CN101892468A - Preparation method of chemically plating Ni-W-P ternary alloy on surface of Mg-Li alloy - Google Patents
Preparation method of chemically plating Ni-W-P ternary alloy on surface of Mg-Li alloy Download PDFInfo
- Publication number
- CN101892468A CN101892468A CN 201010209683 CN201010209683A CN101892468A CN 101892468 A CN101892468 A CN 101892468A CN 201010209683 CN201010209683 CN 201010209683 CN 201010209683 A CN201010209683 A CN 201010209683A CN 101892468 A CN101892468 A CN 101892468A
- Authority
- CN
- China
- Prior art keywords
- alloy
- plating
- ternary
- coating
- binary
- 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
Abstract
The invention relates to a novel method for preparing a modified Mg-Li alloy material. The method comprises the following steps: chemically plating an Ni-P binary alloy coating on the surface of an Mg-Li alloy, chemically plating an Ni-W-P ternary alloy coating, and carrying out heat treatment to further enhance the hardness and corrosion resistance of the coating. The method uses basic nickel carbonate as the main salt, thereby preventing SO4<2->, which exists in the chemical nickel plating process taking nickel sulfate as the main salt, from intensely corroding Mg-Li alloy substrate. The prepared Ni-W-P ternary alloy coating comprises 88-89 wt% of Ni, 3.4-3.8 wt% of W and 7.1-7.3 wt% of P. The average thickness of the Ni-W-P ternary alloy coating is 8-10 mu m, the corrosion potential is -0.35- -0.37 V, the corrosion current density is 0.51*10<-4>-0.53*10<-4> A/cm<2>, and the hardness is 620-740 HV. The method has the advantages of simple technique and low cost. Compared with common preparation methods, the invention is more stable and reliable, and mass production can be easily realized.
Description
Technical field
The invention belongs to light alloy surface modification preparation field, be specifically related to improve the surface property of Mg-Li alloy, prepare the method for corrosion-resistant, anti abrasive Mg-Li alloy material with a kind of Ni-W-P ternary alloy coating.
Background technology
Magnesium lithium alloy is a lightest in the world present alloy material as the novel magnesium alloy of a class, and density only is 1.35～1.65g/cm
3It has kept a lot of excellent performances of magnesium alloy, and as specific rigidity specific tenacity height, good, the normal temperature easily shaping down of forging property, and magnetic shielding is good, be easy to recycle etc., and because the adding of light metal lithium makes the specific rigidity of alloy higher, forging property is better.So as ultralight matter structural metallic materials, magnesium lithium alloy receives increasing concern.Particularly in recent years, be widely used in aerospace field, as be used for making structural partss such as air-fired missile cabin section, aileron covering, wallboard, reinforced bulkhead.In the lightweight of light arm, tank, panzer was made, its potentiality were huge especially.In automotive industry, the Mg-Li sheet alloy will be one of preferred material of car body parts such as car door, luggage boot, seat mount, window frame, chassis.
But magnesium and lithium all are the active metals, and the standard potential of magnesium is-2.37V, and lithium lower (it is active that 3.02V), this has just caused the chemical property of magnesium lithium alloy.Magnesium lithium alloy is easily oxidized in air and water medium, generate loose oxide skin, and this layer oxide compound there is no provide protection.In acidic medium, particularly magnesium lithium alloy can be subjected to the intensive corrosion in the system of chloride ion-containing, so the erosion resistance extreme difference of magnesium lithium alloy.In addition, the hardness of magnesium lithium alloy is lower.These two defectives have seriously restricted the widespread use of magnesium lithium alloy.Therefore, along with the Mg-Li alloy use increasingly extensive, become the focus of domestic and international concern gradually about improving its erosion resistance and Study on Hardness.People competitively adopt different thinkings to realize surface modification to the Mg-Li alloy.
At present, the method for Mg-Li alloy surface modifying mainly contains following several:
(1) chemical conversion embrane method
It is one of magnesium lithium alloy surface-treated common method that chemical conversion is handled.The tradition conversion processing adopts chromyl compound such as chromic salt as treatment agent mostly, forms chromate conversion coating at alloy surface.Though this technology is ripe, film forming properties is also more stable, hexavalent chromium compound has carinogenicity, and environment and human body are had in various degree harm, and strictness is forbidden in metal industry.At present countries in the world are devoted to study that protection effect is good, the conversion processing novel process of chromium-free environment-friendly.For example: people such as Yang Lihui, Jiang Weiwei (research of magnesium lithium alloy chemical conversion rete. electroplate and cover with paint, lacquer, colour wash, etc., the 27th volume, the 6th phase: 29-31) make stannate conversion film and phosphate conversion film on the magnesium lithium alloy surface with chemical transformation, though two kinds of conversion films have improved the erosion resistance of alloy to a certain extent, but two kinds of films do not cover matrix fully, there is micro gap between the particle, so the raising of alloy corrosion resistance is restricted.In addition, people (A chrome-free conversion coating for magnesium-lithium alloy by a phosphate-permanganate solution.Surface ﹠amp such as Zhang Hua, Yao Guangchun; Coatings Technology 202 (2008): 1825-1830) adopt phosphoric acid salt-permanganate conversion fluid to make conversion film at the Mg-10Li-1Zn alloy surface.But many irregular splittings are arranged on this conversion film, and be attached with white block.Behind the 1h, lip-deep crackle is more in the NaCl etchant solution of immersion 3.5%, existing corrosion.Therefore the erosion resistance by chemical transformation processing raising magnesium lithium alloy still is not an effective means.
