 CA CA002069363A patent/CA2069363C/en not_active Expired - Fee Related
- 1992-06-08 JP JP4171482A patent/JP2607002B2/en not_active Expired - Fee Related
- 1992-07-14 EP EP92306432A patent/EP0524760B1/en not_active Expired - Lifetime
- 1992-07-14 DE DE69210704T patent/DE69210704T2/en not_active Expired - Fee Related
- 1992-07-14 SG SG1996000810A patent/SG43778A1/en unknown
- 1992-07-15 KR KR1019920012559A patent/KR950004992B1/en not_active IP Right Cessation
-
1996
- 1996-09-26 HK HK179096A patent/HK179096A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69210704D1 (en) | 1996-06-20 |
| SG43778A1 (en) | 1997-11-14 |
| DE69210704T2 (en) | 1996-10-10 |
| HK179096A (en) | 1996-10-04 |
| CA2069363A1 (en) | 1993-01-23 |
| KR950004992B1 (en) | 1995-05-16 |
| JPH05190250A (en) | 1993-07-30 |
| EP0524760A2 (en) | 1993-01-27 |
| JP2607002B2 (en) | 1997-05-07 |
| EP0524760A3 (en) | 1994-07-13 |
| EP0524760B1 (en) | 1996-05-15 |
| KR930003459A (en) | 1993-02-24 |
| US5180482A (en) | 1993-01-19 |
| TW208046B (en) | 1993-06-21 |
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