CN87100422A - Gold-composite coating of gold-fluorine graphite with self-lubrication and method - Google Patents
Gold-composite coating of gold-fluorine graphite with self-lubrication and method Download PDFInfo
- Publication number
- CN87100422A CN87100422A CN 87100422 CN87100422A CN87100422A CN 87100422 A CN87100422 A CN 87100422A CN 87100422 CN87100422 CN 87100422 CN 87100422 A CN87100422 A CN 87100422A CN 87100422 A CN87100422 A CN 87100422A
- Authority
- CN
- China
- Prior art keywords
- gold
- coating
- plated
- composite coating
- plating solution
- 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.)
- Pending
Links
- 239000011248 coating agent Substances 0.000 title abstract description 21
- 238000000576 coating method Methods 0.000 title abstract description 21
- 238000000034 method Methods 0.000 title abstract description 15
- 239000002131 composite material Substances 0.000 title abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title abstract description 6
- 229910002804 graphite Inorganic materials 0.000 title description 3
- 239000010439 graphite Substances 0.000 title description 3
- 238000005461 lubrication Methods 0.000 title description 2
- KZKGLGIVGQYOTG-UHFFFAOYSA-N [F].[Au] Chemical compound [F].[Au] KZKGLGIVGQYOTG-UHFFFAOYSA-N 0.000 title 1
- 238000007747 plating Methods 0.000 claims abstract description 23
- 238000009713 electroplating Methods 0.000 claims abstract description 10
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 9
- RDBONSWKYPUHCS-UHFFFAOYSA-N 1-undecyl-4,5-dihydroimidazole Chemical compound CCCCCCCCCCCN1CCN=C1 RDBONSWKYPUHCS-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052737 gold Inorganic materials 0.000 abstract description 16
- 238000003756 stirring Methods 0.000 abstract description 12
- 238000000151 deposition Methods 0.000 abstract description 3
- 238000004070 electrodeposition Methods 0.000 abstract description 3
- UJLXKYSGBFPPAD-UHFFFAOYSA-N gold;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Au].OC(=O)CC(O)(C(O)=O)CC(O)=O UJLXKYSGBFPPAD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017398 Au—Ni Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- YWIHFOITAUYZBJ-UHFFFAOYSA-N [P].[Cu].[Sn] Chemical compound [P].[Cu].[Sn] YWIHFOITAUYZBJ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
本发明研究了获取电沉积Au—(CF)n复合镀层的方法，获取的镀层具有自润滑性，以Au—(CF)n镀层为摩擦对偶的摩擦系数，仅为镀钝金摩擦对偶的1/10～1/8。The present invention studies the method for obtaining electrodeposited Au—(CF) n composite coating, and the coating obtained has self-lubricating properties, and the friction coefficient of the friction couple with Au—(CF) n coating is only 1 of the friction couple of plated blunt gold /10～1/8.
本发明是在柠檬酸盐镀金液中加入氟化石墨微粉，通过电沉积得到Au—(CF)n复合镀层的。为了这个目的，同时在镀液中加入表面活性剂、共沉积促进剂。电沉积时采用板泵连续搅拌。在通常电镀工艺条件下取得镀层。被镀覆件可以是挂镀，也可以是滚镀。The present invention adds fluorinated graphite micropowder into the citrate gold plating solution, and obtains Au—(CF) n composite coating through electrodeposition. For this purpose, surfactants and co-deposition accelerators are added to the plating solution at the same time. A plate pump was used for continuous stirring during electrodeposition. The coating is obtained under the usual electroplating process conditions. The plated parts can be rack plated or barrel plated.
Description
本发明为金属表面处理技术领域。The invention relates to the technical field of metal surface treatment.
目前镀金广泛应用于电子工业。世界年耗金量总数的 1/3 应用于电子元件的电镀。这是由于金镀层具有良好的化学稳定性、导电性、接触电阻稳定，适合于电子元件对电性能稳定、可靠的要求。但金的质地柔软，摩擦系数大，耐磨性差。为了克服这些缺点，人们研究各种硬金（合金）电镀，如Au-Cc Au-Ni等，旨在提高镀金层的硬度，增加耐磨性，降低金镀层的摩擦系数。虽在硬度与耐磨性方法取得了一定进展，但摩擦系数下降很有限。特别是电子工业发展要求电连接器芯数日趋增多，摩擦力过大。为使多芯数的电连接器能灵便的连接和分断，降低摩擦力的研究引起了极大兴趣。At present, gold plating is widely used in the electronics industry. One-third of the world's annual gold consumption is used for electroplating of electronic components. This is because the gold plating has good chemical stability, conductivity, and stable contact resistance, which is suitable for the stable and reliable electrical performance requirements of electronic components. However, gold is soft, has a large friction coefficient, and poor wear resistance. In order to overcome these shortcomings, people have studied various hard gold (alloy) electroplating, such as Au-Cc Au-Ni, etc., aiming to improve the hardness of the gold plating layer, increase wear resistance, and reduce the friction coefficient of the gold plating layer. Although some progress has been made in hardness and wear resistance methods, the reduction in friction coefficient is very limited. In particular, the development of the electronics industry requires that the number of cores of electrical connectors is increasing day by day, and the friction force is too large. In order to enable multi-core electrical connectors to be flexibly connected and disconnected, research on reducing friction has aroused great interest.
