Palladium-Based Alloys
20170218481 · 2017-08-03
Inventors
- Arthur S. Klein (Orange, CT, US)
- Edward F. Smith, III (Madison, CT)
- Srinath Viswanathan (West Hartford, CT, US)
Cpc classification
International classification
Abstract
Palladium-based ternary or higher alloys include palladium at about 45-55 wt %, copper about 32-42 wt %, silver at about 8-15 wt %, rhenium at about 0-5 wt %, and optionally one or more modifying elements at up to 1.0 wt %. The alloys are age-hardenable, provide hardness in excess of 350 HK (Knoop, 100 g load), have electrical conductivities above 19.5% IACS (International Annealed Copper Standard), have an elevated temperature strength above 100 ksi at temperatures up to 480° F. (250° C.), and remain ductile (tensile elongation >2%) in their fully age-hardened condition. The alloys may be used in static and moveable electrical contact and probe applications.
Claims
1. A palladium-based ternary or higher alloy, comprising: (a) palladium at about 45-55 wt %; (b) copper at about 32-42 wt %; (c) silver at about 8-15 wt %; (d) rhenium at about 0-5 wt %; and (e) up to 1.0 wt % modifying elements selected from the group consisting of: ruthenium, zirconium, gallium, and zinc, wherein the alloy has a Pd:Cu ratio of about 1.05 to 1.6 by weight, and wherein the alloy has a Pd:Ag ratio of about 3 to 6 by weight.
2. The alloy of claim 1, wherein the palladium is present at about 51-55 wt %, the copper is present at about 32-40 wt %, the silver is present at about 8.5-14 wt %, and the rhenium is present at about 0.5-2.5 wt %.
3. The alloy of claim 1, wherein the palladium is present at about 51-55 wt %, the copper is present at about 32-40 wt %, the silver is present at about 8.5-14 wt %, and zinc is present at about 0.2-0.8 wt %.
4. The alloy of claim 1, wherein a heat-treated electrical conductivity of the alloy exceeds 19.5% IACS.
5. The alloy of claim 1, wherein a heat-treated hardness of the alloy is at least 350 Knoop.
6. The alloy of claim 1, wherein the alloy exhibits a second phase of rhenium.
7. The alloy of claim 1, wherein the alloy is free of one or more of: nickel, chromium, gold, platinum, boron, or iron.
8. The alloy of claim 1, wherein the alloy is age-hardened and maintains a yield strength above 100 ksi at about 60° F. to about 480° F.
9. The alloy of claim 1, wherein the alloy is age-hardened and has a tensile elongation of greater than 2%.
10. A semiconductor probe comprising a palladium-based ternary or higher alloy, the alloy comprising: (a) palladium at about 45-55 wt %; (b) copper at about 32-42 wt %; (c) silver at about 8-15 wt %; (d) rhenium at about 0-5 wt %; and (e) up to 1.0 wt % modifying elements selected from the group consisting of: ruthenium, zirconium, gallium, and zinc, wherein the alloy has a Pd:Cu ratio of about 1.05 to 1.6 by weight, and wherein the alloy has a Pd:Ag ratio of about 3 to 6 by weight.
11. The semiconductor probe of claim 10, wherein the probe configured as a Cobra probe, a cantilever probe, a vertical probe, or a pogo pin probe.
12. The semiconductor probe of claim 10, wherein a heat-treated electrical conductivity of the alloy exceeds 19.5% IACS.
13. The semiconductor probe of claim 10, wherein a heat-treated hardness of the alloy is at least 350 Knoop.
14. The semiconductor probe of claim 10, wherein the alloy exhibits a second phase of rhenium.
15. The semiconductor probe of claim 10, wherein the alloy is free of one or more of: nickel, chromium, gold, platinum, boron or iron.
16. The semiconductor probe of claim 10, wherein the alloy is age-hardened and maintains a yield strength above 100 ksi at about 60° F. to about 480° F.
17. The semiconductor probe of claim 10, wherein the alloy is age-hardened and has a tensile elongation of greater than 2%.
