CN104775143A - Multilayer ultra corrosion resistant nickel-chromium plating part and manufacturing method thereof - Google Patents
Multilayer ultra corrosion resistant nickel-chromium plating part and manufacturing method thereof Download PDFInfo
- Publication number
- CN104775143A CN104775143A CN201510105201.2A CN201510105201A CN104775143A CN 104775143 A CN104775143 A CN 104775143A CN 201510105201 A CN201510105201 A CN 201510105201A CN 104775143 A CN104775143 A CN 104775143A
- Authority
- CN
- China
- Prior art keywords
- nickel dam
- nickel
- dam
- layer
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a multilayer ultra corrosion resistant nickel-chromium plating part and a manufacturing method thereof. The multilayer ultra corrosion resistant nickel-chromium plating part includes a substrate, a pretreatment coating, a base layer, a functional layer and a decorative layer. The pretreatment coating is deposited on the entire substrate, and a copper plate layer is formed on the pretreatment coating; the base layer is formed on the copper plate layer; the functional layer is formed on the base layer and includes a low potential nickel layer and a microporous nickel layer formed on the low potential nickel layer; and the decorative layer is formed on the microporous nickel layer and is a trivalent chromium coating or a hexavalent chromium coating. Based on the micropores on the part surface and chrome plating technology, the low potential nickel layer is added to improve the corrosion resistance of the product, especially the corrosion resistance of trivalent chromium plating product, so as to promote the large scale popularization and application of the trivalent chromium product, which has better environmental protection performance.
Description
Technical field
The present invention relates to the super anti-corrosion nickel plating-chromium parts of a kind of workpiece and the manufacture method thereof with surface plating structure, particularly a kind of multilayer and manufacture method thereof.
In the application, potential difference is the difference of the normal potential integrally recorded separately with adjacent two layers.
Background technology
European market is more and more tighter to environmental requirement, and each main engine plants are more and more higher to the corrosion proof requirement of plating, the corrosion that current trivalent chromium plating cannot meet specific environment requires (reaching salt-fog resistant test 80h and resistance to Russian mud test 336h) simultaneously.
The method that in electroplating industry, the chromium plating again of double layer nickel or three layers of nickel is first plated in general application improves the antiseptic power of workpiece, the double layer nickel technique be widely used has: half light nickel+light nickel+flawless chromium, the three layers of nickel technique be widely used have: half light nickel+light nickel+microporous nickel+flawless chromium, or half light nickel+light nickel+micro-crack nickel+flawless chromium, but because the stress of layers of chrome self is large, industrially be difficult to obtain a kind ofly there is no the chromium electrolytic coating of crackle or hole (comprising sexavalent chrome and trivalent chromium coating) completely, expose after aerial chromium electrolytic coating is passivated, its current potential than nickel just, when running into the corrosive medium in air, just corrosion cell is formed with nickel dam, cause ornamental nickel electrolytic coating in extreme environment, occur a large amount of irregular corrosion, even the corrosion of nickel dam big area causes coming off of layers of chrome.In order to improve the antiseptic power of coating further, microporous nickel and micro-crack nickel are applied on light nickel coating, and micro-crack nickel plates the heavily stressed special nickel dam of one deck on light nickel dam, will produce a large amount of tiny cracks after chromium plating due to stress; And corrosion current disperses by micropore nickel dam in MULTI-LAYER NICKEL, prevent the hot spot of Formation Depth, avoid visible corrosion.Owing to being used alone tiny crack nickel dam, product surface sends out mist, and luminance brightness is poor, and mentions that trivalent chromium is coated with, and owing to being used alone microporous nickel or micro-crack nickel, is limited to corrosion proof raising.
In prior art, as Chinese patent application (publication number: CN102766894 A) relates to a kind of electroplate liquid for micro-crack nickel plating and application thereof, this micro-crack nickel electroplate liquid mainly composed as follows: nickelous chloride: 180 ~ 260 grams per liters, acetic acid: 20 ~ 60 milliliters/liter, ELPELYT MR:80 ~ 120 milliliter/liter, 62A:1 ~ 5 milliliter/liter.In plastic part surface micro-crack nickel electroplating technology flow process be: A. plastic part surface metallizes, B. bright copper, the bright nickel of C. half, D. high-sulfur nickel E. bright nickel, F. microporous nickel, G. washes, H. light chromium, and I. washes, and J. is dry; Although adopt these four layers of nickel nickel plating solutions to carry out at frosting electroplating the erosion resistance that improve plastic component to a certain extent in this technical scheme, but the resistance to corrosion of this technique still cannot reach containing deicer salts (CaCl
2) requirement of corrosive environment, high-sulfur nickel electrolytic coating local has sends out mist phenomenon, in addition in the method because plastic surface process is not in place, cause coating covering power poor, the easy embrittlement of coating, the plastic cement after electroplating processes as trolley part (grid, panel, door handle) afterwards work-ing life short.And about introducing the technique of micro-crack nickel, as Chinese patent application (publication number: CN101705508A) relates to a kind of electroplate liquid for micro-crack nickel plating and application thereof, this micro-crack nickel electroplate liquid mainly composed as follows: nickelous chloride: 180 ~ 260 grams per liters, acetic acid: 20 ~ 60 milliliters/liter, ELPELYT MR:80 ~ 120 milliliter/liter, 62A:1 ~ 5 milliliter/liter, the evaluation physical constraints of the example described in patent documentation is sexavalent chrome plating, does not refer to trivalent chromium plating.
