EP0284699B1 - Composé intermétallique et ses applications - Google Patents
Composé intermétallique et ses applications Download PDFInfo
- Publication number
- EP0284699B1 EP0284699B1 EP87810140A EP87810140A EP0284699B1 EP 0284699 B1 EP0284699 B1 EP 0284699B1 EP 87810140 A EP87810140 A EP 87810140A EP 87810140 A EP87810140 A EP 87810140A EP 0284699 B1 EP0284699 B1 EP 0284699B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- atom
- elements
- compounds
- niai
- percent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 24
- 230000000694 effects Effects 0.000 description 17
- 239000010931 gold Substances 0.000 description 10
- 150000002739 metals Chemical class 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 229910019001 CoSi Inorganic materials 0.000 description 7
- 235000019589 hardness Nutrition 0.000 description 6
- 238000005242 forging Methods 0.000 description 5
- 229910004261 CaF 2 Inorganic materials 0.000 description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 229910005881 NiSi 2 Inorganic materials 0.000 description 3
- 241000607479 Yersinia pestis Species 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000003353 gold alloy Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910000951 Aluminide Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- 229910003322 NiCu Inorganic materials 0.000 description 2
- 229910012990 NiSi2 Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004035 construction material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- -1 AuAl 2 Chemical class 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910002515 CoAl Inorganic materials 0.000 description 1
- 229910018999 CoSi2 Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000960 colored gold Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910000923 precious metal alloy Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910001256 stainless steel alloy Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44C—PERSONAL ADORNMENTS, e.g. JEWELLERY; COINS
- A44C27/00—Making jewellery or other personal adornments
- A44C27/001—Materials for manufacturing jewellery
- A44C27/002—Metallic materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/02—Alloys based on gold
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
Definitions
- DE-PS 659 155 proposes alloying the compound AuA1 2 with aluminum or other soft metals in order to reduce the brittleness. Attempts have also been made to apply the metal by plasma spraying or to create a layer by chemically diffusing Al into Au. The reactions in these processes are difficult to control and the metal is porous. It has therefore not been possible to obtain a colored gold alloy that can be used for jewelry.
- Other colored, intermetallic compounds are also known, such as PtA1 2 , NiAI, CoAi, NiGa, Pdln or GoSi 2 ; PtA1 2 and CoAl are yellow, NiAI is blue, Pdln red, CoSi 2 blue-black. These metals are also usually brittle, which makes it impossible to use the decorative effect of the color for jewelry.
- various compounds, such as AuAl 2 tend to spontaneously decay in reactive media.
- the first two conditions are the selection criteria for the fact that it is a colored material.
- the third condition ensures that this material is also practically usable, i.e. that the brittleness inherent in the intermetallic compounds is usually missing or is only present to an insignificant, no longer disturbing extent and that the metal in air and in aqueous electrolytes is not attacked and does not decompose. Therefore, this material is used for the manufacture of jewelry and jewelry such as watch cases, watch straps, lighters, writing utensils, etc. and of decorated metal goods of all kinds, e.g. of door fittings, spectacular weapons, multicolored watch straps, lighters, etc. suitable.
- the brittle behavior of the intermetallic compounds is the rule rather than the exception and is due to the special microscopic expansion processes in these metals with ordered atomic structures.
- the brittleness manifests itself as small elongation at break and low fracture toughness with the further effect that the metals are sensitive to knocks and nicks and are easily scratched. It has been found that these unfavorable properties can be largely suppressed if a grain size of less than 50 ⁇ m is forced by suitable metallurgical processes.
- This fine granularity required for the material according to the invention can be obtained, for example, by hot working, for example by forging or by hot pressing, with the temperature for this working being between 45% and 80% of the solidification or formation temperature of the phase measured in ° K.
- Another possibility for producing the fine-grained state is that the material is quenched directly and quickly from the liquid state or that it is applied in layers by atomization.
- Table 1 gives an overview of the 12 colored intermetallic compounds that exist, are stable and meet the requirements a) and b) of claim 1.
- Table 2 lists four other compounds that exist only at high temperatures, but can be kept in the metastable state by quenching.
- the combinations of the elements not listed in the tables either do not exist at all as a compound of the formula AB or AB 2 , or they have a different type of cubic crystal structure than the two required. In the latter case, the color effect is missing.
- the color effect occurs only for the structure types CsCI / B 2 and CaF 2 / C1.