Description
BRIEF DESCRIPTIONS OF THE DRAWINGS
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DETAILED DESCRIPTION
[0025] Overview: In the field of test probes, as device sizes decrease, the discrete space on each device available for being contacted by electrical test probes also decreases. At the same time, the increased processing power requires that the test probes carry higher test currents and thereby accommodate higher test temperatures. The result of these requirements is that: 1) test probe diameters must become smaller to ensure they can accurately be placed on the test pads, 2) the increase in test current coupled with the reduced probe diameter creates the requirement for improved electrical conductivity of the test probe material to avoid the danger of probe overheating and failure, 3) as the test temperatures rise, the alloys must exhibit good strength retention throughout the current rise sequence to avoid premature softening and failure during touch down and wipe, and 4) enhanced ductility is needed to allow extensive forming in the aged condition to ensure the tight dimensional tolerances needed in these miniature components.
[0026] Since power dissipation, or heating of the probe, is directly related to its electrical resistance, where:
power dissipated, in Watts=(probe current, in amperes).sup.2×(probe resistance, in Ohms)
it is readily apparent that probe heating is directly proportional to its resistance, and that reducing the test probe's resistance or increasing its electrical conductivity is a critical means to allow the operation of smaller diameter test probes at reasonable temperatures with increased current demands.
[0027] Moreover, in addition to lowering the bulk resistance of the probe wire, it is also imperative to maintain a low contact resistance during repeated touchdown of the probe on to the IC surface. This interfacial resistance is controlled by the normal force exerted on the probe at touchdown and the degree of wipe imposed after initial contact. In order to ensure consistent performance, the probe design must ensure that the overall loads remain in the elastic region through the test cycle. Therefore, under increased current density associated with using smaller diameter probes, it is important that the probe wire not exceed its yield strength at elevated temperatures to prevent softening, gram force reduction and eventually premature failure.
[0028] Additionally, the alloys must resist any oxidation that could increase probe-device contact resistance. The oxidation resistance of noble metal alloys is well known, while the particular advantages of palladium based noble metal alloys are universally recognized.
[0029] In view of these objectives, provided herein are palladium-based alloys which provide electrical conductivity in excess of 19.5% IACS, maintain hardness above 350 HK.sub.0.1 in order to provide wear resistance, and provide oxidation resistance. The alloys include a yield strength in excess of 100 ksi at temperatures up to 480° F. Sufficient ductility in the fully age-hardened condition enables the palladium-based alloy to be formed into finished test probes or electrical contacts, while eliminating the need for post-forming age hardening, thus avoiding attendant risks of thermal distortion of precision formed shapes during said aging treatment.
[0030] Further, and in contrast to prior approaches which do not recognize a correlation between an alloy system's palladium to copper and palladium to silver ratios as they relate to alloy hardenability and electrical conductivity, it has been discovered that a range of an alloy's Pd:Cu ratio achieves both aged hardness and electrical conductivity of a Pd/Cu ternary or higher alloy. In addition, it has been discovered that a range of Pd:Ag ratios in such alloys may further facilitate achieving suitable hardness and conductivity levels.
[0031] Accordingly, implementations provide Pd-based alloys having alloying additions of copper and silver with Pd:Cu and Pd:Ag ratios which provide increased electrical conductivity and sufficient hardness to meet the demands required of current test probes. Particularly, we have found that by properly controlling both the Pd:Cu and Pd:Ag ratios, it is possible to create age hardenable Pd alloys that combine high electrical conductivity, high hardness and excellent elevated temperature properties. Although the phase diagram of
[0032]
[0033] Alloy Compositions: The palladium-based alloys of the present disclosure are ternary or higher alloys. Alloying additions may include copper (Cu), silver (Ag) and/or rhenium (Re). Tables 1 and 2 provide alloy compositions, Pd:Cu and Pd:Ag ratios, and alloy properties of exemplary alloys of the present disclosure. These include any, any combination of, or all of Alloys 1907, 1941, 1910, 1900, 1904, 1859, 1948, 1929, 1933, 1937, 1943, 1930, 1934, 1938, 1935, 1912, 1936, 1931 and 1928.
[0034] The alloys may include palladium at about 45-55 wt %, about 45-50 wt %, about 47-55 wt %, about 50-55 wt %, about 50-54 wt % or about 51-55 wt %.
[0035] Copper may be present in the alloys at about 30-45 wt %, about 30-40 wt %, about 32-40 wt %, about 32-42 wt %, about 35-45 wt %, or about 36-43 wt %.