Summary of the invention
For solving the problem, the invention discloses the super anti-corrosion nickel plating-chromium parts of a kind of multilayer, by organically combining corrosion resistance characteristic and the chemical property of land productivity functional layer MULTI-LAYER NICKEL structure, both ensure that the shiny appearance characteristic of micropore nickel dam, there is again the dual solidity to corrosion of the functional layer comprising microporous nickel, product can be made to reach superelevation solidity to corrosion and structural stability, even if after low potential nickel dam is corroded, micropore nickel dam can play the effect of supporting and delaying to corrode equally.
The super anti-corrosion nickel plating-chromium part components of multilayer disclosed by the invention, these parts comprise:
Base material;
Pre-treatment coating, its deposition over the whole substrate, pre-treatment coating is formed with copper plate; With
Basal layer, it is formed on copper plate; With
Functional layer, it is formed on basal layer, and wherein functional layer comprises low potential nickel dam and is formed at the micropore nickel dam on low potential nickel dam; With
Ornament layer, it is formed on micropore nickel dam, and described ornament layer is the arbitrary of trivalent chromium coating or sexavalent chrome coating.
Preferred as one, the potential difference between micropore nickel dam and low potential nickel dam is within the scope of 10-120mv.
Preferred as one, low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between composite deposite.
Preferred as one, the potential difference between micropore nickel dam and low potential nickel dam is within the scope of 20-100mv.
Preferred as one, when low potential nickel dam adopts the composite deposite of tiny crack nickel dam and high-sulfur nickel dam, between tiny crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mv.Here when corroding arrival low potential nickel dam, because the current potential of tiny crack nickel dam is higher than the current potential of high-sulfur nickel dam, now high-sulfur nickel dam is preferentially corroded by as anodic coating again, extends the corrosion of tiny crack nickel dam, thus improves corrosion-resistant degree further.
The one of the super anti-corrosion nickel plating-chromium part components of multilayer disclosed by the invention is improved, basal layer comprise in half light nickel dam, high-sulfur nickel dam, full light nickel dam, husky fourth nickel dam one or more layers.
The one of the super anti-corrosion nickel plating-chromium part components of multilayer disclosed by the invention is improved, and basal layer is the compound between half light nickel dam and full light nickel dam, and wherein, half light nickel dam is formed on copper plate, and full light nickel dam is formed on half light nickel dam.
The one of the super anti-corrosion nickel plating-chromium part components of multilayer disclosed by the invention is improved, and basal layer is the compound between half light nickel dam and Sha Ding nickel dam, and wherein, half light nickel dam is formed on copper plate, and husky fourth nickel dam is formed on half light nickel dam.
Preferred as one, full light nickel dam or husky fourth nickel dam is arbitrary and potential difference between low potential nickel dam is within the scope of 0-100mv.
Preferred as one, half light nickel dam and full light nickel dam, potential difference between half light nickel dam and husky fourth nickel dam are within the scope of 100-200mv.
The one of the super anti-corrosion nickel plating-chromium part components of multilayer disclosed by the invention is improved, basal layer is half light nickel dam, high-sulfur nickel dam and the compound entirely between light nickel dam, and wherein, half light nickel dam is formed on copper plate, high-sulfur nickel dam is formed on half light nickel dam, and full light nickel dam is formed on high-sulfur nickel dam.
The one of the super anti-corrosion nickel plating-chromium part components of multilayer disclosed by the invention is improved, basal layer is half light nickel dam, compound between high-sulfur nickel dam and Sha Ding nickel dam, and wherein, half light nickel dam is formed on copper plate, high-sulfur nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on high-sulfur nickel dam.
The one of the super anti-corrosion nickel plating-chromium part components of multilayer disclosed by the invention is improved, basal layer is half light nickel dam, full compound between light nickel dam and Sha Ding nickel dam, and wherein, half light nickel dam is formed on copper plate, full light nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on full light nickel dam.
As preferably, the potential difference of micropore nickel dam and low potential nickel dam is 10-120mv.
As preferably, low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between compound.Preferred further, the potential difference between micropore nickel dam and low potential nickel dam is 20-100mv.
As preferably, when low potential nickel dam adopts micro-crack nickel and high-sulfur nickel composite deposite, between tiny crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mv.
The manufacture method of the super anti-corrosion nickel plating-chromium parts of multilayer disclosed by the invention comprises the steps:
Pre-treatment is carried out on the surface of base material;
Pre-treatment coating is deposited over the whole substrate, and copper plate is formed on pre-treatment coating; With
Basal layer is formed on copper plate; With
Low potential nickel dam in functional layer is formed on basal layer; With
Micropore nickel dam in functional layer is formed on low potential nickel dam; With
Be formed at by ornament layer on micropore nickel dam, described ornament layer is the arbitrary of trivalent chromium coating or sexavalent chrome coating.
Here the potential difference between micropore nickel dam and low potential nickel dam is within the scope of 10-120mv.Potential difference controlled within the scope of this, in electroplating process, not easily to occur bubbling at 10-120mv, coating structure is more stable firmly simultaneously, and not easily generation separation is peeled off.Here low potential nickel dam Indirect Electro is plated on copper plate, can also electroplate other coating, be totally referred to as basal layer between low potential nickel dam and copper plate, and basal layer can be the corresponding coating such as half light, Quan Guang, Sha Ding, high-sulfur here.
A first aspect of the present invention provides multilayer super anti-corrosion nickel plating-chromium parts, and it comprises following: matrix; Pre-treatment coating (can comprise electroless nickel layer, bottoming nickel dam arbitrary or the two compound), it is formed on whole matrix; Copper plate, it is formed on pre-treatment coating; Basal layer (arbitrary or multiple compound in full light nickel dam, half light nickel dam, husky fourth nickel dam, high-sulfur nickel dam can be comprised), it is formed on copper plate; Low potential nickel coating, it is formed on basic coating, micropore nickel dam, and it is formed with on low potential nickel dam, and the potential difference wherein between low potential nickel coating and microporous nickel coating is in the scope of 10mV to 120mV; With ornament layer (can be chromium coating, as trivalent chromium coating or sexavalent chrome coating arbitrary), it be formed on microporous nickel coating, and has the one of at least any of microvoid structure and micro-cracked structure.
A second aspect of the present invention provides the manufacture method of the super anti-corrosion nickel plating-chromium parts of multilayer, and it comprises the following steps: be formed at by pre-treatment coating on whole matrix; Copper plate is formed on pre-treatment coating; Be formed at by basal layer on copper plate, wherein basal layer comprises in half light nickel dam, high-sulfur nickel dam, full light nickel dam, husky fourth nickel dam one of at least any; Your low potential nickel coating being formed on basic coating by, be formed at by micropore nickel dam on low potential nickel dam, the potential difference wherein between low potential nickel coating and microporous nickel coating is in the scope of 10mV to 120mV; Ornament layer is formed on micropore nickel dam.
The one of the manufacture method of the super anti-corrosion nickel plating-chromium parts of multilayer disclosed by the invention is improved, basal layer comprise in half light nickel dam, high-sulfur nickel dam, full light nickel dam, husky fourth nickel dam one or more layers.
As preferably, half light nickel dam adopts the plating of plating half light nickel plating bath to form, plate half light nickel plating bath and comprise composition and concentration for (in unit volume plating solution addition): aqueous sulfuric acid nickel 200-300g/L, moisture nickelous chloride 35-50g/L, boric acid 35-50g/L, semi-bright nickel elementary brightening agent 3.0-7.0ml/L (be sure of that the chemical trade (Shanghai) Co., Ltd. of happy think of thinks hereinafter referred to as happy, wheat dolantin science and technology (Suzhou) company limited is hereinafter referred to as wheat dolantin, the BTL MU thought as the happy or NIMAC SF DUCT of wheat dolantin), semi-bright nickel second-class brightener 0.3-1.0ml/L (TL-2 thought as happy or the NIMAC SF LEVELER of wheat dolantin), potential difference adjusting agent 0.8-1.2ml/L (the B benefit thought as happy or the NIMAC SF MAINTENANCE of wheat dolantin), wetting agent 2.0-3.0ml/L (62A thought as happy or the NIMAC32C WETTER of wheat dolantin).When half light nickel dam is coated with, service temperature controls between 50 ~ 60 DEG C, pH value controls between 3.6 ~ 4.6, current density is 2 ~ 5ASD, operating time controls between 12 ~ 24min, make nickel deposition at plated item copper plate on the surface by the mode of direct current electrolysis, require that half light nickel coating thickness is not less than 8 microns.
The object of plating half light nickel here plates the nickel dam of one deck half light, and half light nickel coating is columnar structure, can improve the erosion resistance of coating.
As preferably, full light nickel dam adopts the full light nickel plating bath plating of plating to form, plate full light nickel plating bath and comprise composition and concentration for (in unit volume plating solution addition): aqueous sulfuric acid nickel 220-340g/L, moisture nickelous chloride 40-50g/L, boric acid 35-40g/L, bright nickel softening agent 8-12ml/L (NIMAC14INDEX as happy 63 or the wheat dolantin thought), bright nickel key light agent 0.5-0.9ml/L (66E thought as happy or the NiMac Chanllenger Plus of wheat dolantin), wetting agent 2.0-3.0ml/L (62A thought as happy or the NIMAC32C WETTER of wheat dolantin).When full light nickel dam is coated with, service temperature controls between 50 ~ 60 DEG C, pH value controls between 3.6 ~ 4.6, current density is 2 ~ 5ASD, operating time controls between 9 ~ 20min, by the mode of direct current electrolysis, nickel deposition is plated on half light nickel surface at plated item, light nickel coating thickness of demanding perfection is not less than 5 microns.
The object of plating full light nickel here plates the nickel dam of one deck entire bright, and full light nickel coating is laminate structure, can improve the luminance brightness of coating.
As preferably, high-sulfur nickel dam adopts the plating of plating high-sulfur nickel plating bath to form, plating high-sulfur nickel plating bath comprises composition and concentration is (in unit volume plating solution addition): the concentration of aqueous sulfuric acid nickel is 250-350g/L, the concentration of moisture nickelous chloride is 35-60g/L, the concentration of boric acid is 35-65g/L, the concentration of high sulfur additives is 3-10ml/L, and the concentration of wetting agent is 0.5-3ml/L (62A thought as happy or the NIMAC32C WETTER of wheat dolantin).
As preferably, husky fourth nickel dam adopts the husky fourth nickel plating bath plating of plating to form, plate husky fourth nickel plating bath and comprise composition and concentration is (in unit volume plating solution addition): the concentration of aqueous sulfuric acid nickel is 250-350g/L, the concentration of moisture nickelous chloride is 35-60g/L, the concentration of boric acid is 35-65g/L, the concentration of supplementary additive is 5-20ml/L (the Elpelyt pearlbrite carrier K4 thought as happy or Elpelyt carrier brightener H), the concentration of husky fourth nickel forming agent is 0.1-0.6ml/L (as the happy Elpelyt pearlbrite additive K6AL thought).
In above-mentioned manufacture method, low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between compound.
As preferably, micropore nickel dam adopts the plating of plating microporous nickel plating solution to form, plating microporous nickel plating solution comprises composition and concentration is (in unit volume plating solution addition): aqueous sulfuric acid nickel 300-350g/L, moisture nickelous chloride 50-60g/L, boric acid 40-50g/L, nickel envelope brightening agent 6-12ml/L (NIMAC14INDEX as happy 63 or the wheat dolantin thought), nickel envelope key light agent 4-7.5ml/L (610CFC thought as happy or the NIMAC33 of wheat dolantin), nickel envelope particle 0.2-1.5g/L (ENHANCER thought as happy or the NiMac Hypore XL dispersion agent of wheat dolantin), nickel envelope particle dispersants 0.5-3ml/L, wetting agent 1-5ml/L.When micropore nickel dam is coated with, service temperature controls between 50 ~ 60 DEG C, pH value controls between 3.8 ~ 4.6, and current density is 2 ~ 5ASD, and the operating time controls between 2 ~ 8min, make nickel deposition on plated item by the mode of direct current electrolysis, require that nickel coating thickness is not less than 1.5 microns.
As preferably, tiny crack nickel dam adopts the plating of plating micro-crack nickel plating solution to form, plating micro-crack nickel plating solution comprises composition and concentration is (in unit volume plating solution addition): moisture nickelous chloride: 180-260g/L, acetic acid: 10-40ml/L, PN-1A:40-90g/L, PN-2A:1-5ml/L, wetting agent: 1-5ml/L (62A thought as happy or the NIMAC32C WETTER of wheat dolantin).When tiny crack nickel dam is coated with, service temperature controls between 25 ~ 35 DEG C, pH value controls between 3.6 ~ 4.6, current density is 5 ~ 9ASD, operating time controls between 2 ~ 8min, make nickel deposition at plated item light-plated nickel dam on the surface by the mode of direct current electrolysis, require that micro-crack nickel thickness of coating is not less than 1.0 microns.
As preferably, high-sulfur nickel dam adopts the plating of plating high-sulfur nickel plating bath to form, plating high-sulfur nickel plating bath comprises composition and concentration is (in unit volume plating solution addition): aqueous sulfuric acid nickel 250-350g/L, moisture nickelous chloride 35-60g/L, boric acid 35-65g/L, high sulfur additives 3-10ml/L, wetting agent 0.5-3ml/L (62A thought as happy or the NIMAC32C WETTER of wheat dolantin).When high-sulfur nickel dam is coated with, temperature controls between 55 ~ 65 DEG C, pH is to controlling between 2.0 ~ 3.5, current density is 2 ~ 6ASD, operating time controls between 2 ~ 8min, make nickel deposition plate on basic coating surface at plated item by the mode of direct current electrolysis, high-sulfur nickel layer thickness is not less than 1.0 microns.
In above-mentioned manufacture method, also comprise base material pretreatment process in early stage, at least include surperficial grease treatment process, surface hydrophilic, surface coarsening treatment process, surperficial neutralizing treatment operation, surperficial preimpregnation, surface activation process operation and surperficial dispergation treatment process comprising ABS resin at interior non-metal kind base material pretreatment process in early stage; Metal species base material then can carry out follow-uply being coated with work after surperficial grease treatment process carries out oil removing, the corresponding operation of the non-metallic base being suitable for following statement equally in earlier stage in pretreatment process.
In above-mentioned manufacture method, non-metal kind base material pretreatment process in early stage is specially and base material blank is cleaned degrease in sodium hydroxide, sodium carbonate, tensio-active agent and water glass mixing solutions, immerse after degrease in chromic trioxide and sulfuric acid mixture liquid and carry out surface coarsening process, then put into hydrochloric acid soln and carry out surface neutralization, adopt colloidal palladium solution to carry out surface activation process after neutralization, then in sulphuric acid soln, carry out surperficial dispergation process.
As preferably, the mixing solutions of surperficial grease treatment process comprises composition and concentration is: the concentration of sodium hydroxide is 20-50g/L, and the concentration of sodium carbonate is 10-40g/L, tensio-active agent 1-3g/L, and the concentration of water glass is 10-40g/L.
Here surperficial degrease step can remove greasy dirt and other impurity of substrate surface, impels surface coarsening even, improves binding force of cladding material.
As preferably, the sulphuric acid soln concentration of surface hydrophilic operation is 20-100g/L, whole agent 0.5-2ml/L.
As preferably, the mixed solution of surface coarsening treatment process comprises composition and concentration is: the concentration of chromic trioxide is 330-480g/L, and the concentration of sulfuric acid is 330-480g/L.
As preferably, in surface and the mixing solutions of operation comprises composition and concentration is: hydrochloric acid 30-100ml/L, hydrazine hydrate 15-60ml/L.
As preferably, the concentration of hydrochloric acid solution of surperficial preimpregnation operation is 40-120ml/L.
As preferably, the colloidal palladium solution of surface activation process comprises composition and concentration is: hydrochloric acid 180-280ml/L, and the concentration of Palladous chloride is the concentration 1-6g/L of 20-60ppm, tin protochloride.
Here in colloidal palladium solution, Palladous chloride is covered in substrate surface, for follow-up chemical nickel provides catalytic center, the tin ion of tin protochloride then can be deposited on around palladium ion with chemical combination group too, avoid palladium ion be oxidized in water or in air and come off, the life cycle of colloidal palladium solution can be increased.
As preferably, the sulphuric acid soln concentration of surperficial dispergation treatment process is 40-100g/L.
Surface dispergation process refers to and utilizes sulfuric acid to remove in colloidal palladium solution the tin protochloride be coated on around palladous oxide, is come out by palladium metal particle, makes subsequent chemistry sink nickel technique more smooth and easy.
In above-mentioned manufacture method, pre-treatment coating can comprise the arbitrary or two-layer compound in electroless nickel layer or bottoming nickel dam.When electroless nickel layer and bottoming nickel dam exist simultaneously, then electroless nickel layer is formed on base material, and bottoming nickel dam is formed in electroless nickel layer.
As preferably, plating chemical nickel operation mixing solutions comprises composition and concentration is: the concentration of single nickel salt is 15-40g/L, and the concentration of inferior sodium phosphate is 20-50g/L, and the concentration of ammonium chloride is 10-50g/L, the concentration of Trisodium Citrate is 10-40g/L, and ammoniacal liquor adjust ph is to 8.6-9.2.
Here chemical sinking nickel refers to and deposit the thin conductive layer of one deck in the palladium metal that substrate surface has catalytic activity, and be convenient to the various metal of follow-up plating, in chemical sinking nickel process, single nickel salt provides nickel element; Inferior sodium phosphate is strong reductant, and the nickel element in single nickel salt is reduced into metallic nickel by it; Trisodium Citrate is buffer reagent, and it makes the reaction of inferior sodium phosphate reduced nickel element more mild.
As preferably, the mixing solutions of plating bottoming nickel operation comprises composition and concentration is: the concentration of aqueous sulfuric acid nickel is 180-280g/L, the concentration of moisture nickelous chloride is 35-60g/L, the concentration of boric acid is 35-60g/L, and the concentration of wetting agent is 1-3ml/L (62A thought as happy or the NIMAC32C WETTER of wheat dolantin).
When electroless nickel layer and bottoming nickel dam exist on matrix simultaneously, base material, in chemical sinking nickel, makes substrate surface cover the nickel dam of the conduction of layer by redox reaction; And in plating bottoming nickel, then adopt electrochemical method in chemical nickel, plate one deck nickel, strengthen the electroconductibility of coating further.In this step, aqueous sulfuric acid nickel, moisture nickelous chloride provide nickel ion needed for electrochemical reaction.
In above-mentioned manufacture method, in the mixing solutions of copper plate operation, each component and concentration are: the concentration of copper sulfate is 160-260g/L, the concentration of sulfuric acid is 50-100g/L, the concentration of chlorion is 40-100ppm, the concentration of leveling agent is 0.2-1ml/L (think as happy 1560 sour copper additives series), the concentration of agent of walking is 0.2-1ml/L (think as happy 1561 sour copper additives series), and the concentration of open cylinder agent is 2-10ml/L (think as happy 1562 sour copper additives series).
Here the object of copper plate utilizes the characteristic of copper sulfate to improve luminance brightness and the planarization of substrate surface, and can also improve the toughness of coating entirety.This is because copper coating compares nickel coating and other metal plating, its ductility is better, and after therefore plating sour layers of copper, toughness and the Surface flat of overall coating are improved.
In above-mentioned manufacture method, ornament layer is arbitrary in sexavalent chrome coating or trivalent chromium coating.Wherein trivalent chromium coating can be the trivalent chromium coating of the white chromium coating of trivalent or trivalent black chromium plating or other kind.When ornament layer is trivalent chromium coating, passive film can also be contained at trivalent chromium coating surface.
As preferably, the plating solution of plating sexavalent chrome operation comprises composition and concentration is: the concentration of chromic anhydride is 260-360g/L, the concentration of sulfuric acid is 0.5-3g/L, the concentration of decorative chromium brightening agent is 2.0-3.0ml/L (1120F thought as happy or the 7000C of Japanese chemical metallization), chromium fog inhibitor 0.1-0.4ml/L.Require that chromium coating is not less than 0.1 μm.
As preferably, the plating solution of plating trivalent white chromium operation comprises composition and concentration is: the concentration of moisture chromium chloride is 90-150g/L, the concentration of potassium formiate is 50-100g/L, the concentration of brometo de amonio is 8-25g/L, the concentration of ammonium chloride is 40-60g/L, and the concentration of Repone K is 40-100g/L, and the concentration of sodium acetate is 10-60g/L, the concentration of boric acid is 40-80g/L, and the concentration of wetting agent is 0.5-2.5ml/L.Require that chromium coating is not less than 0.1 μm.