采用电共沉积的方法，使在镀液中能稳定、具有润滑性的粉末，与金属共同在阴极析出，而形成具有自润滑性的复合镀层，是降低摩擦力、提高使用寿命的方法。常用的润滑粉末可以选取石墨、二硫化钼，但二硫化相化学稳定性不好，石墨在真空条件下，润滑性能恶化。因而选取氟化石墨作为润滑剂。The method of electrodeposition is to make the powder that is stable and lubricating in the plating solution precipitate at the cathode together with the metal to form a self-lubricating composite coating, which is a method to reduce friction and increase service life. Commonly used lubricating powders can be selected from graphite and molybdenum disulfide, but the chemical stability of the disulfide phase is not good, and the lubrication performance of graphite deteriorates under vacuum conditions. Therefore, graphite fluoride is selected as a lubricant.
本发明的工艺方法是将化学稳定性好，具有良好润滑性，特别是在真空条件下仍保持良好润滑性的氟化石墨微粉（平均粒径≤0.5μm）加入常用的柠檬酸盐镀金液，按照通常的电镀方法，获取金-氟化石墨复合镀层。这种具有自润滑性能，且又有良好电气性能、化学稳定性好的金-氟化石墨复合镀层，以代替纯金镀层。这样镀层的应用不仅可以降低在滑动摩擦过程的摩擦力，而且在使用寿命相同的条件下，节省黄金。这种自润滑复合镀层，可以用于各种有滑动摩擦的电子元件表面的镀复。在不影响电气性能和可靠性的条件下，减低摩擦阻力，减少磨损，增长使用寿命。特别是用于真空条件下的电子器件摩擦表面的自润滑镀层。The process method of the present invention is to add fluorinated graphite powder (average particle size ≤ 0.5 μm) with good chemical stability and good lubricity, especially still maintaining good lubricity under vacuum conditions, to a commonly used citrate gold plating solution, and obtain a gold-graphite fluoride composite coating according to a common electroplating method. This gold-graphite fluoride composite coating with self-lubricating properties, good electrical properties and good chemical stability can replace the pure gold coating. The application of such a coating can not only reduce the friction force in the sliding friction process, but also save gold under the condition of the same service life. This self-lubricating composite coating can be used for plating the surfaces of various electronic components with sliding friction. Under the condition of not affecting the electrical performance and reliability, the friction resistance is reduced, the wear is reduced, and the service life is increased. In particular, it is used for the self-lubricating coating of the friction surface of electronic devices under vacuum conditions.
氟化石墨是目前憎水性最强物质之一，为使其能均匀的悬浮在镀液中，必须选用适宜的表面活性剂。选定采用十一烷基咪唑啉。先将十一烷基咪唑啉溶于小量蒸馏，再把氟化石墨微粉加入，十一烷基咪唑啉与氟化石墨的重量比为0.08～0.15，用高速搅拌器充分搅拌，搅拌器的转速为10.000～15.000转/分，经2-20分钟搅拌，使氟化石墨充分润滑，成为均匀的糊状。在磁力搅拌器的搅拌情况下将糊状物加入镀液。镀液中事先加入并溶解了共沉积促进剂Ti2SO4，共沉积促进剂的用量为1～5g/e。Graphite fluoride is one of the most hydrophobic substances at present. In order to make it evenly suspended in the plating solution, a suitable surfactant must be selected. Undecyl imidazoline was selected. First, undecyl imidazoline was dissolved in a small amount of distillation, and then the fluorinated graphite powder was added. The weight ratio of undecyl imidazoline to graphite fluoride was 0.08-0.15. It was fully stirred with a high-speed stirrer at a speed of 10.000-15.000 rpm. After stirring for 2-20 minutes, the graphite fluoride was fully lubricated and became a uniform paste. The paste was added to the plating solution under the stirring of a magnetic stirrer. The co-deposition promoter Ti 2 SO 4 was added and dissolved in the plating solution in advance, and the amount of the co-deposition promoter was 1-5 g/e.