- the areas of existence of these two phases, including a substitution of components A or B in the corresponding formulas AB and AB 2 can also be specified as limits of the so-called electron concentration.
- the electron concentration e / a is the sum of the valence electrons per atom in the compound, namely where a i is the concentration in atomic% and v i is the number of valence electrons of component i.
- intermetallic compounds according to the invention achieve an indentation hardness (Vickers hardness) of 4000 to more than 6000 N / mm 2 (Table 1). This makes the materials for jewelry were interesting because these hardnesses are sufficient for a high resistance to abrasion and scratching.
- stainless steel and gold alloys have an indentation hardness of 1500 to 2500 N / mm 2 . Because of the high hardness, however, intermetallic compounds can hardly be processed by sawing, turning, milling and drilling and the shaping is better by grinding, electro-eroding, electrochemical processing, etc. or by forging into the mold at medium and high temperatures.
- Table 1 also shows the density of the intermetallic compounds of interest. For various of these metals, it is small, compared to stainless steel of about 8 g / cm 3 or gold alloys with about 15 g / cm 3 jewelry items should not be heavy and in the case of precious metal alloys, the low density gives a price advantage.
- the alloys of the NiAI system are interesting because of the variable color effects. These are: 50.2Ni49.8AI blue, 50.2Ni40A19.8Si blue-green, 60Ni40A1 yellow, 54Ni6Cu40AI yellow-red, 62Ni38AI yellow.
- the compositions are over-stoichiometric in order to reliably suppress grain boundary embrittlement. The last-mentioned composition even goes beyond the area of existence of the NiAI phase; With a heat treatment (600 - 800 ° C) a small amount of the Ni 3 AlPhase is then excreted and the strength and fracture toughness are massively increased.
- the alloys of the NiAI system are advantageously melted in an induction furnace under vacuum or argon.
- the metal is homogenized and made fine-grained (encapsulated to avoid oxidation) by hot forging or hot pressing.
- the degree of deformation (reduction in cross-section) is at least 6 and the temperature must not exceed 1,200 ° C if the grain size is to be less than 50 ⁇ m (1,000 ° C for grain sizes less than 20 ⁇ m). Any relaxation annealing is carried out at around 800 ° C.
- the Pdln system also shows variable color effects, namely: 50.2Pd49.81n red, 60Pd401n yellow.
- the A component can be partially substituted by Ni, Cu, Au and the B component can be exchanged for Al, Si, e.g. in 43Pd7.2Cu49.81n red, 50.2Pd39.8ln10Al red, 57Pd36in7Si yellow.
- the hardness of the multi-component systems is higher than that of the binary connections.
- the hot forming is carried out at temperatures from 950 to 600 ° C in order to maintain the fine-grained structure.
- AuA1 2 is very brittle and susceptible to the "pest effect".
- the alloys of the system can only be used if the A component is present in excess and the structure is fine-grained.
- the connection is plastically deformable at 400 ° C and higher temperatures.
- a practical upper limit for heat treatments and especially for hot forging or hot pressing for grain refinement is the temperature of 625 ° C, corresponding to the melting point of the neighboring phase AuAI.
- interesting compounds in the system are 34Au66AI (79% by weight Au) purple, 31Au3Cu66AI (75% by weight Au) purple.
- Other possible elements for substitution are Ni, Pt for the A component and up to 8 atomic% Si for the B component.
- PtAl 2 is a chemically very resistant and hard compound of bright yellow color and a density which is lower than that of stainless steel.
- a suitable composition is 34Pt66AI (79 wt% Pt). The metal is formed at temperatures from 1 150 ° C to 800 ° C.
- connections AuGa 2 and Auln 2 have a bright blue color. They have low solidification temperatures and are soft and therefore not very wear-resistant. Their application is limited to non-exposed parts of jewelry, such as clock faces.
- the silicides of Co, Ni are hard and fracture tough and the blue-black color is decorative as a contrasting color.
- the interesting compounds have the composition 34Ni66Si and 34Co66Si.
- Ni and Co are fully interchangeable or up to about 10 atomic% Ni or Co can be substituted by Fe or Cu.
- Hot forging or hot pressing is carried out in the temperature range from 1 150 to 500 ° C for the Co compound and below 966 ° C (eutectic reaction of the Ni-rich phases) for the Ni compound. Very fine-grained structures below 20 ⁇ m are obtained below a temperature of 800 ° C.