As preferably, the plating solution of plating trivalent black chromium operation comprises composition and concentration is: the concentration of moisture chromium chloride is 150-250g/L, the concentration of oxalic acid is 2-5g/L, the concentration of ammonium acetate is 3-10g/L, the concentration of ammonium chloride is 20-40g/L, the concentration of boric acid is 20-41g/L, and the concentration of additive is 0.5-3g/L.Require that chromium coating is not less than 0.1 μm.
Plating micro-crack nickel refer to substrate surface plate one deck all and the coating containing numerous crackle, can corrosion current be disperseed, reduce corrosion electric current density.Plating microporous nickel refers to and plates one deck uniformly containing the coating of numerous non-conductive particulate at plastic surface, can disperse corrosion current further, reduce corrosion electric current density, improve coating corrosion stability comprehensively.
At plating half light nickel, plate in full light nickel step, stablizer all have employed boric acid but not Trisodium Citrate in chemical sinking nickel, this is because plating half light nickel, plate full light nickel step time more pay close attention to the covering power of coating and the compactness of coating.
Tiny crack nickel dam in functional layer, micropore nickel dam or both combine the reason that can play protection against corrosion and protection base material and be; coated metal on workpiece/ground metal extremely easily forms corrosion cell; when anode and cathode current potential is determined, its erosion rate controlled by the ratio of coated metal (negative electrode) surperficial ground metal (anode) exposed area.When only having the hot spot at a place, at this moment cathode/anode ratio is maximum, corrosion current just concentrates on this point, erosion rate just becomes very large, easily inwardly forms pitting, but when metal coating surface exists more potential hot spot, cathode/anode ratio is less, corrosion current is assigned to everywhere, and the electric current originally in hot spot significantly reduces, and erosion rate also reduces greatly.Meanwhile, due to the segmentation between micropore or crackle, coating negative electrode is formed discontinuous, the coating after divided becomes small area by big area, further limit so again cathode/anode ratio.But along with time the passing of asking; when coating surface be subject to extraneous factor impact start to occur large mode-Ⅲ crack time; the potential corrosion cell of tiny crack, microvoid structure will be initiated; thus it is subject to the effect of hot spot to protection; thus just can play double-core and reduce the effect of corrosion electric current density, thus the corrosion-resistant degree of significant increase.
The anticorrosive mechanism of low potential nickel
The first step: when piece surface has corrosive medium, micropore place is exposed to outer nickel dam and is first corroded as anodic coating, the size of corrosion current is determined by the surface-area of coating, under the effect of a large amount of discontinuous micropore, the nickel dam area corroded will increase and discontinuous greatly, and when corrosion current is certain, these " micropores " have disperseed corrosion current greatly, reduce erosion rate, the corrosion speed delayed.
Second step: when corroding arrival low potential nickel dam, comparatively low potential nickel current potential is high due to microporous nickel current potential, and now low potential nickel is preferentially corroded as anodic coating (namely low potential layer is preferentially as sacrifice layer), and the corrosion in microporous nickel is terminated.Under the effect of a large amount of discontinuous tiny crack, the nickel dam area corroded will increase and discontinuous greatly, and when corrosion current is certain, these " micropores " have disperseed corrosion current greatly, again reduce erosion rate, the corrosion speed delayed.
3rd step: to corrode in low potential nickel further to downward-extension until basic coating (comprising the following coating of low potential nickel) time, because the current potential of basic coating is higher than low potential nickel equally, low potential nickel has been regarded anodic coating equally, corrosion now to downward-extension is terminated at basic coating, corrosion position laterally carries out in low potential nickel, delay so again the time of corroding to ground further, greatly fall at the end speed of corrosion.
Compared with prior art, the invention has the advantages that:
1, the present invention is by after base material workpiece pretreatment process premenstruum, and for follow-up low potential nickel dam and the plating of micropore nickel dam lay the first stone, process stabilizing, compatibility is reasonable.
2, substrate surface of the present invention electroplates the micropore nickel dam and low potential nickel dam that obtain, and have high Corrosion Protection, high rigidity, high-wearing feature, binding force of cladding material is good, luminance brightness advantages of higher; Simultaneously there is the micropore nickel dam of noble potential characteristic and there is the MULTI-LAYER NICKEL of low potential characteristic---low potential nickel dam is for functional layer, and with low potential nickel dam for sacrifice layer, micro-electric current of galvanic corrosion can be disperseed with the micropore nickel dam with microvoid structure, delay be corroded generation, formed simultaneously and can also form oxide compound support after oxidation by microvoid structure, after can being subject to comparatively serious corrosion at the low potential nickel dam as sacrifice layer, it is formed and support, reduce part coating damage speed.The low potential nickel dam as sacrifice layer arranged has lower electromotive force; when the generation galvanic corrosion of piece surface coating; low potential nickel dam preferentially corrodes; and when there is micropore nickel dam or tiny crack nickel dam; its micropore or micro-cracked structure can play the micro-electric current of dispersion corrosion equally; when also having a layer structure outside low potential nickel dam, (during as ornament layer or protective layer) can also be supported outboard structure by micropore or micro-cracked structure, the steadiness of strongthener structure simultaneously.The present invention program utilizes the pore texture of microporous nickel and micro-crack nickel in addition, while strongthener structural support performance, can also play the effect reducing quality of coating and expend with reduction raw material.Its micro hole structure can also form large-area sull structure when there is oxidation corrosion simultaneously, thus greatly delays the generation of corrosion.
