CN1094765A - Basic plating method for bright Zn-Ni alloy - Google Patents

Basic plating method for bright Zn-Ni alloy Download PDF

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Publication number
CN1094765A
CN1094765A CN 94100815 CN94100815A CN1094765A CN 1094765 A CN1094765 A CN 1094765A CN 94100815 CN94100815 CN 94100815 CN 94100815 A CN94100815 A CN 94100815A CN 1094765 A CN1094765 A CN 1094765A
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nickel
zinc
grams per
bright
liter
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CN 94100815
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CN1039546C (en
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蔡加勒
周绍民
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Xiamen University
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Xiamen University
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/56Electroplating: Baths therefor from solutions of alloys
    • C25D3/565Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc

Abstract

The present invention is a kind of method of Bright Zinc-Nickel Alloy Plating in Alkaline Baths, in the plating bath except containing zinc oxide, sodium hydroxide, aromatic aldehyde, the title complex that also contains nickel and tetraethylene pentamine, and a kind of product by imidazoles, epoxy chloropropane and tetraethylene pentamine stepwise reaction is made additive, make anode in turn with pure zinc or pure nickel, regulate certain current density and bath temperature, can on conducting base, deposit nickel content and be 6%~25% mirror bright-bright Zn-Ni alloy coating.Nickel content in the coating can recently be controlled by zinc in the plating bath/nickel weight.Can directly be converted into the bright Zn-Ni alloy plating bath to zincate galvanizing liquid by the present invention.