- the intermetallic compounds for example CoSi 2 , NiAI, Pdln, can also be applied as a layer. Ion atomization (in He, Ar discharge) is suitable. Fine-grained, thick layers (of 10 ⁇ m and more) of sufficient ductility are obtained if the deposition is carried out on a heated substrate (for example made of stainless steel).
- the colored intermetallic connections can be connected to common construction materials such as brass, steel, titanium etc. by soldering.
- the solder and the process should be selected so that there is no massive recrystallization of the material, e.g. with melting points of the solder below 900 ° C for NiAI, PtA1 2 , CoSi 2 etc. and below 600 ° C for AuA1 2 .
- a color effect always depends on the surface quality of the body.
- Optical properties of metals are usually described as specular reflection on polished, shiny surfaces.
- light sources are point-like as well as diffuse, and the effect of polished and rough surfaces is different; the rough, polished or chemically etched surface appears much lighter than the polished metal.
- the effect is particularly noticeable for the blue compounds NiAI or CoSi 2 , but less pronounced for the yellow and red metals.
- mechanical deformations e.g. through grinding and polishing, which can interfere with the formation of colors or give gray tones. This undesirable effect can be corrected, for example by tempering the compounds at medium temperatures below recrystallization or by chemically etching away the disturbed surface layer.
- Surface treatment plays an important role in the use of colored metals.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Adornments (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Claims (4)
1. Matière constituée par un composé intermétallique de formule AB ou AB2, caractérisée en ce que
a) A=Fe ou Co ou Ni ou Pd ou Pt ou Au ou un mélange de ces éléments, chacun de ces éléments pouvant être remplacé jusqu'à 15% atomique par du Cu, et
B=AI ou Ga ou In ou Si ou un mélange de ces éléments, A pouvant être présent en un excès pouvant atteindre 15% atomique au-dessus de la valeur stoechiométrique et la matière pouvant contenir jusqu'à 1 % atomique d'impuretés ou d'éléments étrangers,
B=AI ou Ga ou In ou Si ou un mélange de ces éléments, A pouvant être présent en un excès pouvant atteindre 15% atomique au-dessus de la valeur stoechiométrique et la matière pouvant contenir jusqu'à 1 % atomique d'impuretés ou d'éléments étrangers,
b) en ce qu'elle possède une structure cubique du type B2 ou du type C1 et
c) en ce qu'elle présente une granulométrie inférieure à 50 mm.
2. Utilisation de la matière selon la revendication 1 pour la réalisation d'articles de bijouterie et d'articles métalliques décorés.
3. Articles de bijouterie, caractérisés en ce qu'ils sont faits au moins en partie en une matière selon la revendication 1.
4. Articles métalliques décorés, caractérisés en ce que l'élément de décoration est une matière selon la revendication 1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH876/87 | 1987-03-10 | ||
| CH87687 | 1987-03-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0284699A1 EP0284699A1 (fr) | 1988-10-05 |
| EP0284699B1 true EP0284699B1 (fr) | 1990-08-01 |
Family
ID=4197231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP87810140A Expired - Lifetime EP0284699B1 (fr) | 1987-03-10 | 1987-03-11 | Composé intermétallique et ses applications |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4911762A (fr) |
| EP (1) | EP0284699B1 (fr) |
| JP (1) | JPS63235438A (fr) |
| DE (1) | DE3764087D1 (fr) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01123044A (ja) * | 1987-11-09 | 1989-05-16 | Fuji Dies Kk | 金色硬質合金及びそれを被覆した装飾品 |
| AU616739B2 (en) * | 1988-03-11 | 1991-11-07 | Unisearch Limited | Improved solution growth of silicon films |