电镀的工艺条件与一般镀金工艺条件相同。温度控制在30～60℃，电流密度0.05～0.15A/dm2，PH5.2。为使氟化石墨在电镀过程中能均匀的悬浮在镀液中，应采用适当的搅拌。机械涡轮式搅拌或板泵搅拌都能达到这个目的，但溶液搅拌的最好方式是板泵搅拌。搅拌的强度以使微粉能均匀悬浮为适宜。过份剧烈的搅拌对共沉沉积不利。The process conditions of electroplating are the same as those of general gold plating. The temperature is controlled at 30-60℃, the current density is 0.05-0.15A/ dm2 , and the pH is 5.2. In order to make the graphite fluoride evenly suspended in the plating solution during the electroplating process, appropriate stirring should be used. Mechanical turbine stirring or plate pump stirring can achieve this goal, but the best way to stir the solution is plate pump stirring. The intensity of stirring is appropriate to make the micro powder evenly suspended. Excessive stirring is not good for co-precipitation.
通过本工艺方法，可以获取含有氟化石墨体积百分比8～10%的金-氟化石墨复合镀层，其摩擦系数为0.15～0.2，而纯金镀层的摩擦系数为1.5～1.8。而且耐磨性也有明显提高。Through this process, a gold-graphite fluoride composite coating containing 8-10% graphite fluoride by volume can be obtained, and its friction coefficient is 0.15-0.2, while the friction coefficient of the pure gold coating is 1.5-1.8. In addition, the wear resistance is significantly improved.
实施例1：以黄铜块（20×10×4）为试件，在镀槽中挂镀金-氟化石墨复合镀层，镀槽内镀液成份及电镀条件：Example 1: A brass block (20×10×4) was used as a test piece, and a gold-graphite fluoride composite coating was plated in a plating tank. The composition of the plating solution in the plating tank and the electroplating conditions were as follows:
Au（以K〔Au（CN）2〕形式加入 5-7g/LAu (5-7 g/L in the form of K〔Au（CN） 2 〕
（NH4）3C6H5O7100～120g/L(NH 4 ) 3 C 6 H 5 O 7 100～120g/L
氟化石墨 （CF）n（平均粒径≤0.5μm） 30-50g/LGraphite fluoride (CF) n (average particle size ≤ 0.5 μm) 30-50 g/L
H3C6H5O7适量调节镀液PH值H 3 C 6 H 5 O 7 to adjust the pH value of the plating solution
十一烷基咪唑啉 4～6g/LUndecyl imidazoline 4～6g/L
Tl2SO42～3g/LTl 2 SO 4 2～3g/L
PH 5.2～5.8PH 5.2～5.8
t 30～40℃t 30～40℃
DK 0.05～0.15A/dm2 DK 0.05～0.15A/ dm2
板泵连续搅拌Plate pump continuous stirring
以本发明工艺条件镀出的复合镀层中（CF）n，最高体积百分比为14.7%，一般可达5～12%，摩擦系数为0.1～0.15，在镀层厚度达1μm时，可以无孔。耐湿热及抗盐雾性能试验，经72小时，试样无明显变化。In the composite coating plated under the process conditions of the present invention, the maximum volume percentage of (CF) n is 14.7%, generally up to 5-12%, the friction coefficient is 0.1-0.15, and when the coating thickness reaches 1 μm, there is no hole. In the moisture and heat resistance and salt spray resistance test, after 72 hours, the sample has no obvious change.