(2) DLC embrane method
Carry out the processing of diamond-film-like (DLC) on the magnesium lithium alloy surface, effect still has significant limitation, for example: people such as N.Yamauch (DLC coating on Mg-Li alloy.Surface ﹠amp; Coatings Technology 201 (2007): 4913-4918.) adopt the pre-treating technology of SiC polishing Mg-14Li alloy, utilize RF capacitance coupling plasma CVD method to make diamond-film-like (DLC) on its surface.The sample frictional coefficient that obtains is low, wear no resistance, and is corroded in the synthetic perspiration of acid and alkalescence.
(3) anodic oxidation, metal organic coating method
Protect surface treatment with these two kinds of methods, though certain effect is arranged, the solidity to corrosion of magnesium lithium alloy, wear resistance are still undesirable.As the organic coating method, oxygen and vapor permeation easily cause the corrosion of coating, and particularly under the space flight and aviation condition, uitraviolet intensity is big, and coating more subjects to destruction and loses its protection function.And anonizing, because electropotential is very low, ion exchange takes place in magnesium lithium alloy under the current conditions in ionogen having, and generates loose displacement film and causes the surface to be corroded, so anonizing seldom is used for the surface treatment of magnesium lithium alloy.
(4) chemically coated nickel method
Along with constantly improving and raising of chemical plating nickel technology, have report in recent years at the magnesium lithium alloy chemical nickel plating on surface.By contrast, this method obtains many breakthroughs having one's own knack aspect raising magnesium lithium alloy erosion resistance and the hardness.Therefore become present magnesium lithium alloy surfacecti proteon gradually and handle effective means.
A large amount of documents shows, both at home and abroad about the chemical Ni-P plating binary alloy, the research of ternary alloys such as Electroless Plating Ni-W-P, Ni-Cr-P, Ni-Cu-P, Ni-Co-P, Ni-Mo-P, Ni-Fe-P is a lot, but the base material that most research is adopted is soft steel, aluminium alloy or other non-magnesium lithium alloys.In research to magnesium alloy (not comprising magnesium lithium alloy) chemical nickel plating on surface, existing certain achievement.For example, N.EI Mahallawy, people such as A.Bakkar (Electroless Ni-P coating of different magnesium alloys.Surface ﹠amp; Coatings Technology 202 (2008): 5151-5157.) adopt the zincate pre-treating technology, at single nickel salt is in the plating bath of main salt, obtain Ni-P coating respectively at the different last electroless platings of magnesium alloy AZ31, AE42, ZRE1, coating no significant defect or hole, erosion resistance has great raising than the magnesium alloy base material.Liu Zhenmin, people such as Gao Wei (A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment.Applied Surface Science 253 (2006): 2988-2991.) using plasma anodizing (PEO) pre-treatment before the chemical Ni-P plating, effectively prepare the Ni-P base binary alloy plating thereby on AZ91 magnesium alloy base material, make the oxide protective layer.
Research about Mg-Li alloy surface chemical nickel plating still is in the starting stage, and relevant report is few.Reason is that the character that particularly adds the magnesium lithium alloy that forms behind the light metal lithium is especially active because the character of magnesium lithium alloy is very active.Under the room temperature magnesium lithium alloy placed and promptly can be observed tangible reaction about tap water 30s, the hole of macro-corrosion appears in prolongation alloy surface in time.This shows that the so weak solidity to corrosion of Mg-Li alloy is difficult to opposing and contains various ionic chemical plating fluids, this is a great problem of Mg-Li alloy surface chemical nickel plating.People (Electroless Ni-P plating with molybdate pretreatment on Mg-8Li alloy.Journal of Alloys and Compounds such as Yang Lihui, Li Junqing, 467 (2009): 562-566.) adopt pallamine activatory pre-treating technology, with the nickel acetate is the nickel source, make chemical Ni-plating layer on the magnesium lithium alloy surface, coating is fine and close, no significant defect, but distortion born of the same parents shape projection is arranged.Its hardness can reach 350.5HV, and the erosion resistance of alloy is increased, but the chemical Ni-plating layer of individual layer still can not be born the defencive function of magnesium lithium alloy alone, also must be aided with other means.Another measure is to adopt the molybdate pre-treating technology, obtains to make Ni-P coating with similar chemical plating technology again behind the molybdate conversion film on the alloy substrate surface.Wherein, still there is a certain amount of tiny crack in the molybdate conversion film of acquisition, and this method technology is comparatively complicated, is difficult for controlling.People such as Zhang Hua, Wang shulan (Electroless Ni-P plating on Mg-10Li-1Zn alloy.Journal of Alloys and Compounds 474 (2009): 306-310.) with HF acid activation Mg-10Li-1Zn alloy, with NiSO
46H
20 is the nickel source, and the Ni-P coating that electroless plating obtains, the content of P are 7.5wt.%, and freely corroding potential is-0.484V that erosion resistance and hardness all are improved.Though the single nickel salt low price, SO
4 2-Can corrode the Mg-Li alloy base material consumingly, stablize inadequately so this legal system is equipped with nickel-phosphorus alloy coating, handling not strong, very easily cause base material to be corroded and cause the wasting of resources.Therefore this method still has very big limitation.
The comprehensive relatively various surfacecti proteon measures of magnesium lithium alloy, treatment measures such as organic coating, anodic oxidation treatment, DLC film, chemical conversion film all have significant limitation.Nickel chemical plating technology is handled the Mg-Li alloy erosion resistance and the hardness that improves alloy has been obtained certain effect, still, and the difficult problem that Mg-Li alloy surface chemical Ni-P plating binary alloy still has part to be difficult to overcome.The bibliographical information that can find at present, success is at soft steel (J.N.Balaraju, S.M.Jahan, C.Anandan, 4885) and tool steel (F.B.Wu K.S.Rajam, Surf.Coat.Technol.200 (2006):, S.K.Tien, W.Y.Chen, 312.) J.G.Duh, Surf.Coat.Technol.177-178. (2004): Electroless Nickel-Tungsten-Phosphorus Ternary Alloy on the base material such as.But preparation Ni-W-P ternary alloy has higher challenge on complicated base materials such as magnesium alloy, report has people (Electroless deposition of Ni-W-P coating on AZ91D magnesium alloy.Applied Surface Science 253 (2007): be main salt with single nickel salt 5116-5121.) such as Zhang W.X.Huang N., adopt alkali-citric acid salt bath successfully to make the Ni-W-P ternary alloy coating at the AZ91D Mg alloy surface, the coating that obtains is evenly fine and close, tungstenic 4.5wt.%, corrosion resistance nature and surface hardness all are greatly improved.But making ternary Ni-W-P coating at the magnesium lithium alloy substrate surface does not appear in the newspapers as yet.
To the objective of the invention is in order overcoming, the novel method of the Mg-Li alloy of the high preparation surface modification of a kind of good corrosion resistance, hardness new, that the surface has Ni-W-P ternary alloy structure coating to be provided with the existing defective of Mg-Li alloy surface chemical nickel plating treatment process.
Basic design of the present invention is: be subjected to the enlightenment of Electroless Nickel-Tungsten-Phosphorus Ternary Alloy on base materials such as soft steel and tool steel, imagination is in Mg-Li alloy surface Electroless Nickel-Tungsten-Phosphorus Ternary Alloy, and under differing temps, heat-treat, in the hope of obtaining Ni-W-P ternary alloy coating than Ni-P binary coating erosion resistance is better, hardness is higher.Simultaneously, traditional chemical nickel plating is main salt with single nickel salt, but SO
4 2-Can intensive ground corrode the Mg-Li alloy base material, it is main salt that the present invention uses basic nickel carbonate instead, and fully improves pre-treating technology, provides a stabilizing effective processing method that is enclosed within Mg-Li alloy surface Electroless Nickel-Tungsten-Phosphorus Ternary Alloy.
Summary of the invention
The utilization that the invention provides a kind of novelty is in Mg-Li alloy surface Electroless Nickel-Tungsten-Phosphorus Ternary Alloy, and obtain through the subsequent heat treatment row a kind of corrosion-resistant, the novel preparation method of anti abrasive Mg-Li alloy material and new technological line.
Specifically the present invention includes: a) pre-treatment of Mg-Li alloy base material: as processes such as polishing, oil removing, pickling, activation; B) chemical plating fluid preparation: comprise the preparation of Ni-P binary plating bath and ternary Ni-W-P plating bath; C) plating: obtain Ni-P base binary alloy plating and Ni-W-P ternary alloy coating successively at the Mg-Li alloy surface; D) coating thermal treatment obtains the Mg-Li alloy material that the surface has Ni-W-P ternary alloy structure.Its concrete process is as follows:
(1) pre-treatment of base material: the Mg-Li alloy base material is of a size of 25 * 15 * 2mm, with 280
#The silicon carbide abrasive paper for metallograph is smooth smooth and do not have obvious cut with surface finish, with the foreign material and the zone of oxidation of removing substrate surface; Sample ultrasonic cleaning 5～10min in dehydrated alcohol that polishing is good stays the alloy chip on the base material when removing surface and oil contaminant with polishing; At 85%H
3PO
450ml/L and 65%HNO
3Pickling 20～50s in the mix acid liquor of 10ml/L further removes zone of oxidation and makes substrate surface thoroughly clean, and the substrate surface of passivation is simultaneously removed the acid solution that remains in substrate surface with deionized water, in order to avoid acid solution is detained the corrosion base material; Acid activation: adopt 40%HF 250～380ml/L, soak time 5～40min makes substrate surface have catalytic activity; Used pickle solution and acid activation liquid can use about 20 times after the component concentration adjustment of acid repeatedly;
(2) chemical plating fluid preparation:
1. Ni-P binary plating bath: take by weighing basic nickel carbonate with balance weighing apparatus, 2Ni (OH)
21NiCO
34H
2O, 8-15g/L with the suitable quantity of water dissolving, add Trisodium Citrate respectively, Na in the 1000mL beaker
3C
6H
5O
7, 3-10g/L and ammonium bifluoride, NH
4HF
2, 8-15g/L puts into thermostat water bath 80-90 ℃ of following heated and stirred dissolving with beaker, till solution does not have bubble and emits, this beaker is taken out from water-bath, and other gets a 250mL beaker, takes by weighing inferior sodium phosphate, NaH
2PO
22H
2O, 25-35g/L is in the 1000mL beaker that joins after the suitable quantity of water dissolving before this, under agitation add ammonium bifluoride 8-15g/L, add ammoniacal liquor 28-30ml/L and hydrofluoric acid 8-12ml/L, solution PH is adjusted between the 5.0-6.5, be diluted with water to again volume required, stir the back stand-by;
2. Ni-W-P ternary plating bath: get the binary Ni-P plating bath that has prepared, press 15-25g/L and add sodium wolframate, Na
2WO
42H
2O slowly adds proper ammonia, and stirs, and fully dissolves sodium wolframate, with hydrofluoric acid pH value is adjusted to 7～8 then;
(3) plating: in the 1000mL glass beaker of band whipping appts, base material is soaked the Ni-P binary plating bath that places 600～800mL, adopt the digital display thermostat water bath, under water bath with thermostatic control, stir plating, temperature 76-82 ℃, time 25～40min obtains the chemical Ni-P plating base binary alloy plating of Mg-Li alloy; Gained base binary alloy plating sample is immersed in the ternary plating bath, plating under 88 ± 2 ℃ water bath with thermostatic control, time 20～35min makes the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy coating of Mg-Li alloy; Binary after the use and ternary plating bath be capable of circulation the use about 15 times repeatedly after the adjustment of component concentration;
(4) charging: in the high alumina crucible, add the Graphite Powder 99 of oven dry, the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is imbedded in the Graphite Powder 99 protected;
(5) thermal treatment: the crucible after will feeding is put into retort furnace the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is heat-treated, 250～300 ℃ of temperature, and insulation 1h cools to room temperature with the furnace;
(6) sampling: take out product the crucible in retort furnace, thereby obtain the Mg-Li alloy material that the surface has Ni-W-P ternary alloy structure coating.
Coating preparation facilities required for the present invention is simple to operation, mainly is made up of two portions: heating digital display thermostat water bath, plating whipping appts.Between the two effect and mutual relationship are as follows: digital display water bath with thermostatic control Pot devices is used to heat plating bath, realizes the adjustment to plating temperature; The plating whipping appts utilizes it can realize the stirring and the plating of plating bath.Two portions coordinate operation assurance electroless plating is fully carried out.
Coating thermal treatment unit required for the present invention is simple and easy to operate, mainly is made up of three parts: retort furnace, high alumina or plumbago crucible, oven dry Graphite Powder 99.Effect and mutual relationship between the three are as follows: crucible places in the retort furnace, is used to carry the plated state sample; The Graphite Powder 99 embedding plated state sample of oven dry is to prevent the oxidation to sample under hot conditions of air in the retort furnace.
The present invention compares with existing technology of preparing and technology, has following advantage and beneficial effect:
1. adopt new Ni-W-P ternary alloy structure at the Mg-Li alloy surface, coating erosion resistance and hardness are significantly improved, it is main salt that the present invention adopts basic nickel carbonate, and having avoided traditional chemical nickel plating is the existing SO of main salt with single nickel salt
4 2-Can corrode Mg-Li alloy base material drawback consumingly, make in Mg-Li alloy surface Electroless Technique of Ni-W-P Ternary Alloy more stable and reliable.
2. technology of the present invention is simple, is easy to realize industrialization.
This preparation method raw material is easy to get, and the preparation of plating bath, regeneration are simple, and plating is simple, so technological operation is simple; Preparation simultaneously, Equipment for Heating Processing is simple, and the reclaim equiment of plating bath and acid activation liquid is simple, is convenient to the industrialization operation.
3. the plating bath that uses among the present invention, pickle solution and acid activation liquid can recycle repeatedly.
Plating bath, pickle solution and acid activation liquid after the present invention uses can change the source material that can be recycled about 15 times into after the adjustment of component concentration.
Specific embodiments
Example one
(1) pre-treatment of base material: the Mg-Li alloy base material is of a size of 25 * 15 * 2mm, with 280
#The silicon carbide abrasive paper for metallograph is smooth smooth and do not have obvious cut with surface finish, with the foreign material and the zone of oxidation of removing substrate surface; Sample ultrasonic cleaning 10min in dehydrated alcohol that polishing is good stays the alloy chip on the base material when removing surface and oil contaminant with polishing; At H
3PO
4(85%) 50ml/L and HNO
3(65%) pickling 40s in the mix acid liquor of 10ml/L further removes zone of oxidation and makes substrate surface thoroughly clean, the substrate surface of passivation simultaneously; Remove the acid solution that remains in substrate surface with deionized water, in order to avoid acid solution is detained the corrosion base material; Acid activation: adopt HF (40%) 380ml/L, soak time 25min makes substrate surface have catalytic activity; Used pickle solution and acid activation liquid use range 20 times repeatedly after component concentration is adjusted.
(2) chemical plating fluid preparation:
1. Ni-P binary plating bath: take by weighing basic nickel carbonate [2Ni (OH) with balance weighing apparatus
21NiCO
34H
2O] 10g/l in the 1000Ml beaker, with suitable quantity of water dissolving, add Trisodium Citrate [Na respectively
3C
6H
5O
7] 5g/l and ammonium bifluoride [NH
4HF
2] 10g/l, beaker is put into thermostat water bath 90 ℃ of following heated and stirred dissolvings, do not have bubble up to solution and only emit, this beaker is taken out from water-bath, other gets a 250Ml beaker, takes by weighing inferior sodium phosphate [NaH
2PO
22H
2O] 30g/l, in the 1000Ml beaker that joins after the suitable quantity of water dissolving before this, under agitation add ammonium bifluoride [NH
4HF
2] 10g/l, add ammoniacal liquor 30ml/L and hydrofluoric acid 10ml/L, solution PH is adjusted between the 5.0-6.5, be diluted with water to volume requiredly again, the back that stirs is stand-by.
2. Ni-W-P ternary plating bath: get the binary Ni-P plating bath that has prepared, press 20g/l and add sodium wolframate [Na2WO42H
2O], slowly add proper ammonia, and stir, fully dissolve sodium wolframate, with hydrofluoric acid pH value is adjusted to 7～8 then.
(3) plating: in the 1000mL glass beaker of band whipping appts, base material soaked and place 700mLNi-P binary plating bath, adopt the digital display thermostat water bath, under water bath with thermostatic control, stir plating, 76 ± 2 ℃ of temperature, time 30min obtains the chemical Ni-P plating base binary alloy plating of Mg-Li alloy; Gained base binary alloy plating sample is immersed in the 700mL ternary plating bath, stirring plating under 88 ± 2 ℃ water bath with thermostatic control, time 25min makes the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy coating of Mg-Li alloy; Binary after the use and ternary plating bath be capable of circulation the use about 15 times repeatedly after the adjustment of component concentration.
(4) charging: in high alumina crucible or plumbago crucible, add the Graphite Powder 99 of oven dry, the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is imbedded in the Graphite Powder 99 protected.
(5) thermal treatment: the crucible of charging is put into retort furnace the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is heat-treated, 300 ℃ of temperature, insulation 1h cools to room temperature with the furnace.
(6) sampling: take out product the crucible in retort furnace, thereby obtain the Mg-Li alloy material that the surface has Ni-W-P ternary alloy structure coating, its performance evaluation sees Table 3.
Example two
(1) pre-treatment of base material: the Mg-Li alloy base material is of a size of 25 * 15 * 2mm, with 280
#The silicon carbide abrasive paper for metallograph is smooth smooth and do not have obvious cut with surface finish, with the foreign material and the zone of oxidation of removing substrate surface; Sample ultrasonic cleaning 15min in dehydrated alcohol that polishing is good stays the alloy chip on the base material when removing surface and oil contaminant with polishing; At H
3PO
4(85%) 50ml/L and HNO
3(65%) pickling 30s in the mix acid liquor of 10ml/L further removes zone of oxidation and makes substrate surface thoroughly clean, the substrate surface of passivation simultaneously; Remove the acid solution that remains in substrate surface with deionized water, in order to avoid acid solution is detained the corrosion base material; Acid activation: adopt HF (40%) 380ml/L, soak time 20min makes substrate surface have catalytic activity; Used pickle solution and acid activation liquid use range 20 times repeatedly after component concentration is adjusted.
(2) chemical plating fluid preparation:
1. Ni-P binary plating bath: take by weighing basic nickel carbonate [2Ni (OH) with balance weighing apparatus
21NiCO
34H
2O] 8g/l in the 1000Ml beaker, with suitable quantity of water dissolving, add Trisodium Citrate [Na respectively
3C
6H
5O
7] 3g/l and ammonium bifluoride [NH
4HF
2] 8g/l, beaker is put into thermostat water bath 90 ℃ of following heated and stirred dissolvings, do not have bubble up to solution and only emit, this beaker is taken out from water-bath, other gets a 250Ml beaker, takes by weighing inferior sodium phosphate [NaH
2PO
22H
2O] 25g/l, in the 1000Ml beaker that joins after the suitable quantity of water dissolving before this, under agitation add ammonium bifluoride [NH
4HF
2] 8g/l, add ammoniacal liquor 30ml/L and hydrofluoric acid 12ml/L, solution PH is adjusted between the 5.0-6.5, be diluted with water to volume requiredly again, the back that stirs is stand-by.
2. Ni-W-P ternary plating bath: get the binary Ni-P plating bath that has prepared, press 15g/l and add sodium wolframate [Na2WO42H
2O], slowly add proper ammonia, and stir, fully dissolve sodium wolframate, with hydrofluoric acid pH value is adjusted to 7～8 then.
(3) plating: in the 1000mL glass beaker of band whipping appts, base material soaked and place 600mLNi-P binary plating bath, adopt the digital display thermostat water bath, under water bath with thermostatic control, stir plating, 78 ± 2 ℃ of temperature, time 25min obtains the chemical Ni-P plating base binary alloy plating of Mg-Li alloy; Gained base binary alloy plating sample is immersed in the 600mL ternary plating bath, stirring plating under 88 ± 2 ℃ water bath with thermostatic control, time 20min makes the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy coating of Mg-Li alloy; Binary after the use and ternary plating bath be capable of circulation the use about 15 times repeatedly after the adjustment of component concentration.
(4) charging: in high alumina crucible or plumbago crucible, add the Graphite Powder 99 of oven dry, the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is imbedded in the Graphite Powder 99 protected.
(5) thermal treatment: the crucible of charging is put into retort furnace the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is heat-treated, 250 ℃ of temperature, insulation 1h cools to room temperature with the furnace.
(6) sampling: take out product the crucible in retort furnace, thereby obtain the Mg-Li alloy material that the surface has Ni-W-P ternary alloy structure coating, its performance evaluation sees Table 3.
Example three
(1) pre-treatment of base material: the Mg-Li alloy base material is of a size of 25 * 15 * 2mm, with 280
#The silicon carbide abrasive paper for metallograph is smooth smooth and do not have obvious cut with surface finish, with the foreign material and the zone of oxidation of removing substrate surface; Sample ultrasonic cleaning 8min in dehydrated alcohol that polishing is good stays the alloy chip on the base material when removing surface and oil contaminant with polishing; At H
3PO
4(85%) 50ml/L and HNO
3(65%) pickling 20s in the mix acid liquor of 10ml/L further removes zone of oxidation and makes substrate surface thoroughly clean, the substrate surface of passivation simultaneously; Remove the acid solution that remains in substrate surface with deionized water, in order to avoid acid solution is detained the corrosion base material; Acid activation: adopt HF (40%) 380ml/L, soak time 10min makes substrate surface have catalytic activity; Used pickle solution and acid activation liquid use range 20 times repeatedly after component concentration is adjusted.
(2) chemical plating fluid preparation: the preparation of Ni-P binary plating bath sees Table 1c, and the preparation of Ni-W-P plating bath sees Table 2c.
1. Ni-P binary plating bath: take by weighing basic nickel carbonate [2Ni (OH) with balance weighing apparatus
21NiCO
34H
2O] 15g/l in the 1000Ml beaker, with suitable quantity of water dissolving, add Trisodium Citrate [Na respectively
3C
6H
5O
7] 10g/l and ammonium bifluoride [NH
4HF
2] 15g/l, beaker is put into thermostat water bath 80-90 ℃ of following heated and stirred dissolving, do not have bubble up to solution and only emit, this beaker is taken out from water-bath, other gets a 250Ml beaker, takes by weighing inferior sodium phosphate [NaH
2PO
22H
2O] 35g/l, in the 1000Ml beaker that joins after the suitable quantity of water dissolving before this, under agitation add ammonium bifluoride [NH
4HF
2] 15g/l, add ammoniacal liquor 28-30ml/L and hydrofluoric acid 12ml/L, solution PH is adjusted between the 5.0-6.5, be diluted with water to volume requiredly again, the back that stirs is stand-by.
2. Ni-W-P ternary plating bath: get the binary Ni-P plating bath that has prepared, press 25g/l and add sodium wolframate [Na2WO42H
2O], slowly add proper ammonia, and stir, fully dissolve sodium wolframate, with hydrofluoric acid pH value is adjusted to 7～8 then.
(3) plating: in the 1000mL glass beaker of band whipping appts, base material soaked and place 800mLNi-P binary plating bath, adopt the digital display thermostat water bath, under water bath with thermostatic control, stir plating, 78 ± 2 ℃ of temperature, time 20min obtains the chemical Ni-P plating base binary alloy plating of Mg-Li alloy; Gained base binary alloy plating sample is immersed in the 600mL ternary plating bath, stirring plating under 88 ± 2 ℃ water bath with thermostatic control, time 15min makes the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy coating of Mg-Li alloy; Binary after the use and ternary plating bath be capable of circulation the use about 15 times repeatedly after the adjustment of component concentration.
(4) charging: in high alumina crucible or plumbago crucible, add the Graphite Powder 99 of oven dry, the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is imbedded in the Graphite Powder 99 protected.
(5) thermal treatment: the crucible of charging is put into retort furnace the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is heat-treated, 300 ℃ of temperature, insulation 1h cools to room temperature with the furnace.
(6) sampling: take out product the crucible in retort furnace, thereby obtain the Mg-Li alloy material that the surface has Ni-W-P ternary alloy structure coating, its performance evaluation sees Table 3.
The performance evaluation of Ni-W-P ternary alloy coating modification Mg-Li alloy material in each example of table 3.
Claims (3)
1. the preparation method of a Mg-Li alloy surface Electroless Nickel-Tungsten-Phosphorus Ternary Alloy is characterized in that comprising following process:
(1) pre-treatment of base material: the Mg-Li alloy base material is of a size of 25 * 15 * 2mm, with 280
#The silicon carbide abrasive paper for metallograph is smooth smooth and do not have obvious cut with surface finish, with the foreign material and the zone of oxidation of removing substrate surface; Sample ultrasonic cleaning 5～10min in dehydrated alcohol that polishing is good stays the alloy chip on the base material when removing surface and oil contaminant with polishing; At 85%H
3PO
450ml/L and 65%HNO
3Pickling 20～50s in the mix acid liquor of 10ml/L further removes zone of oxidation and makes substrate surface thoroughly clean, and the substrate surface of passivation is simultaneously removed the acid solution that remains in substrate surface with deionized water, in order to avoid acid solution is detained the corrosion base material; Acid activation: adopt 40%HF 250～380ml/L, soak time 5～40min makes substrate surface have catalytic activity; Used pickle solution and acid activation liquid can use about 20 times after the component concentration adjustment of acid repeatedly;
(2) chemical plating fluid preparation:
1. Ni-P binary plating bath: take by weighing basic nickel carbonate with balance weighing apparatus, 2Ni (OH)
21NiCO
34H
2O, 8-15g/L with the suitable quantity of water dissolving, add Trisodium Citrate respectively, Na in the 1000mL beaker
3C
6H
5O
7, 3-10g/L and ammonium bifluoride, NH
4HF
2, 8-15g/L puts into thermostat water bath 80-90 ℃ of following heated and stirred dissolving with beaker, till solution does not have bubble and emits, this beaker is taken out from water-bath, and other gets a 250mL beaker, takes by weighing inferior sodium phosphate, NaH
2PO
22H
2O, 25-35g/L is in the 1000mL beaker that joins after the suitable quantity of water dissolving before this, under agitation add ammonium bifluoride 8-15g/L, add ammoniacal liquor 28-30ml/L and hydrofluoric acid 8-12ml/L, solution PH is adjusted between the 5.0-6.5, be diluted with water to again volume required, stir the back stand-by;
2. Ni-W-P ternary plating bath: get the binary Ni-P plating bath that has prepared, press 15-25g/L and add sodium wolframate, Na
2WO
42H
2O slowly adds proper ammonia, and stirs, and fully dissolves sodium wolframate, with hydrofluoric acid pH value is adjusted to 7～8 then;
(3) plating: in the 1000mL glass beaker of band whipping appts, base material is soaked the Ni-P binary plating bath that places 600～800mL, adopt the digital display thermostat water bath, under water bath with thermostatic control, stir plating, temperature 76-82 ℃, time 25～40min obtains the chemical Ni-P plating base binary alloy plating of Mg-Li alloy; Gained base binary alloy plating sample is immersed in the ternary plating bath, plating under 88 ± 2 ℃ water bath with thermostatic control, time 20～35min makes the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy coating of Mg-Li alloy; Binary after the use and ternary plating bath be capable of circulation the use about 15 times repeatedly after the adjustment of component concentration;
(4) charging: in the high alumina crucible, add the Graphite Powder 99 of oven dry, the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is imbedded in the Graphite Powder 99 protected;
(5) thermal treatment: the crucible after will feeding is put into retort furnace the Electroless Nickel-Tungsten-Phosphorus Ternary Alloy sample is heat-treated, 250～300 ℃ of temperature, and insulation 1h cools to room temperature with the furnace;
(6) sampling: take out product the crucible in retort furnace, thereby obtain the Mg-Li alloy material that the surface has Ni-W-P ternary alloy structure coating.
2. by the preparation method of the described a kind of Mg-Li alloy surface Electroless Nickel-Tungsten-Phosphorus Ternary Alloy of claim 1, it is characterized in that with basic nickel carbonate be main salt, by obtaining the Ni-W-P ternary alloy coating again on the basis that obtains the Ni-P base binary alloy plating at the Mg-Li alloy surface, further improve the hardness and the erosion resistance of coating by thermal treatment.
3. by the preparation method of the described a kind of Mg-Li alloy surface Electroless Nickel-Tungsten-Phosphorus Ternary Alloy of claim 1, it is characterized in that the Ni-W-P ternary alloy coating for preparing, Ni 88～89wt%, W 3.4～3.8wt%, P 7.1～7.3wt%, mean thickness 8～10 μ m, corrosion potential-0.35～-0.37V, corrosion electric current density 0.51 * 10
-4～0.53 * 10
-4A/cm
2, hardness 620～740HV.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010209683 CN101892468A (en) | 2010-06-25 | 2010-06-25 | Preparation method of chemically plating Ni-W-P ternary alloy on surface of Mg-Li alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010209683 CN101892468A (en) | 2010-06-25 | 2010-06-25 | Preparation method of chemically plating Ni-W-P ternary alloy on surface of Mg-Li alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101892468A true CN101892468A (en) | 2010-11-24 |
Family
ID=43101809
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010209683 Pending CN101892468A (en) | 2010-06-25 | 2010-06-25 | Preparation method of chemically plating Ni-W-P ternary alloy on surface of Mg-Li alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101892468A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102965647A (en) * | 2012-11-28 | 2013-03-13 | 山东轻工业学院 | Laser nanocrystallization method of Ni-W-P and Ni-P dual-alloy coating |
| CN103789753A (en) * | 2014-02-24 | 2014-05-14 | 哈尔滨工程大学 | Environment-friendly ultrasonic-assisted magnesium-lithium alloy chemical nickel-phosphate plating process |
| CN103866298A (en) * | 2014-02-27 | 2014-06-18 | 北京航天控制仪器研究所 | Chemical nickel-plating pretreatment method for beryllium product |
| CN107868950A (en) * | 2017-11-24 | 2018-04-03 | 沈阳工业大学 | A kind of TiB2The method of powder surface no-palladium activating chemical plating nickel-molybdenum-phosphorus ternary alloy three-partalloy |
| CN110052681A (en) * | 2011-11-03 | 2019-07-26 | 西门子能源公司 | The nearly ternary eutectic alloy of NI-TI-CR for internal passages of gas turbine components reparation |
-
2010
- 2010-06-25 CN CN 201010209683 patent/CN101892468A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 《吉林大学硕士学位论文》 20061015 何金国 AZ91D镁合金化学镀Ni-P及Ni-W-P的研究 第29页，第34-44页 , 2 * |
| 《材料保护》 20061031 韩玉昌等 Mg-13Li-5Zn合金化学镀镍研究 第38-40页 第39卷, 第10期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110052681A (en) * | 2011-11-03 | 2019-07-26 | 西门子能源公司 | The nearly ternary eutectic alloy of NI-TI-CR for internal passages of gas turbine components reparation |
| CN102965647A (en) * | 2012-11-28 | 2013-03-13 | 山东轻工业学院 | Laser nanocrystallization method of Ni-W-P and Ni-P dual-alloy coating |
| CN102965647B (en) * | 2012-11-28 | 2014-12-24 | 山东轻工业学院 | Laser nanocrystallization method of Ni-W-P and Ni-P dual-alloy coating |
| CN103789753A (en) * | 2014-02-24 | 2014-05-14 | 哈尔滨工程大学 | Environment-friendly ultrasonic-assisted magnesium-lithium alloy chemical nickel-phosphate plating process |
| CN103789753B (en) * | 2014-02-24 | 2015-10-28 | 哈尔滨工程大学 | Environment ultrasonic assisting magnesium lithium alloy chemistry Ni-P-plating technique |
| CN103866298A (en) * | 2014-02-27 | 2014-06-18 | 北京航天控制仪器研究所 | Chemical nickel-plating pretreatment method for beryllium product |
| CN103866298B (en) * | 2014-02-27 | 2016-03-02 | 北京航天控制仪器研究所 | A kind of beryllium material chemical nickel plating pre-treating process |
| CN107868950A (en) * | 2017-11-24 | 2018-04-03 | 沈阳工业大学 | A kind of TiB2The method of powder surface no-palladium activating chemical plating nickel-molybdenum-phosphorus ternary alloy three-partalloy |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100462479C (en) | Chemical plating method for Mg and its alloy | |
| CN104561999B (en) | A kind of method for preparing super-hydrophobic film layer in Mg alloy surface | |
| CN100430520C (en) | Process for copper coating on surface of magnesium and magnesium alloy | |
| CN100464006C (en) | Process for preparing magnesium alloy surface function gradient film | |
| CN102766862B (en) | Treating fluid and method for preparing vanadium-zirconium composite conversion coatings with self-repairing performance on aluminum alloy surfaces through same | |
| CN102242358B (en) | Treatment solution and treatment method for preparing golden cryolite conversion film on surface of aluminum alloy | |
| CN102534732B (en) | Pulse-electrodeposited Ni-Co-P/HBN composite plating and preparation method thereof | |
| Sun et al. | Preparation and corrosion resistance of cerium conversion coatings on AZ91D magnesium alloy by a cathodic electrochemical treatment | |
| CN107937893B (en) | Environment-friendly passivation solution for aluminum or aluminum alloy and preparation method and treatment process thereof | |
| CN100497734C (en) | Chemical treatment method for aluminum alloy surface | |
| CN107267967B (en) | A method of super-hydrophobic copper coating is prepared in aluminum alloy surface | |
| CN101892468A (en) | Preparation method of chemically plating Ni-W-P ternary alloy on surface of Mg-Li alloy | |
| CN103614717B (en) | Wear-resistance film layer prepared by a kind of Mg alloy surface hydrothermal method and preparation technology thereof | |
| CN102392284A (en) | One-step treatment method for coloring and sealing aluminium anodic oxide film | |
| CN105297011A (en) | Method for preparing super-hydrophobic composite film layer on surface of magnesium alloy | |
| CN101696500A (en) | Method for anticorrosion treatment on surface of magnesium alloy material | |
| CN109576740B (en) | Bright black nickel electroplating solution and preparation method thereof, electroplated part and electroplating method of bright black nickel | |
| CN102199767A (en) | Cr-free F-free color passivation solution and passivation method for electroplated Zn-Ni alloy plating layer | |
| CN102477570A (en) | Method for performing black electroplating treatment on aluminum-based carborundum composite | |
| CN102817019A (en) | Plating solution for chemical plating of nickel-phosphorus metal layer on surface of magnesium alloy as well as preparation and use method for plating solution | |
| Pinheiro et al. | Influence of concentration and ph of hexafluorozirconic acid on corrosion resistance of anodized AA7075-T6 | |
| Wang et al. | Fabrication of superhydrophobic Zn-Ni coatings on LA43M magnesium alloy | |
| CN106756969A (en) | A kind of cobalt salt black chemical oxidation liquid and its application for aluminium and aluminium alloy | |
| JP6547232B2 (en) | Plating solution and method of producing plated product | |
| CN105780073B (en) | The method of priming of cyanideless electro-plating nickel on a kind of magnesium lithium alloy |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20101124 |