CN1448538A - Bath and method for coating bright and high anticorrosion alloy layer on metal surface - Google Patents
Bath and method for coating bright and high anticorrosion alloy layer on metal surface Download PDFInfo
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- CN1448538A CN1448538A CN 02113568 CN02113568A CN1448538A CN 1448538 A CN1448538 A CN 1448538A CN 02113568 CN02113568 CN 02113568 CN 02113568 A CN02113568 A CN 02113568A CN 1448538 A CN1448538 A CN 1448538A
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 12
- 239000000956 alloy Substances 0.000 title claims abstract description 12
- 239000011248 coating agent Substances 0.000 title claims description 22
- 238000000576 coating method Methods 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 15
- 229910052751 metal Inorganic materials 0.000 title description 7
- 239000002184 metal Substances 0.000 title description 7
- 238000007747 plating Methods 0.000 claims abstract description 96
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 22
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000002815 nickel Chemical class 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 12
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000004310 lactic acid Substances 0.000 claims abstract description 11
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 30
- 238000005260 corrosion Methods 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 230000007797 corrosion Effects 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 21
- 239000001488 sodium phosphate Substances 0.000 claims description 13
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 13
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- -1 accelerator Chemical compound 0.000 claims description 3
- 238000007772 electroless plating Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 30
- 238000005282 brightening Methods 0.000 abstract description 13
- 239000010935 stainless steel Substances 0.000 abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract 1
- 230000002045 lasting effect Effects 0.000 abstract 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 abstract 1
- 238000005554 pickling Methods 0.000 abstract 1
- 229910000831 Steel Inorganic materials 0.000 description 24
- 239000010959 steel Substances 0.000 description 24
- 229910018104 Ni-P Inorganic materials 0.000 description 23
- 229910018536 Ni—P Inorganic materials 0.000 description 23
- 238000005516 engineering process Methods 0.000 description 18
- 239000011159 matrix material Substances 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- 229910001369 Brass Inorganic materials 0.000 description 7
- 239000010951 brass Substances 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229910001096 P alloy Inorganic materials 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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- Electroplating And Plating Baths Therefor (AREA)
Abstract
The plating liquid contains nickel salt and sodium hypophosphorite as well as c-p reagent synthesized with copper sulfate and lactic acid, complexing agent and/or accelerant. While plating, the plated workpiece is first pre-treated via water washing, deoiling, pickling, etc., then chemically plated inside the plating liquid at 70-98 deg.c for 0.5-6 hr and finally chemically film converted at pH 4.2-5.4 to obtain bright and anticorrosive non-crystalline alloy layer superior to stainless steel 1Cr18 Ni 9Ti. The plating liquid has low cost, lasting brightness, no environmental pollution and no any brightening agent and other chemical reagent added.
Description
The present invention relates to a kind of plating bath and method, belong to the electroless plating field at metallic surface chemical plating of corrosion resisting amorphous alloy layer.
The luminance brightness of metallic surface and solidity to corrosion can not only increase the attractive in appearance of workpiece, and can improve the decorative effect and the surface property of material, and be comparatively extensive in the application in fields such as precision optical machinery, instrument, electronic component, medicine equipment, five metals, ornament.The luminance brightness of metal material surface and solidity to corrosion have a direct impact the use properties of workpiece, and selecting the alloy layer of high brightness and high anti-corrosion is the important means of improving the quality of products.Along with the develop rapidly of science and technology and modern industry, people are more and more higher to ornamental requirement, and wherein, luminance brightness and solidity to corrosion are two big important indicators of metal plating, and the quality of quality of coating and practicality are also closely related with this two big technical indicator.The technology of traditional decoration coating is electrodeposited chromium and electro-coppering.Because electrodeposited chromium exists: (1) cathode efficiency is low, plating speed is slow, power consumption; The chromium mist of chromic acid of (2) taking out of and generation both polluted environment, and sexavalent chrome is bigger to operator's hazardness simultaneously, for this reason, electroplated factory and need expend many energy and spend a lot of money to remove to handle chromic wastewater problem; (3) the dispersion covering power of electroplate liquid is poor; (4) electrodeposited chromium produces tiny crack easily in coating, and the solidity to corrosion variation that makes chromium coating is (referring to " Plating and Surface Finishing " 1997; " modern new surface treatment technologies " Science and Technology of Shanghai technical literature press, 1994).And copper-plating technique endangers health of operators because of adopting the cuprous cyanide and the sodium cyanide of severe toxicity, and serious environment pollution is (referring to " Plating and Surface Finishing " 1999; Wen Sixiong " material protection " 1999).And in the process of being coated with, cathode current density is too high, the hydrogen evolution aggravation, and copper coating easily produces space, pit, and the easy passivation of negative electrode finally causes plating bath aging, influences the quality of coating.The compact structure of copper plate and solidity to corrosion are relatively poor in addition, and the accumulation of the brightening agent degradation production that adds, and often cause that copper plate is coarse, bonding force variation and the obfuscation of low current density district.
Just because of above reason, electroplating industry and environmental administration are devoted to the technology of reform traditional always, and replace severe toxicity with the nickel plating technology of non-environmental-pollution and human body had serious harm and inefficient chromium plating and copper-plating technique.Nickel plating technology is divided into electronickelling and two kinds of technologies of chemical nickel plating,
Because chemical nickel plating has: the thickness of coating at (1) any position of workpiece all basic identical (comprising groove, slit, blind hole etc.); (2) do not need dehydrogenation; (3) do not need DC power supply device and special fixtures, and simple to operate, to save the energy, production efficiency height, cost low, is not subjected to the restriction of part shape size; (4) bath stability is good, and sedimentation velocity is fast, and long service life is easy to safeguard etc.Therefore, it is that the utmost point is hopeful the novel surface intensifying technology with future, in all process of surface treatment, and chemical nickel plating with the fastest developing speed, range of application is the widest (referring to " modern chemistry nickel plating and compound plating new technology " National Defense Industry Press 1999; " Chinese Surface Engineering " 2001).
At present, used chemical nickel-plating solution is divided into alkali plating solution and acidic bath both at home and abroad, and the Ni-P alloy that is coated with from alkali plating solution is a crystalline structure because phosphorus content is lower, and therefore, the solidity to corrosion of Ni-P alloy layer is relatively poor.And it is higher from the Ni-P alloy phosphorus content that acidic bath was coated with, formed phosphatize phosphate coat at coating surface, because the effect of other additive in phosphatize phosphate coat and the plating bath, make coating surface become grey black and coloured settling, can't play decorative effect, and the bright degree of coating is an important indicator of weighing quality of coating, it is extremely important operation during surface finishing is handled, also be for a long time one of the most general technology in the industrial application (referring to press of " chemical nickel plating " Shanghai Communications University, 1996 years; " Plating and SurfaceFinishing " 1999).To this, people adopt the mode of plating back mechanical polishing to make the coating surface light, but electric energy and power that mechanical polishing consumes are big, and the dust of generation is many, and the time is long, is not suitable for handling big, the complex-shaped and irregular workpiece of quantity.In order to change the shortcoming of mechanical polishing process, people adopt the mode of adding elementary brightening agent, second-class brightener, leveling agent, stress relieving agent, wetting agent and other reagent in chemical nickel-plating solution to make the coating surface light, so just in nickel layer, introduced many impurity, nickel layer has been become fragile and the solidity to corrosion variation.Because the decomposition rate of brightening agent is fast, the life-span is short, coating stress is big and consumption is big, price is high, not only workpiece is produced corrosion, and can bring out that ray velocity is slow, leveling property is undesirable, production efficiency is low, the nickel consumption is bigger, the cost height, and make the light hold-time of coating surface not long.Therefore up till now for this reason, still do not have good brightening agent both at home and abroad and improve the luminance brightness of electroless nickel alloy layer and solidity to corrosion simultaneously (referring to " electroplating and finish " 1999; " Metal Finishing " 2000; " electroplating and environmental protection " 1998; " electroplate and cover with paint, lacquer, colour wash, etc. " 2001).
The highly toxic substance pollution on the environment that is brought at chromium plating and copper-plating technique, and add solidity to corrosion variation, the cost height that brightening agent makes nickel layer in the existing nickel chemical plating technology, and the dust that causes of mechanical polishing and labour intensity is big, treatment capacity big, special-shaped workpiece is than problems such as difficulties.
The present invention proposes a kind of any brightening agent can deposit surface-brightening and corrosion resisting amorphous alloy layer from chemical nickel-plating solution processing method and plating bath thereof that do not add.
The present invention has carried out a large amount of tests to solution composition such as the nickel salt in the chemical plating solution, reductive agent, complexing agent, accelerator, buffer reagent and promotor and parameter, successfully never adds the amorphous alloy layer that deposits surface-brightening and high anti-corrosion in the chemical nickel-plating solution of any brightening agent and other additives.
Concrete scheme of the present invention is: a kind of plating bath at metallic surface chemical plating light and corrosion resisting amorphous alloy layer, and it comprises nickel salt, inferior sodium phosphate is characterized in that adding by copper sulfate and the composite C-P reagent of lactic acid.Be used to increase the stability of plating bath and the luminance brightness of metal plating.Described nickel salt is single nickel salt or nickelous chloride.
In the described C-P reagent, the amount of copper sulfate and lactic acid is respectively:
Lactic acid 1.2 * 10
-6～5 * 10
-2Mol.
Described plating bath also comprises complexing agent or accelerator, perhaps complexing agent and accelerator, and accelerator is succsinic acid, complexing agent is an oxysuccinic acid.So that make nickel ion form stable complex compound, prevent oxyhydroxide and hypophosphite precipitation, increase the sedimentation velocity of coating simultaneously.
Described plating bath is made up of following ingredients:
Nickel salt 0.02～0.152mol/L inferior sodium phosphate 0.009～0.425mol/L
Described plating bath is prepared by following method:
1. the nickel salt, inferior sodium phosphate, complexing agent, accelerator, the C-P reagent (copper sulfate+lactic acid) that take by weighing metering are used dissolved in distilled water respectively.
2. the dissolved nickel salt solution is poured in the dissolved enveloping agent solution, mixed.
3. dissolved C-P reagent (copper sulfate+lactic acid) is poured into set by step in the 2 resulting solution, mixed.
4. with consoluet ortho phosphorous acid sodium solution, under vigorous stirring, slowly pour in the solution of 3 preparations set by step, mix.
5. will speed up agent solution and pour into set by step in 4 solution that prepare, and mix.
Another concrete scheme of the present invention is: a kind of method at metallic surface chemical plating light and corrosion resisting amorphous alloy layer is characterized in that:
With plating piece through the washing after, immerse oil removing in the sodium carbonate solution, washing, immerse etch in sulfuric acid and the hydrochloric acid soln then, 4.2～5.4 above-mentioned plating bath is put into pH value and is in cold and hot washing, 70～98 ℃ of electroless platings 0.5～6 hour, washing is carried out chemical conversion film and is handled, washing, dehydrated alcohol cleans, and dries up.
The present invention compared with prior art has following advantage and effect:
The first, owing to do not add any elementary brightening agent, second-class brightener, leveling agent, stress relieving agent and wetting agent in the plating bath, not only the plating bath cost is low, and saved the technology of plating back mechanical polishing, and in strong acid-base brine corrosion media such as sulfuric acid, hydrochloric acid, phosphoric acid, hydrofluoric acid, sodium hydroxide and sodium-chlor, soaked corrosion entirely 48 hours or placed air for a long time, also can keep amorphous alloy layer to have very high light and can variable color, technology is free from environmental pollution.
The second, owing to do not add any brightening agent and other additives in the plating bath, be not subjected to any contaminating impurity, make coating keep original non-crystalline state feature, has high solidity to corrosion, in the strongly-acid corrosive medium, the solidity to corrosion of matrix Q235 steel is improved more than 38 times, meet and exceed the 1Cr18Ni9Ti stainless steel, be much better than brass coating and other non-ferrous metal.If the amorphous alloy layer of plating one deck high anti-corrosion on low-cost low carbon steel substrate, non-ferrous metals such as expensive whole stainless steel, copper, aluminium had both been replaced, saved a large amount of noble metals again, so, high social and economic benefit had.Overcome existing nickel plating technology owing to adding the shortcoming that a large amount of brightening agents become fragile nickel layer and solidity to corrosion reduces in the plating bath.
Three, this plating bath is successfully at the nickel alloy layer of Q235 steel matrix surface deposition amorphous structure, qualitative method test result through coat binding strengths such as thermal shock test method and file methods shows, be up to state standards the fully technical requirements of GB/13913-92 of the bonding force between amorphous alloy layer and the Q235 steel.In addition, with the analysis revealed of electronic probe and metaloscope, amorphous alloy layer combines better with the Q235 steel matrix.
Fig. 1 is chemical plating Mi-P alloy layer provided by the invention, Q235 steel matrix and the stainless X-ray diffractogram of 1Cr18Ni9Ti;
Fig. 2 is the transverse section metallograph (* 300) of Electroless Ni P Amorphous Alloy layer provided by the invention;
Fig. 3 is the transverse section stereoscan photograph (SE * 1000) of Electroless Ni P Amorphous Alloy layer provided by the invention;
Fig. 4 is the electron probe microanalysis result of Electroless Ni P Amorphous Alloy composition of layer provided by the invention;
Further specify the present invention below by embodiment:
Adopting the Q235 steel of 60mm * 15mm * 1.5mm is substrate, with its washing, electrochemical deoiling, washing, acid etching, cold and hot washing, to put into pH value be that 4.4 and 92 ℃ plating bath carries out plating, obtains the Ni-P amorphous alloy layer.
Plating bath preparation: single nickel salt 0.057mol, inferior sodium phosphate 0.226mol, C-P reagent 2.8 * 10
-4Mol, wherein copper sulfate 4 * 10
-6Mol, lactic acid 2.76 * 10
-4Mol.(1) takes by weighing the 0.057mol single nickel salt, use a small amount of dissolved in distilled water; (2) take by weighing 2.8 * 10
-4Mol C-P reagent is used a small amount of dissolved in distilled water; (3) consoluet C-P reagent is poured in the dissolved nickel sulfate solution; (4) take by weighing the 0.226mol inferior sodium phosphate, behind a small amount of dissolved in distilled water, under fully stirring, pour in the above-mentioned solution, mix.(5) the solution pH value is transferred to 4.4, again with distilled water diluting to 1 liter.(6) 90 ℃ of following platings, obtain the Ni-P amorphous alloy layer.
Adopt the Q235 base steel sheet of 60mm * 15mm * 1.5mm, carry out pre-treatment by embodiment 1, prescription changes single nickel salt 0.0761mol into, inferior sodium phosphate 0.227mol, C-P reagent 2.8 * 10
-4Mol, wherein copper sulfate is 0, the pH value of plating bath is transferred to 4.6,92 ℃ of following platings, obtains the Ni-P amorphous alloy layer.
Adopt the Q235 base steel sheet of 60mm * 15mm * 1.5mm, its pretreatment technology is with embodiment 1, and prescription changes single nickel salt 0.0951mol into, inferior sodium phosphate 0.227mol, C-P reagent 2.95 * 10
-4Mol, the pH value of plating bath is transferred to 4.8, and plating in 93 ℃ plating bath obtains the Ni-P amorphous alloy layer.
Embodiment 4
Adopt the Q235 base steel sheet of 60mm * 15mm * 1.5mm, its pretreatment technology is with embodiment 1, and prescription changes single nickel salt 0.0761mol into, inferior sodium phosphate 0.227mol, oxysuccinic acid 0.0224mol, succsinic acid 7.46 * 10
-3Mol, C-P reagent 1.67 * 10
-4Mol, the pH value of plating bath is transferred to 4.8, and plating in 90 ℃ plating bath obtains the Ni-P amorphous alloy layer.
Embodiment 5
Adopt the Q235 base steel sheet of 60mm * 15mm * 1.5mm, its pretreatment technology is with embodiment 1, and prescription changes single nickel salt 0.0761mol into, inferior sodium phosphate 0.227mol, succsinic acid 0.102mol, C-P reagent 2.22 * 10
-4Mol, the pH value of plating bath is transferred to 5.2, and plating in 92 ℃ plating bath obtains the Ni-P amorphous alloy layer.
Embodiment 6
Adopt the Q235 base steel sheet of 60mm * 15mm * 1.5mm, carry out pre-treatment by embodiment 1, prescription changes single nickel salt 0.0761mol into, inferior sodium phosphate 0.227mol, C-P reagent 2.72 * 10
-4Mol, wherein copper sulfate 2 * 10
-5Mol, lactic acid 2.52 * 10
-4Mol, the pH value of plating bath is transferred to 5.0, and plating in 92 ℃ plating bath obtains the Ni-P amorphous alloy layer.
Adopt the Q235 steel matrix surface chemical plating Ni-P alloy of 60mm * 15mm * 1.5mm, on X-ray diffractometer, measure, the X-ray analysis of Ni-P alloy layer, Q235 steel matrix and the stainless weave construction of 1Cr18Ni9Ti the results are shown in Figure 1, as can be seen from the figure, under the plated state situation, the chemical plating Mi-P alloy layer is dispersed the distribution diffraction peak what 45 ° of diffraction angle had been located to occur to widen, illustrates that the Ni-P alloy layer has tangible amorphous structure; And the diffraction peak of Q235 steel matrix in X-ray diffractogram is more sharp-pointed, Fe[110 occurred], Fe[200], Fe[211] and Fe[220] the crystal face diffraction peak, so the Q235 steel matrix is an amorphous structure.Sharp-pointed γ [111], α [110], γ [200], γ [220], α [211] and γ [311] crystal face diffraction peak have appearred in the stainless X ray diffracting spectrum of 1Cr18Ni9Ti, therefore, the 1Cr18Ni9Ti stainless steel is a crystalline structure, from top analysis as can be seen, the present invention's chemical plating Mi-P alloy layer on Q235 steel matrix surface is the amorphous alloy layer.
Adopt the test piece of Q235 steel matrix surface chemical plating Ni-P alloy on metaloscope and scanning electronic microscope, to observe, as shown in Figures 2 and 3, as can be seen from the figure, Ni-P amorphous alloy layer even compact, coating combines well with the Q235 steel matrix.
Electron probe determination is adopted in the Coating composition analysis, and by the electron probe microanalysis (see figure 4), Ni-P amorphous alloy composition of layer is: Ni87.89%, P12.034%.
The sample of Ni-P amorphous alloy layer, matrix Q235 steel, 1Cr18Ni9Ti stainless steel and brass plating layer is placed hydrochloric acid, sulfuric acid, hydrofluoric acid, sodium hydroxide solution respectively, at room temperature soak corrosion test entirely, the results are shown in Table 1.As can be seen from Table 1, in 10% hydrochloric acid soln, the solidity to corrosion of Ni-P amorphous alloy layer is 63 times of matrix Q235 steel, is 4 times of brass plating layer, near the 1Cr18Ni9Ti stainless steel.In 15% sulphuric acid soln, the solidity to corrosion of Ni-P amorphous alloy layer is 38 times of matrix Q235 steel, is 6 times of brass plating layer, is stainless 2 times of 1Cr18Ni9Ti.The solidity to corrosion of Ni-P amorphous alloy layer is 346 times of matrix Q235 steel in 70% phosphoric acid solution, is 50 times of brass plating layer, and is identical with the 1Cr18Ni9Ti stainless steel.In 20% hydrofluoric acid solution, the solidity to corrosion of Ni-P amorphous alloy layer is 42 times of matrix Q235 steel, is 72 times of brass plating layer, is stainless 37 times of 1Cr18Ni9Ti.In sodium hydroxide and sodium chloride solution, the corrosion stability of Ni-P amorphous alloy layer is extremely strong, is not corroded.
Table 1. sample soaks the corrosion test result entirely in each corrosive medium
| Sample | Erosion rate (mg/cm 2·h) | |||||
| 10% | 15% | 70% | 20% | 40% | 15% sodium-chlor | |
| The Ni-P amorphous alloy layer | ????0.278 | ????1.657 | ????0.262 | ????0.201 | ????0 | ????0 |
| The Q235 steel matrix | ????17.593 | ????62.787 | ????90.677 | ????8.535 | ????0.035 | ????0.092 |
| The 1Cr18Ni9Ti stainless steel | ????0.375 | ????3.628 | ????0.331 | ????7.479 | ????0.041 | ????0 |
| The brass plating layer | ????1.104 | ????9.921 | ????13.043 | ????14.398 | ????0 | ????0.055 |
Claims (7)
1, the plating bath of a kind of metallic surface coating bright and high anticorrosion alloy layer, it comprises nickel salt, inferior sodium phosphate is characterized in that adding by copper sulfate and the composite C-P reagent of lactic acid.
2, plating bath according to claim 1 is characterized in that the amount of copper sulfate and lactic acid is respectively in the described C-P reagent:
Copper sulfate 0～8 * 10
-4Mol,
Lactic acid 1.2 * 10
-6～5 * 10
-2Mol.
3, plating bath according to claim 1 is characterized in that described plating bath also comprises complexing agent or accelerator, perhaps complexing agent and accelerator, and accelerator is succsinic acid, complexing agent is an oxysuccinic acid.