实施例2：以磷锡铜材料的电连接器用插针及孔为试件，在镀槽中用滚镀的方法电镀。镀液成份及电镀条件：Example 2: Using phosphorus tin copper material as test pieces for electrical connector pins and holes, electroplating was performed in a plating tank using a barrel plating method. Plating solution composition and electroplating conditions:
Au 以K〔Au（CN）2〕形式加入） 5～7g/LAu added in the form of K〔Au（CN） 2 〕5～7g/L
（NH4）3C6H5O7100～120g/L(NH 4 ) 3 C 6 H 5 O 7 100～120g/L
H3C6H5O7适量调节镀液PN值H 3 C 6 H 5 O 7Adjust the PN value of the plating solution appropriately
十一烷基咪唑啉 4～6g/LUndecyl imidazoline 4～6g/L
Tl2SO42～3g/LTl 2 SO 4 2～3g/L
PH 5.2～5.8PH 5.2～5.8
t 40～45℃t 40～45℃
DK 0.04～0.1A/dm2 DK 0.04～0.1A/ dm2
板泵连续搅拌Plate pump continuous stirring
滚筒（φ45×70） 转速1～3转/分Roller (φ45×70) Speed 1～3 rpm
滚镀筒材料为有机玻璃制作，钻有φ0.5孔。获取电连接器用的插针及孔的镀件。测试接触电阻为1.75～3.00mΩ，而纯金镀件为1.50～2.00mΩ。以Au-（CF）n复合镀件组装的电连接器，断开时拉力为45～80N，而纯金镀件组装的需350～550N。这是因为Au-（CF）n复合镀层的摩擦系数较纯金镀层的摩擦系数明显下降。而电连接器电性能符合要求，断开力仅为纯金镀层的 1/5 ～ 1/8 。The barrel material is made of plexiglass and drilled with a φ0.5 hole. Obtain the plated parts for the pins and holes of the electrical connector. The tested contact resistance is 1.75~3.00mΩ, while the pure gold plated parts are 1.50~2.00mΩ. The electrical connector assembled with Au-(CF) n composite plated parts has a pulling force of 45~80N when disconnected, while the pure gold plated parts require 350~550N. This is because the friction coefficient of the Au-(CF) n composite coating is significantly lower than that of the pure gold coating. The electrical performance of the electrical connector meets the requirements, and the disconnection force is only 1/5~1/8 of that of the pure gold coating.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87100422 CN87100422A (en) | 1987-01-28 | 1987-01-28 | Gold-composite coating of gold-fluorine graphite with self-lubrication and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87100422 CN87100422A (en) | 1987-01-28 | 1987-01-28 | Gold-composite coating of gold-fluorine graphite with self-lubrication and method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN87100422A true CN87100422A (en) | 1988-04-06 |
Family
ID=4812867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87100422 Pending CN87100422A (en) | 1987-01-28 | 1987-01-28 | Gold-composite coating of gold-fluorine graphite with self-lubrication and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN87100422A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371502C (en) * | 2004-02-27 | 2008-02-27 | 台湾积体电路制造股份有限公司 | Electrochemical plating electrolyte and method for plating metal on plating surface |
-
1987
- 1987-01-28 CN CN 87100422 patent/CN87100422A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100371502C (en) * | 2004-02-27 | 2008-02-27 | 台湾积体电路制造股份有限公司 | Electrochemical plating electrolyte and method for plating metal on plating surface |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5667659A (en) | Low friction solder electrodeposits | |
| US5601696A (en) | Silver plating baths and silver plating method using the same | |
| US20200115815A1 (en) | Coated articles, electrodeposition baths, and related systems | |
| JP4675626B2 (en) | Bronze electrodeposition method and electrolyte | |
| US3892637A (en) | Method of treatment of metal surfaces | |
| US4076598A (en) | Method, electrolyte and additive for electroplating a cobalt brightened gold alloy | |
| US20120121925A1 (en) | Coated articles, electrodeposition baths, and related systems | |
| EP1930478A1 (en) | Electrolyte composition and method for the deposition of quaternary copper alloys | |
| EP2755819B1 (en) | Silver alloy coated articles | |
| EP0636713A2 (en) | Alcaline cyanide baths for electroplating copper-tin alloys coatings | |
| EP3816326B1 (en) | Acidic aqueous binary silver-bismuth alloy electroplating compositions and methods | |
| CN87100422A (en) | Gold-composite coating of gold-fluorine graphite with self-lubrication and method | |
| Krishnan et al. | Electroplating of Copper from a Non-cyanide Electrolyte | |
| JPS5937354B2 (en) | Gold alloy electroplating baths and gold alloys | |
| Jordan | Lead-free Tin alloys as substitutes for Tin-lead alloy plating | |
| US4470886A (en) | Gold alloy electroplating bath and process | |
| Mason et al. | Alloy gold deposits: Have they any industrial use? | |
| JPS6023197B2 (en) | Method for composite electrodeposition of boron nitride and metal | |
| JPS61223194A (en) | Electrodeposition bath of gold/tin alloy film | |
| Jordan | Electrodeposition of Tin-Lead Alloys | |
| US3738920A (en) | Plating tarnish-inhibited bright silver alloy | |
| CA1045577A (en) | Electrodeposition of bright tin-nickel alloy | |
| CN113737236B (en) | High-corrosion-resistance composite coating and preparation method and application thereof | |
| CN113388870B (en) | A composite plating solution and preparation method thereof, electroplating method and coating formed therefrom | |
| JPS6070197A (en) | Silver alloy plating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |