CN102260892A - Titanium and titanium alloy pre-plating solution and electroplating method - Google Patents
Titanium and titanium alloy pre-plating solution and electroplating method Download PDFInfo
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Abstract
The invention provides a titanium and titanium alloy pre-plating solution, which comprises gold sodium sulfite, an electroconductive salt, a complexing agent, a brightening agent and a pH buffer and has a pH value of 9-11. The invention also provides a titanium and titanium alloy electroplating method, which comprises placing titanium and titanium alloy in the pre-plating solution for pre-plating, and electroplating a cyanide-free white copper-tin alloy, wherein the pre-plating solution is provided by the invention. In the titanium and titanium alloy electroplating method provided by the invention, cyanide-free gold pre-plating is used for replacing nickel pre-plating rendering, thereby increasing the bonding force between titanium as well as titanium alloy and the plating layer and reducing pitting; and at the same time, a cyanide-free white copper-nickel alloy system is used to replace a common nickel plating process, so that the problems of human body allergy to nickel and cyanide pollution to the environment are solved.
Description
Technical field
The present invention relates to a kind of metal electroplating solution and electro-plating method, relate in particular to pre-plating bath of a kind of titanium or titanium alloy and electro-plating method, belong to field of metal surface treatment technology.
Background technology
Titanium is the novel metal of 21 century after steel, aluminium, magnesium.From the 1950's, titanium develops so far as a kind of structural metal, and more and more countries is recognized the importance of titanium alloy in the world, in succession it is researched and developed, and has obtained fine application at numerous areas.The outward appearance of titanium is similar to steel, is silver gray, has gloss.The titanium alloy principal feature is the fusing point height, and tensile strength is big, the hardness height, and plasticity-is strong, and density is little, the specific tenacity height; The titanium of equal quality is more durable than aluminium and steel; Nontoxic, nonmagnetic, high temperature resistant; Corrosion resistance is 15 times of common stainless steel, and seawater is had more particularly resistance to corrosion.The unusual characteristic of these of titanium, be widely used in fields such as aircraft, guided missile, steamer, automobile, oil, chemical industry, biomedicines, especially nonpolarity, the supraconductivity of titanium niobium alloy of titanium, the characteristics such as hydrogen storage ability of ferro-titanium are being brought into play important role at the top science and high-tech area.But along with science and technology development, the expansion day by day of titanium material Application Areas and the variation of working conditions, the titanium surface treatment technology of material also more and more comes into one's own.
Titanium belongs to easy passive metal, because in the environment that oxide compound exists, the surface very easily forms one deck and approaches and fine and close and ten minutes stable oxide film, and avoids the corrosion of environment; And, in treating processes, coating and basal body binding force significantly being descended just because of the existence of this one deck oxide film, the foaming phenomenon appears easily.
The electro-plating method that titanium or titanium alloy is commonly used is: 1. plate pre-treatment-nickel preplating-tetra-sodium copper facing-acid copper-plating-bright nickel plating-gold-plated (silver-plated); 2. plate pre-treatment-chemical nickel-tetra-sodium copper facing-acid copper-plating-bright nickel plating-gold-plated (silver-plated).Above-mentioned technology is nickel layer, because nickel produces irritated or infringement to human skin, European Union has finished legislative procedure, and passed through relevant nickeliferous detection method to metal, in formal announcement the on July 20th, 1999, in six months of on January 20th, 2000 tolerances at the expiration the time, just must not meet the product of rule regulation to the market release.In order to reduce the murder by poisoning of nickel to human body, adopt gunmetal to replace the method for nickel coating, also be referred to as nickel-free electroplating, the nickel-free electroplating technology of current comparative maturity has cyaniding copper-nickel alloy tin electroplating technology etc.The copper-nickel alloy process of tin comparative maturity that cyanogen is arranged, but prussiate is a severe toxicity, can pollute environment.
Summary of the invention
The technical problem to be solved in the present invention is the defective that existing titanium or titanium alloy plating electroplate liquid contains the very big cyanogen of the nickel of forbidding and toxicity, thereby a kind of titanium or titanium alloy electroplate liquid and electro-plating method of cyanide-free and nickel-free are provided.
The invention provides the pre-plating bath of a kind of titanium or titanium alloy, this pre-plating bath comprises gold sodium sulfide, conducting salt, complexing agent, brightening agent and pH buffer reagent; The pH of described electroplate liquid is 9-11.
The present invention also provides a kind of titanium or titanium alloy electro-plating method, and this method comprises titanium or titanium alloy is placed on carries out in the pre-plating bath electroplating no cyamelide copper tin after the preplating; Wherein, described pre-plating bath is a pre-plating bath of the present invention.
The present invention for nickel preplating bottoming, increases the bonding force of titanium or titanium alloy and coating by the non-cyanide pre-plating Jin Dynasty, reduces pit, utilizes no cyamelide copper tin system to replace the nickel plating technology of using always simultaneously, and the solution human body is to the pollution to environment of the allergy of nickel and cyanogen.
Embodiment
The invention provides the pre-plating bath of a kind of titanium or titanium alloy, this pre-plating bath comprises gold sodium sulfide, conducting salt, complexing agent, brightening agent and pH buffer reagent; The pH of described electroplate liquid is 9-11.
The pre-plating bath of titanium or titanium alloy of the present invention utilizes pre-gold-plated the bottoming to obtain good titanium alloy base material and the bonding force between electrolytic coating, utilizes no cyamelide copper tin to replace usual nickel layer again, finishes cyanide-free and nickel-free electroplating technology truly.
According to the pre-plating bath of titanium or titanium alloy provided by the present invention, for the bonding force and the surface effect that make titanium or titanium alloy and plated metal better, preferably, the content of described gold sodium sulfide is 2-10g/L, the content of described conducting salt is 40-80g/L, the content of described complexing agent is 10-20g/L, and the content of described brightening agent is 5-10g/L, and the content of described pH buffer reagent is 5-10g/L.
According to the pre-plating bath of titanium or titanium alloy provided by the present invention, in order to make this preplating liquid phase to stable, work-ing life is longer, is difficult for decomposing, separating out, and preferably, described conducting salt is at least a in S-WAT, vitriolate of tartar, trisodium phosphate, the sodium sulfate; Described complexing agent is at least a in ethylenediamine tetraacetic acid (EDTA), Methionin, quadrol, the ethylene diamine tetra methylene phosphonic acid; Described brightening agent is at least a in Tripotassium Citrate, benzylidene-acetone, butynediol, asccharin, thiocarbamide, the methyl sodium disulfonate; Described pH buffer reagent is at least a of borax, boric acid.
The present invention also provides a kind of titanium or titanium alloy electro-plating method, and this method comprises titanium or titanium alloy is placed on carries out in the pre-plating bath electroplating copper-nickel alloy tin after the preplating; Wherein, described pre-plating bath is a pre-plating bath of the present invention.
According to titanium or titanium alloy electro-plating method provided by the present invention, in order further to improve the quality of coating, the condition of described preplating is: temperature 20-35 ℃, and current density 0.1-0.15A/dm
2, time 0.5-1min.
It is the technology that various plating known in those skilled in the art does not have cyamelide copper tin that described plating does not have cyamelide copper tin.The present invention adopts the no cyamelide copper tin plating bath of the FSC of U.S. DIS model, and electroplate liquid formulation is: potassium pyrophosphate 250-350g/L, preferred 320g/L; Cupric pyrophosphate 5-12g/L, preferred 10g/L; Stannous pyrophosphate 15-35g/L; Complexing agent FCS-A 80-120ml/L; Stablizer FCS-B 10-30m1/L; Photo etching FCS-C 10-20ml/L; Cathode current density 0.5-1A/dm
2, workpiece is immersed in the plating bath, plating temperature is 15-30 ℃; PH value 8.0-8.8; Time is 5-15min.
According to titanium or titanium alloy electro-plating method provided by the present invention, preferably, before preplating, titanium or titanium alloy is carried out pre-treatment.Described pre-treatment comprises polishing, removing oil-removing wax and surface adjustment.
The purpose of described polishing is to remove burr that former material itself produces in press casting procedure, oxide skin etc., reduces the roughness on surface, and raising minute surface brightness effect also strengthens subsequent disposal or the laggard electroplating of sandblast.Of the present inventionly be finished to mechanical polishing, for example carry out in conjunction with lamb hair buff polishing gimmick with button cloth wheel.
Described removing oil-removing wax comprises ultrasonic wave paraffin removal, catholyte oil removing and anode electrolysis oil removing.Described ultrasonic wave paraffin removal is a technology known in those skilled in the art, and as adopting the roc Feng Yu industry PF-160C of Science and Technology Ltd. Wax removal water, opening cylinder concentration is 30ml/L; Temperature is 65 ℃, time 5min.Described catholyte oil removing adopts the roc Feng Yu industry PF-713 of Science and Technology Ltd. model anode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 5s.Described anode electrolysis oil removing adopts the roc Feng Yu industry PF-713 of Science and Technology Ltd. model anode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 5s.
Described surface adjustment mainly is an oxidation film layer of removing the titanium or titanium alloy surface.It is nitric acid 61ml/L-81ml/L that liquid is adjusted on described surface, is preferably 71ml/L; Hydrofluoric acid 61ml/L-81ml/L is preferably 71ml/L; Hydrogen peroxide 418ml/L-438ml/L is preferably 428ml/L; Ethylene glycol 204ml/L-224ml/L is preferably 214ml/L; Fluorion can be removed the inhomogeneous rete of grey black.Treatment temp is 20-35 ℃, time 5min-10min.
According to titanium or titanium alloy electro-plating method provided by the present invention, preferably, after electroplating copper-nickel alloy tin, titanium or titanium alloy is carried out electroplated decoration coating.
Described decorative coating can be the various coating that metal or alloy that decorative coating uses forms that can be used as known in those skilled in the art.The present invention adopts and electroplates white chromium and electroplate rose gold.
The white chromium of described plating adopts the white chromium of company's T VC-trivalent that starts, and electroplate liquid formulation is: TVC-BC opens cylinder agent 400-450g/L, preferred 420g/L; TVC-CAT stablizer 55-75g/L, preferred 65g/L; TVC-MS wetting agent 2-5ml/L, preferred 3ml/L; TVC-EXT complexing agent 1-3ml/L, preferred 2ml/L; Trivalent chromium 20-25g/L, preferred 22g/L; Anode is the special-purpose anode of trivalent chromium; Continuous filtration is also taked mechanical stirring or pneumatic blending; The red-tape operati temperature exists: 28-35 ℃, be preferably 32 ℃; PH value: 2.5-3.0 is preferably 2.8; Cathode current density: 8-30A/dm
2, be preferably 14A/dm
2Time is 1-5min.
Described plating rose gold adopts the rose gold plating bath of autogamy, and electroplate liquid formulation is: golden 8-15g/L is preferably 12g/L; Sodium sulphite anhydrous 99.3 120-150g/L is preferably 130g/L; Dipotassium hydrogen phosphate 30-50g/L is preferably 40g/L; Tripotassium Citrate 80-100g/L is preferably 90g/L; Repone K 100-120g/L is preferably 110g/L; Brightening agent 0.5-1.5g/L is preferably 1.0g/L; Stablizer 0.2-0.3g/L; Adopt the graphite cake anode, the red-tape operati temperature exists: 50-60 ℃, be preferably 55 ℃; PH value: 8.5-9.0; Cathode current density: 0.1-0.5A/dm
2, the time is 20-60s.
According to titanium or titanium alloy electro-plating method provided by the present invention, preferably, in preplating with electroplate between the copper-nickel alloy tin, electroplate between copper-nickel alloy tin and the electroplated decoration coating and all will carry out activation treatment.The purpose of described activation treatment is to remove the oxide film on titanium or titanium alloy surface.Described activation solution is H
2SO
4: 5% (massfraction); Time 1-2min; Ambient operation.
Titanium or titanium alloy electro-plating method of the present invention can make the bonding force between base material and coating good, and sticking power is good; The technology environmental protection, all pollution-free to operator and environment; Technology is simple to operation, and streamlining is uncomplicated, and is easy to maintenance, is easy to mass production; Plate out that product appearance light, porosity are low, covering power and covering power be good; Adopt titanium alloy cyanide-free and nickel-free technology to replace the nickel layer electroplating technology, reduce allergy and the technology environmental protection of nickel to human body, the property filled and led up is good, good covering power and have antiseptic power preferably, and coating stress is less, and does not crack; This process application scope is wide, and is all suitable to multiple titanium alloy stamping parts, comprises Gr1, ZTA1, models such as TC1.
Below in conjunction with embodiment the present invention is described in further details.
Embodiment 1
1) mechanical polishing
Titanium alloy Gr1 pre-treatment: carry out in conjunction with lamb hair buff polishing gimmick with button cloth wheel, remove burr that former material itself produces, oxide skin etc. in press casting procedure, reduce surperficial roughness.
2) ultrasonic wave paraffin removal
Titanium alloy after will handling through step (1) carries out paraffin removal, and Wax removal water adopts the roc Feng Yu industry PF-160C of Science and Technology Ltd. Wax removal water, and opening cylinder concentration is 30ml/L; Temperature is 65 ℃, time 5min.
3) catholyte oil removing
Titanium alloy after will handling through step (2) carries out the catholyte oil removing, and the catholyte oil removing adopts the roc Feng Yu industry PF-514 of Science and Technology Ltd. model negative electrode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 1min.
4) anode electrolysis oil removing
Titanium alloy after will handling through step (3) carries out the anode electrolysis oil removing, and the anode electrolysis oil removing adopts the roc Feng Yu industry PF-713 of Science and Technology Ltd. model anode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 5s.
5) surface is adjusted
Titanium alloy after will handling through step (4) carries out surface adjustment, and it is nitric acid 71ml/L that liquid is adjusted on the surface, hydrofluoric acid 71ml/L, hydrogen peroxide 428ml/L, ethylene glycol 214ml/.Treatment temp is 30 ℃, time 8min.
6) preplating
Titanium alloy after will handling through step (5) carries out preplating, and pre-plating bath is that the sulfurous acid gold is patched up 4g/L, S-WAT 48g/L, vitriolate of tartar 7.5g/L, EDTA 15g/L, Tripotassium Citrate 7.5g/L, borax 7.5g/L.30 ℃ of temperature, pH value 10, current density 0.15A/dm
2, time 1min.
7) activation
Titanium alloy after will handling through step (6) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
8) electroplate no cyamelide copper tin
Titanium alloy after will handling through step (7) is electroplated no cyamelide copper tin, electroplates the no cyamelide copper tin plating bath that no cyamelide copper tin adopts the FSC of U.S. DIS model, and electroplate liquid formulation is: potassium pyrophosphate 320g/L; Cupric pyrophosphate 10g/L; Stannous pyrophosphate 20g/L; Complexing agent FCS-A 100ml/L; Stablizer FCS-B 20ml/L; Photo etching FCS-C 15ml/L; Cathode current density 1A/dm
2, workpiece is immersed in the plating bath, plating temperature is 25 ℃; PH value 8.0; Time is 10min.
9) activation
Titanium alloy after will handling through step (8) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
10) electroplate white chromium
Titanium alloy after will handling through step (9) is electroplated white chromium, electroplates white chromium and adopts the white chromium of company's T VC-trivalent that starts, and electroplate liquid formulation is: TVC-BC opens cylinder agent 420g/L; TVC-CAT stablizer 65g/L; TVC-MS wetting agent 3ml/L; TVC-EXT complexing agent 2ml/L; Trivalent chromium 22g/L; Anode is the special-purpose anode of trivalent chromium; Continuous filtration is also taked mechanical stirring or pneumatic blending; The red-tape operati temperature is 32 ℃; The pH value is 2.8; Cathode current density is 14A/dm
2Time is 3min.
More than all adopt washing between each step.
Obtain product A 1 by above processing.
Embodiment 2
1) mechanical polishing
Titanium alloy ZTi1 pre-treatment: carry out in conjunction with lamb hair buff polishing gimmick with button cloth wheel, remove burr that former material itself produces, oxide skin etc. in press casting procedure, reduce surperficial roughness.
2) ultrasonic wave paraffin removal
Titanium alloy after will handling through step (1) carries out paraffin removal, and Wax removal water adopts the roc Feng Yu industry PF-160C of Science and Technology Ltd. Wax removal water, and opening cylinder concentration is 30ml/L; Temperature is 65 ℃, time 5min.
3) catholyte oil removing
Titanium alloy after will handling through step (2) carries out the catholyte oil removing, and the catholyte oil removing adopts the roc Feng Yu industry PF-514 of Science and Technology Ltd. model negative electrode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 1min.
4) anode electrolysis oil removing
Titanium alloy after will handling through step (3) carries out the anode electrolysis oil removing, and the anode electrolysis oil removing adopts the roc Feng Yu industry PF-713 of Science and Technology Ltd. model anode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 5s.
5) surface is adjusted
Titanium alloy after will handling through step (4) carries out surface adjustment, and it is nitric acid 61ml/L that liquid is adjusted on the surface; Hydrofluoric acid 61ml/; Hydrogen peroxide 418ml/L; Ethylene glycol 204ml/L; Treatment temp is 20 ℃; Time 5min.
6) preplating
Titanium alloy after will handling through step (5) carries out preplating, and pre-plating bath is that the sulfurous acid gold is patched up 2g/L, trisodium phosphate 40g/L, quadrol 10g/L, thiocarbamide 5g/L, boric acid 5g/L.20 ℃ of temperature, pH value 9, current density 0.15A/dm
2, time 1min.
7) activation
Titanium alloy after will handling through step (6) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
8) electroplate no cyamelide copper tin
Titanium alloy after will handling through step (7) is electroplated no cyamelide copper tin, electroplates the no cyamelide copper tin plating bath that no cyamelide copper tin adopts the FSC of U.S. DIS model, and electroplate liquid formulation is: potassium pyrophosphate 320g/L; Cupric pyrophosphate 10g/L; Stannous pyrophosphate 25g/L; Complexing agent FCS-A 100ml/L; Stablizer FCS-B 20ml/L; Photo etching FCS-C 15ml/L; Cathode current density 1A/dm
2, workpiece is immersed in the plating bath, plating temperature is 30 ℃; PH value 8.0; Time is 10min.
9) activation
Titanium alloy after will handling through step (8) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
10) electroplate rose gold
Titanium alloy after will handling through step (8) is electroplated rose gold, electroplates rose gold and is: gold sodium sulfide 12g/L; Sodium sulphite anhydrous 99.3 130g/L; Dipotassium hydrogen phosphate 40g/L; Tripotassium Citrate 90g/L; Repone K 110g/L; Brightening agent 1.0g/L; Stablizer 0.25g/L; Adopt the graphite cake anode; Continuous filtration; The red-tape operati temperature is 55 ℃; PH value: 9.0; Cathode current density: 0.5A/dm
2, the time is 40s.
More than all adopt washing between each step.
Obtain product A 2 by above processing.
Embodiment 3
1) mechanical polishing
Titanium alloy T C1 pre-treatment: carry out in conjunction with lamb hair buff polishing gimmick with button cloth wheel, remove burr that former material itself produces, oxide skin etc. in press casting procedure, reduce surperficial roughness.
2) ultrasonic wave paraffin removal
Titanium alloy after will handling through step (1) carries out paraffin removal, and Wax removal water adopts the roc Feng Yu industry PF-160C of Science and Technology Ltd. Wax removal water, and opening cylinder concentration is 30ml/L; Temperature is 65 ℃, time 5min.
3) catholyte oil removing
Titanium alloy after will handling through step (2) carries out the catholyte oil removing, and the catholyte oil removing adopts the roc Feng Yu industry PF-514 of Science and Technology Ltd. model negative electrode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time lmin.
4) anode electrolysis oil removing
Titanium alloy after will handling through step (3) carries out the anode electrolysis oil removing, and the anode electrolysis oil removing adopts the roc Feng Yu industry PF-713 of Science and Technology Ltd. model anode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 5s.
5) surface is adjusted
Titanium alloy after will handling through step (4) carries out surface adjustment, and it is nitric acid 81ml/L that liquid is adjusted on the surface, hydrofluoric acid 81ml/L, and hydrogen peroxide 438ml/L, ethylene glycol 224ml/L, treatment temp is 25 ℃; Time 10min.
6) preplating
Titanium alloy after will handling through step (5) carries out preplating, and pre-plating bath is that the sulfurous acid gold is patched up 10g/L, S-WAT 70g/L, sodium sulfate 10g/L, ethylene diamine tetra methylene phosphonic acid 20g/L, methyl sodium disulfonate 10g/L, borax 10g/L.25 ℃ of temperature, pH value 10, current density 0.15A/dm
2, time 1min.
7) activation
Titanium alloy after will handling through step (6) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
8) electroplate no cyamelide copper tin
Titanium alloy after will handling through step (7) is electroplated no cyamelide copper tin, electroplates the no cyamelide copper tin plating bath that no cyamelide copper tin adopts the FSC of U.S. DIS model, and electroplate liquid formulation is: potassium pyrophosphate 320g/L; Cupric pyrophosphate 10g/L; Stannous pyrophosphate 20g/L; Complexing agent FCS-A 100ml/L; Stablizer FCS-B 20ml/L; Photo etching FCS-C15ml/L; Cathode current density 1A/dm
2, workpiece is immersed in the plating bath, plating temperature is 20 ℃; PH value 8.5; Time is 10min.
9) activation
Titanium alloy after will handling through step (8) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
10) electroplate white chromium
Titanium alloy after will handling through step (9) is electroplated white chromium, electroplates white chromium and adopts the white chromium of company's T VC-trivalent that starts, and electroplate liquid formulation is: TVC-BC opens cylinder agent 420g/L; TVC-CAT stablizer 65g/L; TVC-MS wetting agent 3ml/L; TVC-EXT complexing agent 2ml/L; Trivalent chromium 222g/L; Anode is the special-purpose anode of trivalent chromium; Continuous filtration is also taked mechanical stirring or pneumatic blending; The red-tape operati temperature is 32 ℃; PH2.8; Cathode current density is 14A/dm
2Time is 3min.
More than all adopt washing between each step.
Obtain product A 3 by above processing.
Comparative Examples 1
1) mechanical polishing
Titanium alloy Gr1 pre-treatment: carry out in conjunction with lamb hair buff polishing gimmick with button cloth wheel, remove burr that former material itself produces, oxide skin etc. in press casting procedure, reduce surperficial roughness.
2) ultrasonic wave paraffin removal
Titanium alloy after will handling through step (1) carries out paraffin removal, and Wax removal water adopts the roc Feng Yu industry PF-160C of Science and Technology Ltd. Wax removal water, and opening cylinder concentration is 30ml/L; Temperature is 65 ℃, time 5min.
3) catholyte oil removing
Titanium alloy after will handling through step (2) carries out the catholyte oil removing, and the catholyte oil removing adopts the roc Feng Yu industry PF-514 of Science and Technology Ltd. model negative electrode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 1min.
4) anode electrolysis oil removing
Titanium alloy after will handling through step (3) carries out the anode electrolysis oil removing, and the anode electrolysis oil removing adopts the roc Feng Yu industry PF-713 of Science and Technology Ltd. model anode to remove oil-bound distemper, opens cylinder amount 50g/L; 65 ℃ of temperature; Current density 5A/dm
2Time 5s.
5) surface is adjusted
Titanium alloy after will handling through step (4) carries out surface adjustment, and it is nitric acid 81ml/L that liquid is adjusted on the surface, hydrofluoric acid 81ml/L, and hydrogen peroxide 438ml/L, ethylene glycol 224ml/L, treatment temp is 25 ℃; Time 10min.
6, the pre-copper facing of prussiate
Titanium alloy after will handling through step (5) carries out the pre-copper facing of prussiate, the pre-copper facing of prussiate is for adopting the alkali copper electrolyte of the Dongyang SML of scientific ﹠ trading Co., Ltd. model, solution preparation and operational condition are as follows: cuprous cyanide 60g/l, NaCN 85g/l, NaOH 2g/l, liquid 40ml/l, SML-36ml/l, SML-45ml/l are cut in promise.55 ℃ of temperature, cathode current density 1A/dm
2PH value 9.5; Time 3min.
7, electroplating bright acid copper
Titanium alloy after will handling through step (6) carries out electroplating bright acid copper, and electroplating bright acid copper adopts the Ultra acid copper plating solution of Atotech company, and electroplate liquid formulation is: CuSO
4.5H
2O 220g/L; H
2SO
450g/L; Chlorion 100mg/L; Open cylinder agent ULTRA Make Up 8ml/L; Fill and lead up agent ULTRA A 0.5ml/L; Brightening agent ULTRAB0.5ml/L; Cathode current density 4A/dm
2, anode is phosphor-copper (0.03～0.06% phosphorus), air or mechanical stirring; Continuous filtration; Workpiece is immersed in the plating bath, and temperature is 25 ℃, and the time is 30min.
8, activation
Titanium alloy after will handling through step (7) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
9, electroplate no cyamelide copper tin
Titanium alloy after will handling through step (8) is electroplated no cyamelide copper tin, electroplates the no cyamelide copper tin plating bath that no cyamelide copper tin adopts the FSC of U.S. DIS model, and electroplate liquid formulation is: potassium pyrophosphate 320g/L; Cupric pyrophosphate 10g/L; Stannous pyrophosphate 25g/L; Complexing agent FCS-A 100ml/L; Stablizer FCS-B 20ml/L; Photo etching FCS-C 15ml/L; Cathode current density 0.8A/dm
2, workpiece is immersed in the plating bath, plating temperature is 20 ℃; PH value 8.5; Time is 10min.
10) activation
Titanium alloy after will handling through step (9) activates, and activation solution is H
2SO
45% (massfraction); Time 1min, ambient operation.
11) electroplate white chromium
Titanium alloy after will handling through step (10) is electroplated white chromium, electroplates white chromium and adopts the white chromium of company's T VC-trivalent that starts, and electroplate liquid formulation is: TVC-BC opens cylinder agent 420g/L; TVC-CAT stablizer 65g/L; TVC-MS wetting agent 3ml/L; TVC-EXT complexing agent 2ml/L; Trivalent chromium 222g/L; Anode is the special-purpose anode of trivalent chromium; Continuous filtration is also taked mechanical stirring or pneumatic blending; The red-tape operati temperature is 32 ℃; PH2.8; Cathode current density is 14A/dm
2Time is 3min.
More than all adopt washing between each step.
Obtain product B 1 by above processing.
Testing method: with product A 1-A3 and B1 carry out the test of hundred lattice cuttves, vibrate wear-resisting test, SaltSprayTest and temperature shock test.Test result sees Table 1.
Testing standard:
The test of (1) hundred lattice cutter
The standard of test: ISO 2409.
Test procedure: use the knife back of surgical knife or specified intersection cutter on coating, to draw 12 road cuts, article two, scratch mutually at an angle of 90, so that form grid from the teeth outwards, cut be spaced apart 1mm (if surface too only standardized the fork of I, i.e. 2 road cuts).Guarantee to be cut to body material.Otherwise cut again the position of Ying Zaixin.Direction along cut is brushed 5 times with brush.3M adhesive tape (600 or similar model) is bonded on the surface, with finger tip that wiping belt is tight, guarantee to contact with the good of coating, in 5 minutes, tear adhesive tape well-regulated open off adhesive tape at 0.5-1 in second with 60 ° angle from the free end of adhesive tape.
Accept standard: 0 grade and 1 grade of reception.Cut for an intersection does not allow angle of cut perk or becomes big.
0 grade: the edge of otch is level and smooth fully, and the square of grid does not all peel off.
1 grade: peel off and be subjected to this part that influences can not be obviously greater than 5%.
2 grades: peel off and be subjected to this part that influences, and be no more than 15% obviously greater than 5%.
3 grades: peel off and be subjected to this part that influences, and be no more than 35% greater than 15%.
4 grades: peel off and be subjected to this part that influences, and be no more than 65% greater than 35%.
(2) vibrate wear-resisting test
Yellow circular cone:
Abrasive particle RKF 10K (3 parts)
Green pyramid:
Abrasive particle RKFK15P (1 part)
Sanitising agent:
Sanitising agent FC120
Test duration: 2h
Fill abrasive mixt (all about 15 liters) in the groove of test machine: 3 parts of RKF 10K (yellow circular cone) and 1 part of RKK 15P (green pyramid).Newly must be immersed in earlier and go up machine idle running 4 hours in 2 premium on currency with abrasive particle.In checkout procedure, per half hour, must add about 0.5 liter of water.At most 50-60 man-hour, change one time abrasive particle.
Before test and in the whole test process, abrasive material must wet.Therefore, before each test, must add 1 premium on currency, open machine simultaneously.In groove, add the 0.1-0.2 liter before the test
The mixture of clean-out system FC120 and water (1 deciliter of clean-out system is joined 5 premium on currency).Afterwards test products is put into groove.In wear test course, per half hour, must add about 0.5 liter of water.Accept standard: the 1h workpiece corner is not leaked copper, and 2h workpiece planarization part is not leaked copper.
(3) SaltSprayTest
Spraying (NaCl accounts for 5% of quality, pH 6.5-7.2) 2 hours under 35 ℃ of conditions, then+40 ℃, 80% humidity was placed 168 hours.Accept standard: working properly after placing 2 hours, there are not oxidation of any visible burn into and distortion (not flushable after the test)
(4) temperature shock test
-40/85 ℃, each temperature keeps 2H, and totally 5 cycles, continued 20 hour less than 3 minutes switching time, at room temperature recovered 2 hours after test is finished
Machinery: performance is normal; Accept standard: mechanical part not breakage is not out of shape.
Table 1
| Product | The test of hundred lattice cuttves | Vibrate wear-resisting test | The temperature shock test | SaltSprayTest |
| A1 | 0 grade | The corner does not have show-through material situation | Mechanical part not breakage is not out of shape | There are not oxidation of any visible burn into and distortion |
| A2 | 0 grade | The corner does not have show-through material situation | Mechanical part not breakage is not out of shape | There are not oxidation of any visible burn into and distortion |
| A3 | 0 grade | The corner does not have show-through material situation | Mechanical part not breakage is not out of shape | There are not oxidation of any visible burn into and distortion |
| B1 | 0 grade | The corner does not have show-through material situation | Mechanical part not breakage is not out of shape | Slight corrosion is arranged |
By table 1 as can be seen, titanium or titanium alloy electroplate liquid cyanide-free and nickel-free of the present invention, performances such as wear resistance, solidity to corrosion can both reach requirement simultaneously.
Claims (9)
1. pre-plating bath of titanium or titanium alloy, it is characterized in that: this pre-plating bath comprises gold sodium sulfide, conducting salt, complexing agent, brightening agent and pH buffer reagent; The pH of described electroplate liquid is 9-11.
2. the pre-plating bath of titanium or titanium alloy according to claim 1, it is characterized in that: the content of described gold sodium sulfide is 2-10g/L, the content of described conducting salt is 40-80g/L, the content of described complexing agent is 10-20g/L, the content of described brightening agent is 5-10g/L, and the content of described pH buffer reagent is 5-10g/L.
3. the pre-plating bath of titanium or titanium alloy according to claim 2 is characterized in that: described conducting salt is at least a in S-WAT, vitriolate of tartar, trisodium phosphate, the sodium sulfate; Described complexing agent is at least a in ethylenediamine tetraacetic acid (EDTA), Methionin, quadrol, the ethylene diamine tetra methylene phosphonic acid; Described brightening agent is at least a in Tripotassium Citrate, benzylidene-acetone, butynediol, asccharin, thiocarbamide, the methyl sodium disulfonate; Described pH buffer reagent is at least a of borax and boric acid.
4. titanium or titanium alloy electro-plating method is characterized in that: this method comprises titanium or titanium alloy is placed on carries out in the pre-plating bath electroplating no cyamelide copper tin again after the preplating; Wherein, described pre-plating bath is any described pre-plating bath of claim 1-3.
5. titanium or titanium alloy electro-plating method according to claim 4, the condition of described preplating is: temperature 20-35 ℃, current density 0.1-0.15A/dm
2, time 0.5-1min.
6. titanium or titanium alloy electro-plating method according to claim 5 is characterized in that: before preplating to titanium or titanium alloy polish, removing oil-removing wax and surface adjust.
7. titanium or titanium alloy electro-plating method according to claim 6 is characterized in that: it is nitric acid 61ml/L-81ml/L that used adjustment liquid is adjusted on described surface, hydrofluoric acid 61ml/L-81ml/L, hydrogen peroxide 418ml/L-438ml/L, ethylene glycol 204ml/L-224ml/L.
8. titanium or titanium alloy electro-plating method according to claim 7 is characterized in that: after electroplating copper-nickel alloy tin titanium or titanium alloy is carried out electroplated decoration coating.
9. titanium or titanium alloy electro-plating method according to claim 8 is characterized in that: pre-gold-plated and electroplate between the copper-nickel alloy tin, electroplate between copper-nickel alloy tin and the electroplated decoration coating and all will carry out activation treatment.
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