4, plating bath according to claim 1 is characterized in that described nickel salt is single nickel salt or nickelous chloride.
5, plating bath according to claim 1 is characterized in that described plating bath is made up of following ingredients:
Nickel salt 0.02～0.152mol/L inferior sodium phosphate 0.009～0.425mol/L
Complexing agent 0～0.224mol/L C-P reagent 1.2 * 10
-7～0.34mol/L
Accelerator 0～0.170mol/L.
6, a kind of method of preparing plating bath as claimed in claim 1 is characterized in that described plating bath follows these steps to preparation:
A, the nickel salt that takes by weighing metering, inferior sodium phosphate, complexing agent, accelerator, C-P reagent are used dissolved in distilled water respectively.
B, dissolved nickel salt solution are poured in the dissolved enveloping agent solution, mix.
C, dissolved C-P reagent is poured into set by step in the 2 resulting solution, mixed.
D, with consoluet ortho phosphorous acid sodium solution, under vigorous stirring, slowly pour into set by step in the solution of 3 preparations, mix.
E, will speed up agent solution and pour into set by step in 4 solution that prepare, and mix.
7, a kind of method at metallic surface chemical plating light and corrosion resisting amorphous alloy layer, it is characterized in that: plating piece after washing, is immersed oil removing in the sodium carbonate solution, washing, immerse etch in sulfuric acid and the hydrochloric acid soln then, cold and hot washing, put into pH value and be 4.2～5.4 plating bath, 70～98 ℃ of electroless platings 0.5～6 hour, washing, carrying out chemical conversion film handles, washing, dehydrated alcohol cleans, and dries up.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101906626A (en) * | 2010-07-23 | 2010-12-08 | 中国矿业大学 | A kind of ternary amorphous alloy for scale inhibition and its preparation method |
| CN105177641A (en) * | 2015-10-27 | 2015-12-23 | 姜少群 | Nickel-plated steel shell |
| CN113310776A (en) * | 2021-05-17 | 2021-08-27 | 东方电气集团东方锅炉股份有限公司 | Etchant for testing welding joint of S31042 and T91 or T92 dissimilar steel and preparation method thereof |
| CN113652676A (en) * | 2021-07-06 | 2021-11-16 | 深圳市信维通信股份有限公司 | Low-stress chemical copper plating solution and preparation method thereof |
| CN114318459A (en) * | 2022-01-27 | 2022-04-12 | 重庆建设工业(集团)有限责任公司 | Functional plating solution and preparation method and application thereof |
| JP7733848B1 (en) * | 2025-03-26 | 2025-09-03 | 上村工業株式会社 | Electroless nickel plating film, electroless nickel plating bath, and method for producing electroless nickel plating film |
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2002
- 2002-04-03 CN CN 02113568 patent/CN1204290C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906626A (en) * | 2010-07-23 | 2010-12-08 | 中国矿业大学 | A kind of ternary amorphous alloy for scale inhibition and its preparation method |
| CN101906626B (en) * | 2010-07-23 | 2012-05-23 | 中国矿业大学 | A kind of ternary amorphous alloy for scale inhibition and its preparation method |
| CN105177641A (en) * | 2015-10-27 | 2015-12-23 | 姜少群 | Nickel-plated steel shell |
| CN113310776A (en) * | 2021-05-17 | 2021-08-27 | 东方电气集团东方锅炉股份有限公司 | Etchant for testing welding joint of S31042 and T91 or T92 dissimilar steel and preparation method thereof |
| CN113310776B (en) * | 2021-05-17 | 2022-11-29 | 东方电气集团东方锅炉股份有限公司 | Etchant for inspection S31042 and T91 or T92 dissimilar steel welding joint and preparation method thereof |
| CN113652676A (en) * | 2021-07-06 | 2021-11-16 | 深圳市信维通信股份有限公司 | Low-stress chemical copper plating solution and preparation method thereof |
| CN114318459A (en) * | 2022-01-27 | 2022-04-12 | 重庆建设工业(集团)有限责任公司 | Functional plating solution and preparation method and application thereof |
| JP7733848B1 (en) * | 2025-03-26 | 2025-09-03 | 上村工業株式会社 | Electroless nickel plating film, electroless nickel plating bath, and method for producing electroless nickel plating film |
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