3, in addition, the present invention selects the plating solution little to environmental influence when filling a prescription and choosing as far as possible, make electroplating technology more environmental protection, further, coating combines firmly, is evenly distributed, longer service life, make the finished product no matter can meet the requirement of user in outward appearance or performance, make the technique of gained of the present invention have the higher market competitiveness.
Accompanying drawing explanation
Fig. 1 is the coating structure schematic diagram (taking ABS as part base material) of an embodiment of the super anti-corrosion nickel plating-chromium parts of multilayer of the present invention.
Fig. 2 is the coating structure schematic diagram (taking ABS as part base material) of an embodiment of the super anti-corrosion nickel plating-chromium parts of multilayer of the present invention.
Fig. 3 is the coating structure schematic diagram (taking ABS as part base material) of an embodiment of the super anti-corrosion nickel plating-chromium parts of multilayer of the present invention.
Fig. 4 is the coating structure schematic diagram (taking ABS as part base material) of an embodiment of the super anti-corrosion nickel plating-chromium parts of multilayer of the present invention.
Fig. 5 is the coating structure schematic diagram (taking ABS as part base material) of an embodiment of the super anti-corrosion nickel plating-chromium parts of multilayer of the present invention.
The nickel plating parts of Fig. 6 prior art metallograph after CASS72 hour, in Fig. 6, (a) is the front metallograph of sample after experiment, and in Fig. 6, (b) be side (section) metallograph of experiment sample afterwards.
Fig. 7 nickel plating parts of the present invention CASS metallograph after 72 hours, in Fig. 7, (a) is the front metallograph of sample after experiment, and in Fig. 7, (b) is the side metallograph of sample after experiment.
The picture carried out after 168 and 336 hours tested by the nickel plating component corrosion cream of Fig. 8 prior art.
The picture carried out after 168 and 336 hours tested by Fig. 9 nickel plating component corrosion of the present invention cream.
Figure 10 MULTI-LAYER NICKEL corrosion principle of the present invention figure (taking ABS as part base material).
The potential difference schematic diagram of a kind of embodiment of Figure 11 nickel plating of the present invention and or chromium parts (low potential nickel dam is the arbitrary of high-sulfur nickel dam or tiny crack nickel dam, and basal layer is the compound of half light nickel dam and full light nickel dam).
The potential difference schematic diagram of a kind of embodiment of Figure 12 nickel plating of the present invention and or chromium parts (low potential nickel dam is the arbitrary of high-sulfur nickel dam or tiny crack nickel dam, and basal layer is the compound of half light nickel dam and husky fourth nickel dam).
The potential difference schematic diagram of a kind of embodiment of Figure 13 nickel plating of the present invention and or chromium parts (low potential nickel dam is the arbitrary of high-sulfur nickel dam or tiny crack nickel dam, and basal layer is the compound of half light nickel dam, high-sulfur nickel dam and full light nickel dam).
The potential difference schematic diagram of a kind of embodiment of Figure 14 nickel plating of the present invention and or chromium parts (low potential nickel dam is the arbitrary of high-sulfur nickel dam or tiny crack nickel dam, and basal layer is the compound of half light nickel dam, high-sulfur nickel dam and husky fourth nickel dam).
The potential difference schematic diagram of a kind of embodiment of Figure 15 nickel plating of the present invention and or chromium parts (low potential nickel dam is the arbitrary of high-sulfur nickel dam or tiny crack nickel dam, and basal layer is the compound of half light nickel dam, full light nickel dam and husky fourth nickel dam).
The potential difference schematic diagram (low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam, and basal layer is the compound of half light nickel dam and full light nickel dam) of a kind of embodiment of Figure 16 nickel plating of the present invention and or chromium parts.
The potential difference schematic diagram (low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam, and basal layer is the compound of half light nickel dam and husky fourth nickel dam) of a kind of embodiment of Figure 17 nickel plating of the present invention and or chromium parts.
The potential difference schematic diagram (low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam, and basal layer is the compound of half light nickel dam, high-sulfur nickel dam and full light nickel dam) of a kind of embodiment of Figure 18 nickel plating of the present invention and or chromium parts.
The potential difference schematic diagram (low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam, and basal layer is the compound of half light nickel dam, high-sulfur nickel dam and husky fourth nickel dam) of a kind of embodiment of Figure 19 nickel plating of the present invention and or chromium parts.
The potential difference schematic diagram (low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam, and basal layer is the compound of half light nickel dam, full light nickel dam and husky fourth nickel dam) of a kind of embodiment of Figure 20 nickel plating of the present invention and or chromium parts.
Reference numerals list:
1, base material; 2, pre-treatment coating; 21, vacancy is corroded;
3, copper plate; 31, surface micropore; 32, corrosion hole;
4, functional layer; 141, low potential nickel dam; 142, micropore nickel dam;
6, basal layer; 61, high-sulfur nickel dam; 62, half light nickel dam;
63, full light nickel dam; 64, husky fourth nickel dam; 801, corrosive medium; 802, ornament layer;
805, erosional surface; 808, bottoming nickel dam; 809, electroless nickel layer;
810, ABS substrate.