Description

Basic plating method for bright Zn-Ni alloy
The invention belongs to the alloy plating field.
The present invention is a kind of Bright Zinc-Nickel Alloy Plating in Alkaline Baths technology, can in the alkali zinc nickel alloy electroplating bath, on the conducting base negative electrode, deposit nickel content and be 6%~25% mirror bright-bright Zn-Ni alloy coating.
Zinc-nickel alloy electroplating technology has acid and two kinds of systems of alkalescence.Former studies and application acid system are many.Alkaline system is because to have dispersive ability good, can not occur active condition no coating district, grasp easily, cost is lower, can continue to use advantage such as alkaline zinc plating equipment, has caused concern both domestic and external in recent years.
United States Patent (USP) 4861442 discloses the alkali zinc nickel alloy electroplating bath of a kind of PH 〉=11, it consists of zinc 3~30 grams per liters, nickel 0.2~20 grams per liter, alkaline hydrated oxide 20~300 grams per liters, amino alcohol polymkeric substance 0.05~10 grams per liter, nickel Synergist S-421 95 1~20 moles/mole nickel ion, amino acid and/or amino acid salts.
United States Patent (USP) 4877496 discloses a kind of alkali zinc nickel alloy electroplating bath, it consists of zinc 4~30 grams per liters, nickel 0.05~4 grams per liter, alkaline hydrated oxide 50~200 grams per liters, Synergist S-421 95 4~110 grams per liters, main brightener 0.1~10 grams per liter, this main brightener are one or more amine and 3-halogen-1, the reaction product of 2 propylene oxide, auxiliary brightener contain a kind of aromatic aldehyde at least.
United States Patent (USP) 4889602 discloses the alkali zinc nickel alloy electroplating bath of a kind of PH>11, it consists of zinc 1~70 grams per liter, nickel 0.6~118 grams per liter, and aliphatic amide is no more than 16 grams per liters, aliphatic amine polymer is no more than 20 grams per liters, can obtain haply zn-ni alloy deposits uniformly.
Day disclosure special permission bulletin 01298192[89298192] a kind of alkali zinc nickel alloy electroplating bath is disclosed, it consists of Zn 2+5~20 grams per liters, Ni 2+0.4~4.0 grams per liters, (Zn/Ni(wt) 4~12.5), trolamine 15~60 grams per liters, brightening agent and N-aminoethyl quadrol, quadrol, diethylenetriamine, triethylene tetramine, sequestrant 〉=0.04 such as tetraethylene pentamine and/or five ethene hexamines mole can obtain the evenly zn-ni alloy deposits of light.
Purpose of the present invention is intended to develop a kind of new basic plating method for bright Zn-Ni alloy, but obtaining the nickel content regulated at will, surface mirror is bright-light, antiseptic property is better than pure zinc coating, the zn-ni alloy deposits that the pure zinc coating of hardness ratio is high.And can directly be converted into the alkali zinc nickel alloy electroplating bath to zincate galvanizing liquid by the present invention.
Of the present invention being described in detail as follows.
According to the present invention, described below plating bath form and operational condition under, can on plating pieces such as iron and steel, obtain nickel content and be 6%~25% mirror bright-bright Zn-Ni alloy coating.
Electroplate liquid of the present invention is composed as follows: zinc oxide (ZnO) 4~10 grams per liters, 6~8 grams per liters preferably, sodium hydroxide (NaOH) 90~120 grams per liters, 90~110 grams per liters preferably, aromatic aldehyde 0.2~0.4 grams per liter, 2~30 milliliters/liter of nickel complexes, zinc in the plating bath/nickel weight ratio is 3~10, preferably 6~8,0.3~4 milliliter/liter of ZN-11 additive.Said aromatic aldehyde can be selected piperonylaldehyde or aubepine for use.Said nickel complex is single nickel salt (NiSO 46H 2O) with tetraethylene pentamine [NH 2(CH 2CH 2NH) 3CH 2CH 2NH 2] the title complex aqueous solution that generates of reaction back, the amount of single nickel salt and tetraethylene pentamine is respectively that 375 grams and 500 restrain in every liter of such title complex aqueous solution.Said ZN-11 additive is to be 1: 1 in molar ratio at imidazoles and epoxy chloropropane, in 60~70 ℃ of synthetic products, add tetraethylene pentamine, the tetraethylene pentamine and the imidazoles mol ratio of adding are 2: 1, and then with epoxy chloropropane by with the imidazoles mol ratio be 2: 1, in 60~70 ℃ of further synthetic products.
The present invention adopts pure zinc and pure nickel web wheel stream to make anode or is 3~5 to mix and make anode by the nickel plate and the area ratio of zine plate, and adopting the metal trough of plastic inner lining is coating bath.
According to the present invention, employed current density is 0.2~10 ampere/square decimeter, preferably 0.5~4 ampere/square decimeter; Service temperature is 15~65 ℃, preferably 25~35 ℃.
The plating piece surface of handling according to technical recipe of the present invention and operational condition is mirror bright-light, nickel content (weight ratio) is 6%~25% in the coating.Nickel content can be by the zinc in the plating bath/nickel than control in the coating, and when zinc/nickel content was in 10%~15% scope in the coating when nickel ratio was 6~8, the coating erosion resistance is higher more than 3 times than pure zinc coating.The present invention can adopt pure zinc or pure nickel plate to make anode, and also have bath stability, advantage such as dispersive ability is good, and employed current density is wide, and easy and simple to handle being easy to grasped, and cost is lower, be convenient to industrial production.Zinc-platedly in the domestic electroplating industry account for 70%, wherein majority is a zincate galvanizing, can directly be converted into the electroplating bright admiro to it by the present invention.