[0036] Silver may be present in the alloys at about 8-25 wt %, about 8-20 wt %, about 8-16 wt %, about 8-15 wt %, about 8-14 wt %, about 8.5-14 wt %, about 8-13 wt %, about 8-12 wt %, about 8-11 wt %, about 9-15 wt %, about 9-14 wt %, about 9-13 wt %, about 9-12 wt %, about 9-11 wt %, or about 8-10 wt %.
[0037] Rhenium may be present in the alloys at about 0-5 wt %, about 0.5-5 wt %, about 0.5-4.5 wt %, about 0.5-4 wt %, about 0.5-3.5 wt %, about 0.5-3.0 wt %, about 1.1-3.0 wt %, about 0.5-2.5 wt %, about 0.5-2.0 wt %, or about 0.5-1.5 wt %.
[0038] Zinc may be present in the alloys at about 0-3 wt %, about 0.1-1.0 wt %, about 0.2-0.7 wt %, about 0.5-3 wt %, about 1.0-3.0 wt %, or about 0.5-1.5 wt %.
[0039] The palladium-based alloys may additionally include up to about 1 percent of modifying elements including ruthenium, zirconium, gallium, and zinc.
[0040] The alloys of the present disclosure may consist exclusively of the specifically recited elements, such that the alloys are in a substantially pure form. For instance, where palladium is present in at least 50 wt % of the alloy, palladium makes up the remainder of the recited alloys, to the exclusion of all other (non-recited) substituents. Alternatively, it is to be understood that the presently recited palladium-based alloys may also comprise other substituents as well as those specifically recited, as may advantageously be desired. The recited alloys may also contain various impurities and other small amounts of matter, but in such amounts so as not to effect the advantageous properties of the inventive alloys. Preferably, such trace amounts of material will be present in less than 1000 ppm.
[0041] The alloys of the present disclosure may be free of nickel, chromium, gold, platinum, boron, iron, zinc, gallium and bismuth, as well as any other elemental addition. With respect to at least nickel, chromium, gold, platinum, boron, iron, these may be excluded from the disclosed alloys as being harmful to either or both electrical conductivity or aged hardness. For instance, Alloy 1856 is a Pd—Cu—Ag alloy with an alloying addition of Nickel, which results in a significant drop in conductivity (11.3 IACS) and has reduced properties compared to the Pd—Cu—Ag ternary Alloy 1943 (51.5 Pd-37.5 Cu-10.9 Ag). Alloy 1879 is another Pd—Cu—Ag alloy with an alloying addition of Chromium, which also results in a significant drop in conductivity (7.3 IACS) compared to Alloy 1943. Various trace elements may be present due to their unintentional introduction during casting and processing of the alloy as is well known by those skilled in metal casting and processing.
[0042] Alloy Ratios and Properties:
[0043] A weight ratio of palladium to copper may be at, or about, 1.05 and up to, or up to about, 1.6 by weight. A weight ratio of palladium to silver may be at, or about, 3 and up to, or up to about, 6 by weight.
[0044] The alloy in its fully age-hardened condition may have a hardness of at least 350 HK.sub.0.1, electrical conductivity of at least 19.5% IACS, tensile elongation greater than 2% in 2 inches, elevated temperature yield strength at 480° F. of at least 100 ksi.
[0045] Turning to the figures,
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[0048] The discovery that, after age hardening, only one section within the ordered region shown on the palladium copper phase diagram with a specific range of Pd:Cu ratios of about 1.05 and 1.6, yielded a combination of both high hardness and exceptionally high conductivity, was unexpected. Generally, it is assumed that for all compositions within the ordered phase field would yield roughly similar hardness.
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[0051] Particularly, turning to
[0052] The results show the palladium-based alloys with an addition of rhenium at 1.5 wt % had a tensile elongation of 8.2%, at 0.5 wt % had a tensile elongation of 5.71%. Each if these is an improvement over alloys containing no rhenium additions, which has a tensile elongation of 2.2%.
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[0054] In terms of the elevated temperature properties of these alloys, the effect of Re is very strong. As a shown in
[0055] An exemplary palladium-based alloy of the present disclosure (Alloy 1938) includes the following nominal composition:
palladium 51.5 wt %,
copper 36.5 wt %,
silver 10.5 wt %,
and rhenium 1.5 wt %.
[0056] Based on the composition of the alloy, the palladium to copper and palladium to silver ratios are: Pd:Cu ratio 1.41 by weight, and Pd:Ag ratio 4.9 by weight.
[0057] Alloy 1938 has a ductility that enables it to be fabricated into fine wire, with diameters below 0.004 in., using normal in-process anneals and drawn on conventional wire processing equipment. Final annealing of this wire by strand annealing at 900° C. (followed by an immediate water quench) softened the alloy and put it into a disordered condition, which is requisite for subsequent artificial age hardening. It was age hardened by heating it to 710° F. and holding it at that temperature for 90 min. Cooling to room temperature is not rate sensitive and took 1-2 hours. A protective atmosphere was maintained during all thermal treatments. After such annealing and aging heat treatments, the tensile and electrical properties of the 0.004 in. diameter wire fabricated from the alloy were:
TABLE-US-00001 Electrical 0.2% Hardness Conductivity UTS Y.S. Elongation Modulus (HK) (% IACS) (ksi) (ksi) (% in 2 in.) (ksi × 10.sup.6 psi) 451 27.96 191 148 13.3 18.7
[0058] The addition of rhenium with heat treatment further enhances ductility and can provide a microstructure suitable for probe tips used in electrical testing. For example, the table below illustrates the effects of initial cold work and heat treat temperature on the mechanical properties and conductivity for Alloy 1938.
TABLE-US-00002 Mechanical Properties of Alloy 1938 after Initial Cold Work and Heat Treatment of .004″ dia. wire HT Hardness UTS 0.2% YS Elongation Conductivity Condition conditions (Hk) (ksi) (ksi) % (% IACS) Annealed 227 110.1 83.9 24.2 5.8 HT from anneal 710 F., 90 min 412 181.2 157.3 6.49 24.9 HT from anneal 650 F., 6 hr 425 191.9 162.1 7.46 25.6 Cold Worked 339 196.9 156.1 2.17 6.1 HT from CW 710 F., 90 min 441 210.8 156.1 12.9 26.2 HT from CW 650 F., 6 hr 449 217.2 198.1 13.1 26.9
[0059] Table 1 lists the nominal alloy compositions, Pd:Cu and Pd:Ag ratios of exemplary palladium-based alloys of the present disclosure, while other alloy compositions and ratios are provided for purposes of distinction from the palladium-based alloys of Applicant's invention. Table 2 lists the conductivity, hardness, yield strength, and tensile elongation values of these various alloys.
TABLE-US-00003 TABLE 1 Alloy compositions and elemental ratios (by weight) Alloy Pd Cu Ag Re Other Code (wt %) (wt %) (wt %) (wt %) (wt %) Pd:Cu Pd:Ag 1907 47 43 9.75 0.25 Ga 1.09 4.82 1941 47.5 40 11 1.5 1.19 4.32 1910 50 40 8.5 1.5 1.25 5.88 1900 50 40 9.5 0.5 Zr 1.25 5.26 1904 50 40 9.6 0.25 Ga 1.25 5.21 0.15 Zr 1859 50 40 9.95 .05B 1.25 5.03 1948 49.2 39.3 10 1.5 1.25 4.92 1929 51.4 37.3 10.65 0.5 Zn 1.38 4.83 0.15 Ga 1933 51.5 37.3 10.7 0.5 Zn 1.38 4.81 1937 51.5 37.3 10.7 0.5 1.38 4.81 1943 51.6 37.5 10.9 1.38 4.73 1930 51.5 37 10 1.5 1.39 5.15 1934 51.5 36.5 10.5 1.5 Zn 1.41 4.9 1938 51.5 36.5 10.5 1.5 1.41 4.9 1935 51.4 36.3 10.3 1.5 0.5 Zn 1.42 4.99 1912 50 35 13.5 1.5 1.43 3.7 1936 51.4 35.4 10.2 1.5 1.5 Zn 1.45 5.04 1931 51.5 34.3 12.7 1.5 1.5 4.06 1928 51.5 34.2 9.8 4.5 1.51 5.26 Reduced Properties 1879 50 40 9.2 .8 Cr 1.25 5.44 Cr containing 1856 50 40 9.32 .68Ni 1.25 5.36 Ni containing 1945 38.5 46.5 13.5 1.5 0.83 2.85 Low Pd:Cu + Low Pd:Ag 1932 43 43 12.5 1.5 1 3.44 Low Pd:Cu 1913 45 30 25 1.5 1.8 Low Pd:Ag 1946 54.5 33 11 1.5 1.65 4.95 Hi Pd:Cu 1924 55 30 13.5 1.5 1.83 4.07 Hi Pd:Cu 1925 60 32 6.5 1.5 1.88 9.23 Hi Pd:Cu + Hi Pd:Ag 1926 65 26 7.5 1.5 2.5 8.67 Hi Pd:Cu + Hi Pd:Ag Paliney 7 35 14 30 Au = 10 2.5 1.17 Hi Pd:Cu + Pt = 10 Low Pd:Ag Zn = 1 H3C 40 29.9 29 Zn = 1 1.34 1.38 Low Pd:Ag B = .1
TABLE-US-00004 TABLE 2 Alloy compositions, elemental ratios (by weight), and key properties (conductivity, hardness, room and elevated temperature yield strengths, and room temperature tensile elongation) (Heat treat conditions 60 to 90 minutes at 710° F.) Cond Hardness in. in. YS YS % El Alloy Ann/Age Ann/Age @RT @480° F. (RT) Code Pd:Cu Pd:Ag (% IACS) (Hk) (ksi) (ksi) Ann/Age 1907 1.09 4.82 19.8 378 132 101 2.1 1941 1.19 4.32 20.4 392 165 137 4.5 1910 1.25 5.88 25.5 369 117 119 24.4 1900 1.25 5.26 24.3 400 1904 1.25 5.21 23.4 361 1859 1.25 5.03 21.9 359 1948 1.25 4.92 22.7 397 139 135 9.8 1929 1.38 4.83 24.5 385 156 4.4 1933 1.38 4.81 26.4 404 140 134 3.2 1937 1.38 4.81 23.2 399 164 152 5.7 1943 1.38 4.73 26.6 392 142 133 2.2 1930 1.39 5.15 26.3 400 146 4.0 1934 1.41 4.9 24.6 392 163 4.2 1938 1.41 4.9 24.6 428 165 165 8.2 1935 1.42 4.99 24.6 423 161 163 6.0 1912 1.43 3.7 23.6 456 198 169 5.3 1936 1.45 5.04 24.5 411 166 166 3.2 1931 1.5 4.06 22.5 460 193 3.2 1928 1.51 5.26 24.5 425 170 4.6 Reduced Properties 1879 1.25 5.43 7.3 352 Low conductivity 1856 1.25 5.36 11.3 339 Low Cond/Hard 1945 0.83 2.85 7.7 310 113 48 15.0 Low Cond/Hard 1932 1 3.44 7.0 253 95 82 17.9 Low Cond/Hard 1913 1.5 1.8 18.3 511 160 132 0.9 Low Cond/elong 1946 1.65 4.95 5.7 221 83 61 23.2 Low 1924 1.83 4.07 5.3 229 93 64 16.0 conductivity 1925 1.88 9.23 4.8 224 88 66 18.6 and Low 1926 2.5 8.67 3.7 228 94 94 21.4 Hardness And Low Strength Paliney 7 2.5 1.17 5.5 350 183 155 2.2 H3C 1.34 1.38 14.0 450 256 129 2.5
[0060] Exemplary uses for the alloys of the present disclosure are in the fields of electrical testing and medical devices. With respect to electrical testing, the alloys may be used in static and moveable electrical contact and probe applications. For instance, the alloys may be included as a component of a probe, a slip ring assembly (either as the ring or brush), or sliding contacts in applications such as a potentiometric sensor. Probes may include electrical probes used in connection with semiconductor testing. Semiconductor test probes may be formed as the alloys of the present disclosure, or the alloys may form a portion of the probe and a probe tip may be coupled thereto. The test probes may be configured as Cobra probes, cantilever probes, pogo pin probes and vertical probes.
[0061] From the above description and drawings, it will be understood by those of ordinary skill in the art that the particular embodiments shown and described are for purposes of illustration only and are not intended to limit the scope of the present invention. Those of ordinary skill in the art will recognize that the present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. References to details of particular embodiments are not intended to limit the scope of the invention.