| US4802933A (en) * | 1988-04-21 | 1989-02-07 | Allied-Signal Inc. | Nickel-palladium based brazing alloys |
| JPH02185936A (ja) * | 1989-01-12 | 1990-07-20 | Agency Of Ind Science & Technol | 洋紅色を有する金合金 |
| US5045280A (en) * | 1989-10-04 | 1991-09-03 | Mintek | Intermetallic compounds |
| JPH04176846A (ja) * | 1990-11-09 | 1992-06-24 | Seiko Instr Inc | カラー金合金 |
| US5380482A (en) * | 1991-10-18 | 1995-01-10 | Aspen Research, Inc. | Method of manufacturing ingots for use in making objects having high heat, thermal shock, corrosion and wear resistance |
| US6242104B1 (en) | 1995-10-27 | 2001-06-05 | Implico B.V. | Precious metal composition and artifacts made therefrom |
| JP2002275560A (ja) * | 2001-03-13 | 2002-09-25 | National Institute Of Advanced Industrial & Technology | （Ｃｏ１−ｘＮｉｘ）Ｓｉ２及び（Ａｕ１−ｘＮｉｘ）Ａｌ２，（Ａｕ１−ｘＣｕｘ）Ａｌ２金属間化合物及びそれを用いた装飾品 |
| US6613275B1 (en) * | 2002-07-19 | 2003-09-02 | Metalor Technologies Sa | Non-precious dental alloy |
| EP2322316B1 (fr) | 2008-07-24 | 2014-05-14 | Tanaka Kikinzoku Kogyo K.K. | Métal de charge de brasage au-ga-in |
| SE534817C2 (sv) * | 2010-05-04 | 2012-01-10 | Förfarande för att producera ett kristallint ytskikt | |
| EP2402467B1 (fr) | 2010-06-30 | 2015-06-17 | The Swatch Group Research and Development Ltd. | Alliage d'or à dureté améliorée |
| JP6837631B2 (ja) * | 2017-02-23 | 2021-03-03 | 学校法人東京理科大学 | 含ブループラチナ装飾品又は含イエロープラチナ装飾品 |
| EP3527679A1 (fr) * | 2018-02-19 | 2019-08-21 | Richemont International SA | Composite de platine comprenant des particules de platine intermétalliques |
| EP4053299A1 (fr) * | 2021-03-01 | 2022-09-07 | Richemont International SA | Alliage d'or violet à comportement mécanique amélioré |
| KR102924939B1 (ko) * | 2021-03-29 | 2026-02-09 | 갓코호우징 도쿄리카다이가쿠 | 금 합금 및 금 합금의 제조 방법 |
| US11268174B1 (en) | 2021-06-10 | 2022-03-08 | Chow Sang Sang Jewellery Company Limited | Jewelry alloy |
| CN113652643A (zh) * | 2021-08-13 | 2021-11-16 | 杭州兴宸科技有限公司 | 一种粉末冶金靶材紫金镀膜方法 |
| CN115011833B (zh) * | 2021-12-21 | 2023-08-29 | 昆明理工大学 | 一种改善紫色18k金铝合金韧性的配方及其制备方法 |
| EP4407055A1 (fr) * | 2023-01-27 | 2024-07-31 | Jean-Claude Puippe | Procédé d'obtention d'un composant en alliage palladium-indium ayant une bonne aptitude au façonnage |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE659155C (de) * | 1935-09-29 | 1938-04-26 | Degussa | Verwendung farbiger Goldlegierungen fuer Schmuckstuecke |
| JPS5315446B2 (fr) * | 1972-10-19 | 1978-05-25 | ||
| AT333067B (de) * | 1974-09-20 | 1976-11-10 | Plansee Metallwerk | Schmuckstuck |
| GB2005649A (en) * | 1977-09-22 | 1979-04-25 | Johnson Matthey Co Ltd | Electrodes |
| FR2541312B1 (fr) * | 1983-02-21 | 1987-11-27 | Inst Metallurg Im Baiko | Alliage a base de palladium |
| DE3307039C2 (de) * | 1983-02-28 | 1987-04-30 | Institut elektrochimii Ural'skogo naučnogo centra Akademii Nauk SSSR, Sverdlovsk | Werkstück aus Palladium mit einer mittels Schmelzflußelektrolyse aufgebrachten Schicht |
| FR2564037B1 (fr) * | 1984-05-11 | 1986-10-03 | Inst Francais Du Petrole | Structure alveolaire destinee a recouvrir une surface curviligne et procede de realisation |
| JPS6130642A (ja) * | 1984-07-20 | 1986-02-12 | Tokuriki Honten Co Ltd | Ｋ１８カラツト紫金 |
-
1987
- 1987-03-11 EP EP87810140A patent/EP0284699B1/fr not_active Expired - Lifetime
- 1987-03-11 DE DE8787810140T patent/DE3764087D1/de not_active Expired - Lifetime
-
1988
- 1988-02-23 US US07/159,326 patent/US4911762A/en not_active Expired - Lifetime
- 1988-03-10 JP JP63055076A patent/JPS63235438A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| EP0284699A1 (fr) | 1988-10-05 |
| JPS63235438A (ja) | 1988-09-30 |
| DE3764087D1 (de) | 1990-09-06 |
| US4911762A (en) | 1990-03-27 |
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