CN1289864A - Surface activating process of Ti and Ti alloy for bright electroplating - Google Patents
Surface activating process of Ti and Ti alloy for bright electroplating Download PDFInfo
- Publication number
- CN1289864A CN1289864A CN 99119772 CN99119772A CN1289864A CN 1289864 A CN1289864 A CN 1289864A CN 99119772 CN99119772 CN 99119772 CN 99119772 A CN99119772 A CN 99119772A CN 1289864 A CN1289864 A CN 1289864A
- Authority
- CN
- China
- Prior art keywords
- acid
- weight
- phenylsulfonic
- trimethyl
- titanium
- 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.)
- Granted
Links
Abstract
A surface activating process for Ti or Ti-alloy includes removing permanent passivated film from surface of workpiece and putting it in activating liquid, which is an aqueous solution containing sulfuric acid and/or nitric acid (40-95 wt.%) and the C10-C20 ammonium trimethylhalide plus one or more C1-C4 alkyl and/or halogen substituted or not substituted benzenesulfonic acid. Said Ti or Ti-ally can be used for bright electroplating.
Description
The invention belongs to the activation solution that uses in a kind of titanium or titanium alloy surface activating process that is applicable to bright plating and this method.
Because the metal titanium activity is strong, under conditions of air, the surface forms the oxide film of the very thick densification of one deck in long-term exposure, make titanium and alloy surface passivation thereof, in electroplating process, cause the sticking power of metal plating and titanium and alloy substrates thereof not strong, do not reach the electroplating technology requirement.So, before plating, must eliminate passive film and replacement with the activation film, guarantee titanium and alloy surface active state thereof, be the key that obtains the good electrolytic coating of sticking power.At present, mainly adopt etching, thermal treatment and extraordinary plating means to improve sticking power in the world.The Yamaoka of Japan Mitsubishi Electric Corp. etc. discloses a kind of electro-plating method that is suitable for titanium and alloy surface thereof in its patent JP 04,202,779 (92,202,779).At first vacuum high-temperature is handled and is eliminated stress, and etching is removed surperficial 5-20 micron in hydrochloric acid then, carries out media layer again and electroplates.Resulting plating media layer makes between this media layer and titanium or its alloy and carries out the metallographic phase mutual diffusion by 540 ℃ of following thermal treatments, strengthens sticking power.Then electroplating parts is placed the electroplating solution with the ability of filling and leading up to electroplate and fill and lead up processing, this moment, electrolytic coating thickness reached 10 microns, carried out bright plating again.[Tran.IMF.1996 such as Zhang, 74 (1), 25] adopt etching method, carry out etching at titanium and surface thereof with HF, in hydrochloric acid and Titanium Trichloride Solution, activate again, because etching produces certain roughness, so method can not directly be met the required bright plating layer of metallic surface finish.Above-mentioned example shows existing method, and not only technology is loaded down with trivial details, and the plating piece surface brightness also has loss, falls far short with the decorative electroplating technical requirements.And in the etching liquid that uses owing to contain a large amount of have pernicious murder by poisoning and strong corrosion material HF, aspect operation and liquid waste disposal, all very bother, the harm to environment during scale production is inevitable.
The purpose of this invention is to provide the titanium or titanium alloy surface activating process that a kind of bright plating is used.
Another object of the present invention provides employed activation solution in the titanium or titanium alloy surface activating process that a kind of bright plating uses.
Common titanium workpiece surface has thicker passive film, and it consists of TiO
2, can remove passive film with electrochemical reduction method.In the strong alkali solution that contains Sodium Fluoride and Neutral ammonium fluoride, make the titanium surface by highdensity cathodic current, produce intensive cathodic polarization and very high cathodic polarization potential, behind the certain hour, because the acting in conjunction of the electrochemical reduction of negative electrode and the atomic hydrogen of cathodic reaction, the titanium surface passivated membrane can be eliminated.After the passive film of compact structure was eliminated, the titanium surface still can very fast formation oxide film in air, but compares with the aerial workpiece of long-term exposure, and thinner thickness, structure be not fine and close, be dissolved in the acidic activated solution easily, and active titanium is promptly come out.Meanwhile, the hydrogen ion in the activation solution obtains electronics and forms labile atom hydrogen, is adsorbed on the titanium surface, and wherein a part forms black hydrogenation titanium film with active titanium.Add tensio-active agent in the activation solution, form monomolecular adsorption layer on activation film surface under given conditions, stop that titanium metal and alloy thereof further corrode.This unimolecular layer can be used as the blocking layer simultaneously, keeps the chemically reactive of activation film in air.
The invention provides a kind of titanium and alloy surface activating treatment process thereof, comprise that titanium or titanium alloy workpiece surface treatment with surface finish are glossy surface, remove surperficial permanent passive film, put it into temperature then and be in 40-70 ℃ the activation solution, soak time is 0.5-2.5 hour, described activation solution is a kind of aqueous solution, it contains the sulfuric acid of 40-95% (weight) and/or the strong acid of nitric acid, with total amount be the trimethyl-ammonium halide of C10-C20 of 0.05-0.5% (weight) and one or more with the alkyl of one or more C1-C4 and/or halogen replacement or the Phenylsulfonic acid that do not replace, wherein, the ratio of the trimethyl-ammonium halide of described replacement or Phenylsulfonic acid that does not replace and C10-C20 is 6-8: 1.
The operation of removing surperficial permanent passive film in the method for the present invention can be undertaken by method well known in the prior art.For example, be to put into the MF that contains weight ratio 10% and 50% MOH strong alkali aqueous solution, M=Na, K, Li behind the glossy surface with titanium or its alloy sample surface treatment.Its pH=14, and keep ammoniacal liquor content 5% with the form of constantly adding.Make the titanium surface by highdensity cathodic current 5 ± 1Am/dm
2, the cathodic polarization time is 15 minutes, thereby eliminates owing to be exposed to the thicker passive film that titanium in the air and alloy surface thereof generate.
In the method for the present invention, the strong acid that activation solution contains is the mixture of strong acid preferably, is preferably the mixture of sulfuric acid and nitric acid; The gross weight that is preferably based on activation solution especially is respectively sulfuric acid 37-80 weight %, the mixture of nitric acid 3-15 weight %.Additive is the mixture of Phenylsulfonic acid series compound and trimethyl-ammonium halide compound.Described Phenylsulfonic acid series compound is one or more Phenylsulfonic acids that replaces or do not replace with alkyl and/or the halogen of one or more C1-C4.Be preferably one or more that from Phenylsulfonic acid, tosic acid and m-toluene sulfonic acid, select, be preferably Phenylsulfonic acid, tosic acid and m-toluene sulfonic acid and use simultaneously.Described haloalkyl ammonium series compound is the trimethyl-ammonium halide of C10-C20.Preferred cetyl trimethylammonium bromide.Thereby preferred additives is the mixture of Phenylsulfonic acid, tosic acid, m-toluene sulfonic acid and cetyl trimethylammonium bromide in the method for the present invention.Wherein, the ratio of the trimethyl-ammonium halide of described replacement or Phenylsulfonic acid that does not replace and C10-C20 is 6-8: 1, and preferred 7: 1.
The compound method of activation solution of the present invention is successively sulfuric acid and nitric acid to be dissolved in respectively in the deionized water, then additive is added in the solution.
In the method for the present invention, activation temperature is 40-70 ℃, and optimum temps is 50-60 ℃; After soak time was 0.5-2.5 hour, optimum activating time was 1.0-1.5 hour.At this moment the surface generates the activation film of one deck black.Take out and use deionized water rinsing, promptly can be used for Direct Electroplating bright metal coating in the weakly alkaline electroplate liquid, have good sticking power between resulting electrolytic coating and the substrate.
The present invention also provides a kind of activation solution that is used for titanium or its alloy surface activating treatment process, described activation solution is a kind of aqueous solution, it contains the sulfuric acid of 40-95% (weight) and/or the strong acid of nitric acid, with total amount be the trimethyl-ammonium halide of C10-C20 of 0.05-0.5% (weight) and one or more with the alkyl of one or more C1-C4 and/or halogen replacement or the Phenylsulfonic acid that do not replace, wherein, the ratio of the trimethyl-ammonium halide of described replacement or Phenylsulfonic acid that does not replace and C10-C20 is 6-8: 1.
The strong acid that activation solution of the present invention contains is the mixture of strong acid preferably, is preferably the mixture of sulfuric acid and nitric acid; The gross weight that is preferably based on activation solution especially is sulfuric acid 37-80 weight %, the mixture of nitric acid 3-15 weight %.Additive is the mixture of Phenylsulfonic acid series compound and trimethyl-ammonium halide compound.Described Phenylsulfonic acid series compound is one or more Phenylsulfonic acids that replaces or do not replace with alkyl and/or the halogen of one or more C1-C4.The example of this compound comprises Phenylsulfonic acid, chlorobenzenesulfonic acid, bromobenzene sulfonic acid, tosic acid, to ethyl phenenyl azochlorosulfonate acid, to propylbenzene sulfonic acid, to butylbenzene sulfonic acid, a toluene sulfonic acide, between ethyl phenenyl azochlorosulfonate acid, a propylbenzene sulfonic acid, a butylbenzene sulfonic acid, o-methyl-benzene sulfonic acid, adjacent ethyl phenenyl azochlorosulfonate acid, adjacent butylbenzene sulfonic acid, the chloro toluene sulfonic acide, chloro ethyl phenenyl azochlorosulfonate acid, bromomethyl Phenylsulfonic acid, the bromoethyl Phenylsulfonic acid, bromo butylbenzene sulfonic acid, etc.Be preferably from Phenylsulfonic acid, chlorobenzenesulfonic acid, one or more that select in tosic acid and the m-toluene sulfonic acid are preferably Phenylsulfonic acid, tosic acid and m-toluene sulfonic acid and use simultaneously.Described trimethyl-ammonium halide compound is the trimethyl-ammonium halide of C10-C20.The example of this compound comprises, tetradecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, palmityl trimethyl ammonium chloride, cetyl trimethylammonium bromide, preferred cetyl trimethylammonium bromide.Thereby preferred additives is the mixture of Phenylsulfonic acid, tosic acid, m-toluene sulfonic acid and cetyl trimethylammonium bromide in the method for the present invention.Wherein, the part by weight of the trimethyl-ammonium halide of described replacement or Phenylsulfonic acid that does not replace and C10-C20 is 6-8: 1, and preferred 7: 1.
The various components of using among the present invention all can obtain by commercial sources, or can prepare by means commonly known in the art.
The bright plating that titanium after this activation and alloy thereof are suitable for slight alkalinity copper and cobalt, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion is in its surface growth.The sticking power test is qualified according to crooked experiment and the rasion experiment of U.S. testing standard ASTM B571.
(2cm * 0.5cm * 0.1cm) spend respectively by doubling 180 in order will carry out the thin electroplating bright copper layer and the sample of bright cobalt layer after above-mentioned activation treatment for the testing procedures of crooked experiment, under 4 times of magnifying glasses, observe, as do not have disengaging and peeling phenomenon, show that electrolytic coating has sticking power preferably.Nearly one goes on foot 180 degree of doubling repeatedly, up to ground titanium or its alloy permanent damage, observes under 10 times of magnifying glasses, as not having separation and peeling off, then shows the sticking power ideal.The testing procedures of rasion experiment for will after above-mentioned activation treatment, carry out thicker electroplating bright copper layer and and the sample (2cm * 0.5cm * 0.1cm) saw respectively of bright cobalt layer, prolong kerf with rasp and sentence miter angle, from the substrate of titanium and alloy thereof to the rasion of electrolytic coating direction, as do not have layering and peel off, show that then sticking power is splendid.The electron microscope experiment shows that reactivation process is harmless to the titanium surface, and the luminance brightness of the electrolytic coating that the light plating obtains is not less than former titanium and alloy surface luminance brightness thereof by traditional mechanical polishing or chemical surface polishing.
Present method characteristics are: do not need etching and extraordinary plating means to improve the sticking power of electrolytic coating at titanium and alloy surface thereof, and unnecessary heat treatment step, operating procedure and equipment are simple, low production cost; To titanium and the free of losses of alloy surface luminance brightness thereof, be suitable for the conventional electroplating process of weakly alkaline of multiple metal; Because no HF etching process has been avoided the harm to environment and operator when scale operation.
The present invention is further described for following embodiment.Content wherein all is weight percentage except that specifying, the ratio between the component is a weight ratio.
Embodiment 1:
The titanium that long-term exposure is formed passive film in air leads to 5Am/dm in 50% sodium hydroxide, 10% Sodium Fluoride and 5% (weight) ammonia soln
2After the cathodic current electrolysis 15 minutes, immerse 60% sulfuric acid, 5% nitric acid, additive total amount and be 0.1% (the compound ratio is for to chlorobenzenesulfonic acid: tosic acid: m-toluene sulfonic acid: cetyl trimethylammonium bromide=1: 1: 1: in the activation solution 0.5), and 50 ℃ of activation films that obtain stable black after following 1 hour.The electrochemical activity of this film can keep the time of foot length in air, titanium after this activation and alloy thereof are suitable for the processing requirement of conventional pyrophosphate salt bright copper plating, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion promptly can be as the media layer of further plating precious metal in its surface growth to 1 micron.The sticking power test is according to the crooked experiment of U.S. testing standard ASTM B571, and qualification rate 100% shows that present method satisfies the technical requirements of general electroplating industry to electrolytic coating sticking power.
Embodiment 2:
As described in embodiment 1, identical only to reduce sulfuric acid content in preparation during activation solution be 40% in other condition, and nitric acid content is 3%, and additive level is 0.05%, 40 ℃ activate the activation film that obtains stable black after 2.5 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional metaphosphate bright plating cobalt, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion promptly can be electroplated the media layer (≤1 micron) of precious metal as a nearly step in its surface growth to 1 micron.The sticking power test is according to the crooked experiment of U.S. testing standard ASTM B571, qualification rate 100%.
Embodiment 3:
As described in embodiment 1, identical only to improve sulfuric acid content in preparation during activation solution be 80% in other condition, and nitric acid content is 15%, and additive level is 0.5%, 70 ℃ activate the activation film that obtains stable black after 1.0 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional pyrophosphate salt bright copper plating, because the existence of activation film, the copper electrolytic coating of guaranteeing strong adhesion can be used as functional electric coating and uses in its surface growth to 5 micron.The sticking power test is according to the rasion experiment of U.S. testing standard ASTM B571, qualification rate 100%.
Embodiment 4:
As described in embodiment 1, identical only to improve sulfuric acid content in preparation during activation solution be 80% in other condition, and nitric acid content is 15%, and additive level is 0.5%, 40 ℃ activate the activation film that obtains stable black after 1.5 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional pyrophosphate salt bright copper plating, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion promptly can be electroplated the media layer of precious metal as a nearly step in its surface growth to 1 micron.The sticking power test is according to the crooked experiment of U.S. testing standard ASTM B571, qualification rate 100%.
Embodiment 5:
As described in embodiment 2, identical only to improve sulfuric acid content in preparation during activation solution be 65% in other condition, nitric acid content is 10%, additive level is 0.5% and (adjusts the compound ratio for to chlorobenzenesulfonic acid: tosic acid: m-toluene sulfonic acid: cetyl trimethylammonium bromide=1: 0.5: 0.5: 0.25), 60 ℃ activate the activation film that obtains stable black after 1.0 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional metaphosphate bright plating cobalt, because the existence of activation film, the cobalt electrolytic coating of guaranteeing strong adhesion can be used as functional electric coating and uses in its surface growth to 5 micron.The sticking power test is according to the rasion experiment of U.S. testing standard ASTM B571, qualification rate 100%.
Embodiment 6:
As described in embodiment 1, identical only to improve sulfuric acid content in preparation during activation solution be 80% in other condition, nitric acid content is 15%, additive level is that 0.5% (the compound ratio is a tosic acid: m-toluene sulfonic acid: o-toluene sulfonic acid: tetradecyl trimethyl ammonium chloride=1: 1: 1: 0.5), 50 ℃ activate the activation film that obtains stable black after 1.2 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional pyrophosphate salt bright copper plating, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion can be used as the media layer of further plating precious metal in its surface growth to 1 micron.The sticking power test is according to the crooked experiment of U.S. testing standard ASTMB571, qualification rate 100%.
Embodiment 7:
As described in embodiment 1, identical only to improve sulfuric acid content in preparation during activation solution be 80% in other condition, nitric acid content is 15%, additive level is that 0.5% (the compound ratio is a tosic acid: m-toluene sulfonic acid: o-toluene sulfonic acid: tetradecyl trimethyl ammonium chloride=1: 1: 1: 0.5), 50 ℃ activate the activation film that obtains stable black after 1.2 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional metaphosphate bright plating cobalt, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion can be used as the media layer of further electroplated metal layer in its surface growth to 1 micron.The sticking power test is according to the crooked experiment of U.S. testing standard ASTMB571, qualification rate 100%.
Embodiment 8:
As described in embodiment 1, identical only to improve sulfuric acid content in preparation during activation solution be 70% in other condition, nitric acid content is 10%, additive level is that 0.3% (the compound ratio is a chlorobenzenesulfonic acid: an ethyl phenenyl azochlorosulfonate acid: adjacent ethyl phenenyl azochlorosulfonate acid: tetradecyl trimethyl ammonium chloride=1: 1: 1: 0.5), 60 ℃ activate the activation film that obtains stable black after 1.5 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional pyrophosphate salt bright plating cobalt, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion can be used as the media layer of further electroplated metal layer in its surface growth to 1 micron.The sticking power test is according to the crooked experiment of U.S. testing standard ASTM B571, qualification rate 100%.
Embodiment 9:
As described in embodiment 1, identical only to improve sulfuric acid content in preparation during activation solution be 75% in other condition, nitric acid content is 10%, additive level is that 0.3% (the compound ratio is a tosic acid: a propylbenzene sulfonic acid: adjacent propyl sulfonic acid: palmityl trimethyl ammonium chloride=1: 1: 1: 0.5), 50 ℃ activate the activation film that obtains stable black after 1.5 hours down, reach embodiment 1 described performance.Titanium after this activation and alloy thereof are suitable for the processing requirement of conventional pyrophosphate salt bright plating cobalt, because the existence of activation film, the electroplated metal layer of guaranteeing strong adhesion can be used as the media layer of further electroplated metal layer in its surface growth to 1 micron.The sticking power test is according to the crooked experiment of U.S. testing standard ASTMB571, qualification rate 100%.
Claims (16)
1. titanium or titanium alloy surface activating treatment process, comprise that titanium or titanium alloy workpiece surface treatment with surface finish are glossy surface, remove surperficial permanent passive film, put it into temperature then and be in 40-70 ℃ the activation solution, soak time is 0.5-2.5 hour, described activation solution is the sulfuric acid of a kind of aqueous solution of being made up of following component: 40-95% (weight) and/or the strong acid of nitric acid, with total amount be the C10-C20 trimethyl-ammonium halide of 0.05-0.5% (weight) and one or more with the alkyl of one or more C1-C4 and/or halogen replacement or the Phenylsulfonic acid that do not replace, wherein, the part by weight of the trimethyl-ammonium halide of described replacement or Phenylsulfonic acid that does not replace and C10-C20 is 6-8: 1.
2. in accordance with the method for claim 1, the strong acid of the wherein said activation solution aqueous solution is the sulfuric acid of 37-80% (weight) and the nitric acid of 3-15% (weight) based on the gross weight of the activation solution aqueous solution.
3. in accordance with the method for claim 1, wherein said replacement or the Phenylsulfonic acid that does not replace are from Phenylsulfonic acid, chlorobenzenesulfonic acid, bromobenzene sulfonic acid, tosic acid, to ethyl phenenyl azochlorosulfonate acid, to propylbenzene sulfonic acid, to butylbenzene sulfonic acid, a toluene sulfonic acide, between ethyl phenenyl azochlorosulfonate acid, between propylbenzene sulfonic acid, a butylbenzene sulfonic acid, o-methyl-benzene sulfonic acid, adjacent ethyl phenenyl azochlorosulfonate acid, adjacent butylbenzene sulfonic acid, chloro toluene sulfonic acide, chloro ethyl phenenyl azochlorosulfonate acid, the bromomethyl Phenylsulfonic acid, one or more that select in bromoethyl Phenylsulfonic acid and the bromo butylbenzene sulfonic acid.
4. in accordance with the method for claim 3, wherein said replacement or the Phenylsulfonic acid that do not replace are one or more that select from Phenylsulfonic acid, tosic acid and m-toluene sulfonic acid.
5. in accordance with the method for claim 1, wherein said replacement or the Phenylsulfonic acid that do not replace are the mixtures of Phenylsulfonic acid, tosic acid and m-toluene sulfonic acid.
6. in accordance with the method for claim 1, the trimethyl-ammonium halide of wherein said C10-C20 is tetradecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, palmityl trimethyl ammonium chloride or cetyl trimethylammonium bromide.
7. in accordance with the method for claim 1, the trimethyl-ammonium halide of wherein said C10-C20 is a cetyl trimethylammonium bromide.
8. in accordance with the method for claim 1, the part by weight of the trimethyl-ammonium halide of wherein said replacement or Phenylsulfonic acid that does not replace and C10-C20 is 7: 1.
9. in accordance with the method for claim 1, wherein activation temperature is 50-60 ℃, and soak time is 1.0-1.5 hour.
10. in accordance with the method for claim 1, wherein, the operation of the surperficial permanent passive film of described removal is performed such: will put into the MF that contains weight ratio 10% and 50% MOH strong alkali aqueous solution by the workpiece that light is handled, wherein M is Na, K or Li, its pH value is 14, and keep ammoniacal liquor content 5% with the form of constantly adding, make the titanium surface by highdensity cathodic current 5 ± 1Am/dm
2, the cathodic polarization time is 15 minutes, thereby eliminates owing to be exposed to the thicker passive film that titanium in the air and alloy surface thereof generate.
11. activation solution that is used for titanium or titanium alloy surface activating treatment process, this activation solution is the sulfuric acid of a kind of aqueous solution of being made up of following component: 40-95% (weight) and/or the strong acid of nitric acid, with total amount be the C10-C20 trimethyl-ammonium halide of 0.05-0.5% (weight) and one or more with the alkyl of one or more C1-C4 and/or halogen replacement or the Phenylsulfonic acid that do not replace, wherein, the part by weight of the trimethyl-ammonium halide of described replacement or Phenylsulfonic acid that does not replace and C10-C20 is 6-8: 1.
12. according to the described activation solution of claim 11, the strong acid of the wherein said activation solution aqueous solution is the sulfuric acid of 37-80% (weight) based on the gross weight of the activation solution aqueous solution, the nitric acid of 3-15% (weight).
13. according to the described activation solution of claim 11, wherein said replacement or the Phenylsulfonic acid that does not replace are one or more that select from Phenylsulfonic acid, tosic acid and m-toluene sulfonic acid.
14. according to the described activation solution of claim 11, wherein said replacement or the Phenylsulfonic acid that does not replace are the mixtures of Phenylsulfonic acid, tosic acid and m-toluene sulfonic acid.
15. according to the described activation solution of claim 11, the trimethyl-ammonium halide of wherein said C10-C20 is a cetyl trimethylammonium bromide.
16. according to the described activation solution of claim 11, the part by weight of the trimethyl-ammonium halide of wherein said replacement or Phenylsulfonic acid that does not replace and C10-C20 is 7: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119772A CN1125196C (en) | 1999-09-28 | 1999-09-28 | Surface activating process of Ti and Ti alloy for bright electroplating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119772A CN1125196C (en) | 1999-09-28 | 1999-09-28 | Surface activating process of Ti and Ti alloy for bright electroplating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289864A true CN1289864A (en) | 2001-04-04 |
| CN1125196C CN1125196C (en) | 2003-10-22 |
Family
ID=5281091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99119772A Expired - Fee Related CN1125196C (en) | 1999-09-28 | 1999-09-28 | Surface activating process of Ti and Ti alloy for bright electroplating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1125196C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313635C (en) * | 2004-11-02 | 2007-05-02 | 江苏大学 | Flame spray welding process for titanium alloy surface wearable coating |
| CN101012571B (en) * | 2006-12-31 | 2010-05-19 | 湖南纳菲尔新材料科技股份有限公司 | Anode poling processing technique before electric plating |
| CN101768747B (en) * | 2009-12-28 | 2011-12-28 | 江苏麟龙新材料股份有限公司 | Method for carrying out surface activating treatment on surface of titanium alloy |
| CN104005059A (en) * | 2014-06-11 | 2014-08-27 | 沈阳飞机工业（集团）有限公司 | Method for electroplating chromium on TC1 titanium alloy and TC2 titanium alloy |
| CN104032343A (en) * | 2014-05-14 | 2014-09-10 | 蚌埠富源电子科技有限责任公司 | Novel electroplating pre-treatment technology for titanium and titanium alloy |
| CN111733417A (en) * | 2020-06-11 | 2020-10-02 | 华东交通大学 | Method for low-temperature copper infiltration on surface of titanium or titanium alloy |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2813814A (en) * | 1954-08-05 | 1957-11-19 | Parker Rust Proof Co | Composition and process for forming phosphate coatings on titanium and zirconium |
| JPH0649181B2 (en) * | 1986-06-23 | 1994-06-29 | 住友電気工業株式会社 | Method for producing polyimide-coated linear body |
| JPH04289175A (en) * | 1991-01-12 | 1992-10-14 | Nishiyama Stainless Chem Kk | Method for plating titanium or titanium alloy material with noble metal |
| JPH0625890A (en) * | 1992-02-06 | 1994-02-01 | Riken Corp | Electroplating method |
| DE19533748C2 (en) * | 1995-09-12 | 2000-09-14 | Rasant Alcotec Beschichtungste | Activation solution for the pretreatment of metallic materials for galvanic metal coating from non-aqueous electrolytes, use and method |
-
1999
- 1999-09-28 CN CN99119772A patent/CN1125196C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313635C (en) * | 2004-11-02 | 2007-05-02 | 江苏大学 | Flame spray welding process for titanium alloy surface wearable coating |
| CN101012571B (en) * | 2006-12-31 | 2010-05-19 | 湖南纳菲尔新材料科技股份有限公司 | Anode poling processing technique before electric plating |
| CN101768747B (en) * | 2009-12-28 | 2011-12-28 | 江苏麟龙新材料股份有限公司 | Method for carrying out surface activating treatment on surface of titanium alloy |
| CN104032343A (en) * | 2014-05-14 | 2014-09-10 | 蚌埠富源电子科技有限责任公司 | Novel electroplating pre-treatment technology for titanium and titanium alloy |
| CN104005059A (en) * | 2014-06-11 | 2014-08-27 | 沈阳飞机工业（集团）有限公司 | Method for electroplating chromium on TC1 titanium alloy and TC2 titanium alloy |
| CN111733417A (en) * | 2020-06-11 | 2020-10-02 | 华东交通大学 | Method for low-temperature copper infiltration on surface of titanium or titanium alloy |
| CN111733417B (en) * | 2020-06-11 | 2022-05-31 | 华东交通大学 | Method for low-temperature copper infiltration on surface of titanium or titanium alloy |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1125196C (en) | 2003-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109825866B (en) | Preparation method of alloy self-repairing corrosion-resistant micro-arc oxidation coating | |
| KR20030010509A (en) | Al alloy member having excellent corrosion resistance | |
| CN1861842A (en) | Immersion method | |
| KR20110139654A (en) | Aluminum oxide film remover and method for surface treatment of aluminum or aluminum alloy | |
| CN1125196C (en) | Surface activating process of Ti and Ti alloy for bright electroplating | |
| JPH0347999A (en) | Support metal having improved surface mor- phology | |
| KR20140020829A (en) | Process for electroless deposition of metals using highly alkaline plating bath | |
| JP3506827B2 (en) | Surface-treated aluminum material and method for producing the same | |
| US5356527A (en) | Method for rinsing copper or copper base alloy foil after an anti-tarnish treatment | |
| EP3059335A2 (en) | Surface modifiers for ionic liquid aluminum electroplating solutions, processes for electroplating aluminum therefrom, and methods for producing an aluminum coating using the same | |
| Notoya et al. | Benzotriazole and tolyltriazole as corrosion inhibitors for copper and brasses | |
| CN111945215B (en) | Deplating solution and deplating method | |
| CN110685000B (en) | High-corrosion-resistance coating, preparation method, electrolyte and application thereof | |
| JP5352204B2 (en) | Surface-treated aluminum material for vacuum equipment | |
| KR100618165B1 (en) | Electrolytic method of and compositions for stripping electroless nickel | |
| EP0375179B1 (en) | Copper plating process for difficult to plate metals | |
| CN1477237A (en) | Brass-plating process in alkaline solution and its electroplating solution formula | |
| CN1641075A (en) | Magnesium and Mg alloy surface activating method and surface palting method | |
| JP2006500476A (en) | Electrolytic coating of materials with aluminum, magnesium, or an alloy of aluminum and magnesium | |
| JPH09302499A (en) | Aluminum material | |
| CN116855252A (en) | Ag etching solution, preparation method and application thereof | |
| JPS5887275A (en) | Stripping method for sn layer on cu and cu alloy | |
| CN110616432A (en) | Zirconium-containing film layer removing liquid and use method thereof | |
| CN117661058A (en) | Pre-plating solution for titanium alloy plating processing and titanium alloy composite material | |
| JP3500239B2 (en) | Electrolytic etching solution and electrolytic etching method for precipitation strengthened copper alloy products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20031022 Termination date: 20120928 |