The present invention is further illustrated with embodiment below.
Embodiment 1-7:
Plating bath is formed: zinc oxide 4 grams per liters, and sodium hydroxide 90 grams per liters, 4.8 milliliters/liter of nickel complexes, zinc/nickel weight ratio is 8.0, piperonylaldehyde 0.3 grams per liter, 0.5 milliliter/liter of ZN-11 additive.The above-mentioned plating bath of preparation is 1 liter in 1.2 liters of plastic channel, makes anode with pure zinc or pure nickel plate, makes negative electrode with 2.5 square centimeters of iron plates, electroplates 10 minutes with different current densities at 28 ℃, and the result is as follows:
Embodiment 1234567
Current density (A/dm2) 0.5 12468 10
Coating nickel content (Wt.%) 8.2 9.3 9.7 10.2 10.5 10.7 11.1
Current efficiency (%) 44.9 36.7 32.5 27.3 22.8 18.2 13.3
The bright mirror of the bright mirror of the bright mirror of the bright mirror of the bright mirror of the bright mirror of coating appearance mirror is bright
Embodiment 8-13:
Plating bath is formed: zinc oxide 6 grams per liters, and sodium hydroxide 100 grams per liters, 9.4 milliliters/liter of nickel complexes, zinc/nickel weight ratio is 6.1, aubepine 0.3 grams per liter, 0.5 milliliter/liter of ZN-11 additive.The above-mentioned plating bath of preparation is 1 liter in 1.2 liters of plastic channel, makes anode with pure zinc or pure nickel plate, makes negative electrode with 2.5 square centimeters of iron plates, electroplates 10 minutes with different current densities at 30 ℃, and the result is as follows:
Embodiment 89 10 11 12 13
Current density (A/dm2) 0.5 12468
Coating nickel content (Wt.%) 11.7 12.2 12.8 13.3 13.9 14.3
Current efficiency (%) 63.4 52.1 42.2 39.2 33.5 21.4
The bright mirror of the bright mirror of the bright mirror of the bright mirror of the bright mirror of coating appearance mirror is bright
Embodiment 14-16:
Plating bath is formed: zinc oxide 10 grams per liters, and sodium hydroxide 100 grams per liters, 16 milliliters/liter of nickel complexes, zinc/nickel weight ratio is 5.8, aubepine 0.3 grams per liter, 1 milliliter/liter of ZN-11 additive.The above-mentioned plating bath of preparation is 1 liter in 1.2 liters of plastic channel, makes anode with pure zinc or pure nickel plate, makes negative electrode with 2.5 square centimeters of iron plates, electroplates 10 minutes with different current densities at 25 ℃, and the result is as follows:
Embodiment 14 15 16
Current density (A/dm2) 124
Coating nickel content (Wt.%) 12.5 13.2 14.1
Current efficiency (%) 73.3 55.1 43.5
The bright mirror of the bright mirror of coating appearance mirror is bright
Embodiment 18:
Plating bath is formed: industrial oxidation zinc 8 grams per liters, industrial sodium hydroxide 120 grams per liters, prepare 18 liters of plating baths with 20 liters of porcelain grooves or plastic channel, with the nickel plate is anode, iron plate is a negative electrode, handled 24 hours with 0.1 ampere/square decimeter (0.6 ampere of total current) energising, add 11.4 milliliters/liter of nickel complexes then, zinc in the solution/nickel weight ratio is 6.7, piperonylaldehyde 0.3 grams per liter, 0.5 milliliter/liter of ZN-11 additive, 28 ℃ of temperature, make anode with nickel plate or zine plate, with long 160 millimeters ψ=20 * 2(millimeters) iron pipe make negative electrode, electroplated 40 minutes with 2.8 ampere electric currents, the outside zn-ni alloy deposits of iron pipe is full light as a result, its nickel content 13%, 16 millimeters of the dark platings in the inner two ends of iron pipe.
Embodiment 19:
Plating bath is formed with embodiment 18, with long 160 millimeters ψ=20 * 2(millimeters) iron pipe make negative electrode, make anode with pure zinc or pure nickel plate, insert iron wire simultaneously in the iron pipe and make supplementary anode, electroplated 50 minutes with 2.8 ampere electric currents at 28 ℃, all plate the zn-ni alloy deposits of light as a result inside and outside the iron pipe, its nickel content 13%.
Embodiment 20-25:
Be converted into the bright Zn-Ni alloy plating bath with the zincate galvanizing liquid in 3 years of factory's continuous production by the present invention.Zincate galvanizing liquid is formed: zinc oxide 5.7 grams per liters, sodium hydroxide 96 grams per liters, DE(factory universal additive, by dimethylin propane and epoxy chloropropane 1: 1 in molar ratio 5 milliliters/liter of temperature (product that reacts under 90 ℃ of conditions), vanillin food grade,1000.000000ine mesh 0.2 grams per liter, EDTA disodium 0.1 grams per liter.Get 2 liters of above-mentioned plating baths and place 2.2 liters of plastic channel, add 9.4 milliliters/liter of nickel complexes, zinc/nickel weight ratio is 5.8, aubepine 0.2 grams per liter, 0.5 milliliter/liter of ZN-11 additive is made anode with pure zinc or pure nickel plate, makes negative electrode with 2.5 square centimeters of iron plates, electroplate with different current densities at 28 ℃, the result is as follows:
Embodiment 20 21 22 23 24 25
Current density (A/dm2) 0.2 12468
Coating nickel content (Wt.%) 11.5 12.9 13.8 13.8 14.2 14.5
Current efficiency (%) 53.6 46.2 41.5 36.7 29.2 19.8
Coating outward appearance light light light light light light

Claims (6)

1, a kind of method of Bright Zinc-Nickel Alloy Plating in Alkaline Baths, said method will be at a kind of zinc oxide (ZnO) that contains, and carries out in the plating bath of sodium hydroxide (NaOH) and a kind of aromatic aldehyde, and said aromatic aldehyde can be selected piperonylaldehyde or aubepine for use; Feature of the present invention is that said plating bath also contains a kind of nickel complex and a kind of called after ZN-11 additive, and said nickel complex is single nickel salt (NiSO 46H 2O) with tetraethylene pentamine [NH 2(CH 2CH 2NH) 3CH 2CH 2NH 2] the back complex solution that generates of reaction, in every liter of such fluid,matching, the amount of single nickel salt and tetraethylene pentamine is respectively 375 grams and 500 grams, said ZN-11 additive is to be 1: 1 in molar ratio at imidazoles and epoxy chloropropane, under 60~70 ℃ of conditions, add tetraethylene pentamine in the synthetic product, the tetraethylene pentamine of adding is 2: 1 with the mol ratio of imidazoles, and then with epoxy chloropropane by with the imidazoles mol ratio be 2: 1, in 60~70 ℃ times further reacted products; In the said plating bath, the oxidation zinc concentration is 4~10 grams per liters, naoh concentration is 90~120 grams per liters, and aromatic aldehyde concentration is 0.2~0.4 grams per liter, 2~30 milliliters/liter of nickel complexes, 0.3~4 milliliter/liter of ZN-11 additive, zinc in the plating bath/nickel weight ratio is 3~10, makes anode in turn with pure zinc and pure nickel, or mixes with zine plate than the nickel plate that is 3~5 with area and to make anode, in current density is 0.2~10 ampere/square decimeter, and temperature is to electroplate under 15~65 ℃ the condition.
2,, it is characterized in that said oxidation zinc concentration is 6~8 grams per liters according to the said method of claim 1.
3,, it is characterized in that said naoh concentration is 90~110 grams per liters according to the said method of claim 1.
4,, it is characterized in that said zinc-nickel weight ratio is 6~8 according to the said method of claim 1.
5,, it is characterized in that said current density is 0.5~4 ampere according to the said method of claim 1.
6,, it is characterized in that said electroplating temperature is 25~35 ℃ according to the said method of claim 1.
CN94100815A 1994-01-24 1994-01-24 Basic plating method for bright Zn-Ni alloy Expired - Fee Related CN1039546C (en)

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Cited By (14)

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CN1117177C (en) * 1999-01-21 2003-08-06 马冲 Main component of brightening agent for galvanization and brightening agent prepared from it
CN101942684A (en) * 2010-10-09 2011-01-12 济南德锡科技有限公司 Alkaline electroplating Zn-Ni alloy additive, electroplating solution and preparation method
CN102653872A (en) * 2012-04-16 2012-09-05 昆明理工大学 Electroplate liquid of alkaline zinc-nickel alloy
CN102677109A (en) * 2012-05-31 2012-09-19 南京工程学院 Method for preparing thickness-adjustable gamma-crystal-form zinc-nickel alloy on surface of methane tank
CN103320821A (en) * 2013-07-12 2013-09-25 贵阳华科电镀有限公司 Alkaline zinc-cobalt alloy electroplating liquid
CN103451693A (en) * 2013-07-29 2013-12-18 山东建筑大学 Pulse electroplating method for alkaline zinc-nickel alloy with stable nickel content
CN103469259A (en) * 2013-09-22 2013-12-25 无锡阳工机械制造有限公司 Alkaline plating solution for metal galvanization
CN104404584A (en) * 2014-12-22 2015-03-11 常熟市伟达电镀有限责任公司 Zinc-nickel alloy electroplating technique
CN104651889A (en) * 2015-03-04 2015-05-27 武汉风帆电镀技术股份有限公司 High-corrosion-resistance gamma crystalline phase zinc-nickel alloy electroplating additive and electroplating liquid
CN105239115A (en) * 2015-10-22 2016-01-13 广州超邦化工有限公司 Alkaline zinc-nickel alloy electroplating solution with high stability
CN106086948A (en) * 2016-08-11 2016-11-09 太仓市凯福士机械有限公司 A kind of high temperature resistant type electroplate liquid additive
CN109267122A (en) * 2018-11-21 2019-01-25 上海聆轩化工商行 A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation process
CN110760907A (en) * 2019-12-05 2020-02-07 佛山市南海高益美环保实业有限公司 Alkaline cyanide-free electroplating zinc-nickel alloy additive and electroplating solution
CN111593378A (en) * 2020-04-20 2020-08-28 常州新纪元材料科技有限公司 Preparation of high corrosion-resistant alkaline zinc-nickel alloy electroplating solution and components of additive

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DE4023466C1 (en) * 1990-07-24 1991-06-27 Hoesch Stahl Ag, 4600 Dortmund, De Electrical coating of steel strip - using zinc on zinc-nickel alloy then treating strip as anode in electrolyte soln.

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1117177C (en) * 1999-01-21 2003-08-06 马冲 Main component of brightening agent for galvanization and brightening agent prepared from it
CN101942684A (en) * 2010-10-09 2011-01-12 济南德锡科技有限公司 Alkaline electroplating Zn-Ni alloy additive, electroplating solution and preparation method
CN102653872A (en) * 2012-04-16 2012-09-05 昆明理工大学 Electroplate liquid of alkaline zinc-nickel alloy
CN102653872B (en) * 2012-04-16 2014-11-05 昆明理工大学 Electroplate liquid of alkaline zinc-nickel alloy
CN102677109B (en) * 2012-05-31 2015-10-21 南京工程学院 Tank for sewage gas surface thickness adjustable γ crystal formation zinc-nickel alloy preparation method
CN102677109A (en) * 2012-05-31 2012-09-19 南京工程学院 Method for preparing thickness-adjustable gamma-crystal-form zinc-nickel alloy on surface of methane tank
CN103320821B (en) * 2013-07-12 2016-08-10 贵阳华科电镀有限公司 A kind of Alkaline Zinc Cobalt Alloy Plating liquid
CN103320821A (en) * 2013-07-12 2013-09-25 贵阳华科电镀有限公司 Alkaline zinc-cobalt alloy electroplating liquid
CN103451693B (en) * 2013-07-29 2015-08-26 山东建筑大学 A kind of alkaline zinc-nickel alloy pulse plating method of nickel stable content
CN103451693A (en) * 2013-07-29 2013-12-18 山东建筑大学 Pulse electroplating method for alkaline zinc-nickel alloy with stable nickel content
CN103469259A (en) * 2013-09-22 2013-12-25 无锡阳工机械制造有限公司 Alkaline plating solution for metal galvanization
CN104404584A (en) * 2014-12-22 2015-03-11 常熟市伟达电镀有限责任公司 Zinc-nickel alloy electroplating technique
CN104651889A (en) * 2015-03-04 2015-05-27 武汉风帆电镀技术股份有限公司 High-corrosion-resistance gamma crystalline phase zinc-nickel alloy electroplating additive and electroplating liquid
CN105239115A (en) * 2015-10-22 2016-01-13 广州超邦化工有限公司 Alkaline zinc-nickel alloy electroplating solution with high stability
CN106086948A (en) * 2016-08-11 2016-11-09 太仓市凯福士机械有限公司 A kind of high temperature resistant type electroplate liquid additive
CN109267122A (en) * 2018-11-21 2019-01-25 上海聆轩化工商行 A kind of non-cyanide alkali Zinc-nickel alloy electroplating liquid and its preparation process
CN110760907A (en) * 2019-12-05 2020-02-07 佛山市南海高益美环保实业有限公司 Alkaline cyanide-free electroplating zinc-nickel alloy additive and electroplating solution
CN111593378A (en) * 2020-04-20 2020-08-28 常州新纪元材料科技有限公司 Preparation of high corrosion-resistant alkaline zinc-nickel alloy electroplating solution and components of additive

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