Embodiment
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, following embodiment should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
Below the coating structure of the super anti-corrosion nickel plating-chromium parts of multilayer of the present invention is described, here base material of the present invention can adopt metal, plastics and other can be suitable for the parts of plating.
Constructive embodiment 1
As shown in Figure 1, the super anti-corrosion nickel plating-chromium parts of multilayer of the present embodiment, these parts comprise: base material 1 (ABS material); Pre-treatment coating 2 comprises electroless nickel layer 809, bottoming nickel dam 808 and copper plate 3, and electroless nickel layer 809 is deposited on whole base material 1, and bottoming nickel dam 808 is deposited in electroless nickel layer 809, and bottoming nickel dam 808 is formed copper plate 3; With basal layer 6, it is formed on copper plate 3, and wherein basal layer 6 comprises half light nickel dam 62 and full light nickel dam 63, half light nickel dam 62 is formed on copper plate 3, and full light nickel dam 63 is formed on half light nickel dam 62; With functional layer 4, it is formed on the full light nickel dam 63 of basal layer 6, wherein functional layer 4 comprises low potential nickel dam 141 and micropore nickel dam 142, wherein for high-sulfur nickel dam and tiny crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, tiny crack nickel dam be formed on high-sulfur nickel dam low potential nickel dam 141; Also can be that tiny crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on tiny crack nickel dam), micropore nickel dam 142 is formed on low potential nickel dam 141; With ornament layer 802, it is formed on micropore nickel dam 142, wherein ornament layer is the white chromium coating of trivalent, and full potential difference between light nickel dam 63 and low potential nickel dam 141 is within the scope of 0-100mv here, and the potential difference between half light nickel dam 62 and full light nickel dam 63 is within the scope of 100-200mv.
Constructive embodiment 2
As shown in Figure 2, the super anti-corrosion nickel plating-chromium parts of multilayer of the present embodiment, these parts comprise: base material 1 (ABS material); Pre-treatment coating 2 comprises electroless nickel layer 809, bottoming nickel dam 808 and copper plate 3, and electroless nickel layer 809 is deposited on whole base material 1, and bottoming nickel dam 808 is deposited in electroless nickel layer 809, and bottoming nickel dam 808 is formed copper plate 3; With basal layer 6, it is formed on copper plate 3, and wherein basal layer 6 comprises half light nickel dam 62 and Sha Ding nickel dam 64, half light nickel dam 62 is formed on copper plate 3, and husky fourth nickel dam 64 is formed on half light nickel dam 62; With functional layer 4, it is formed on the husky fourth nickel dam 64 of basal layer 6, wherein functional layer 4 comprises low potential nickel dam 141 and micropore nickel dam 142, wherein for high-sulfur nickel dam and tiny crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, tiny crack nickel dam be formed on high-sulfur nickel dam low potential nickel dam 141; Also can be that tiny crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on tiny crack nickel dam), micropore nickel dam 142 is formed on low potential nickel dam 141; With ornament layer 802, it is formed on micropore nickel dam 142, wherein ornament layer is the white chromium coating of trivalent, and the potential difference here between husky fourth nickel dam 64 and low potential nickel dam 141 is within the scope of 0-100mv, and the potential difference between half light nickel dam 62 and full light nickel dam 63 is within the scope of 100-200mv.
Constructive embodiment 3
As shown in Figure 3, the super anti-corrosion nickel plating-chromium parts of multilayer of the present embodiment, these parts comprise: base material 1 (ABS material); Pre-treatment coating 2 comprises electroless nickel layer 809, bottoming nickel dam 808 and copper plate 3, and electroless nickel layer 809 is deposited on whole base material 1, and bottoming nickel dam 808 is deposited in electroless nickel layer 809, and bottoming nickel dam 808 is formed copper plate 3; With basal layer 6, it is formed on copper plate 3, and wherein basal layer 6 comprises half light nickel dam 62, high-sulfur nickel dam 61 and full light nickel dam 63, half light nickel dam 62 and is formed on copper plate 3, high-sulfur nickel dam 61 is formed on half light nickel dam 62, and full light nickel dam 63 is formed on high-sulfur nickel dam 61; With functional layer 4, it is formed on the full light nickel dam 63 of basal layer 6, wherein functional layer 4 comprises low potential nickel dam 141 and micropore nickel dam 142, wherein for high-sulfur nickel dam and tiny crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, tiny crack nickel dam be formed on high-sulfur nickel dam low potential nickel dam 141; Also can be that tiny crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on tiny crack nickel dam), micropore nickel dam 142 is formed on low potential nickel dam 141; With ornament layer 802, it is formed on micropore nickel dam 142, and wherein ornament layer is the white chromium coating of trivalent.
Constructive embodiment 4
As shown in Figure 4, the super anti-corrosion nickel plating-chromium parts of multilayer of the present embodiment, these parts comprise: base material 1 (ABS material); Pre-treatment coating 2 comprises electroless nickel layer 809, bottoming nickel dam 808 and copper plate 3, and electroless nickel layer 809 is deposited on whole base material 1, and bottoming nickel dam 808 is deposited in electroless nickel layer 809, and bottoming nickel dam 808 is formed copper plate 3; With basal layer 6, it is formed on copper plate 3, wherein basal layer 6 comprise half light nickel dam 62, high-sulfur nickel dam 61 and Sha Ding nickel dam 64, half light nickel dam 62 be formed on copper plate 3, high-sulfur nickel dam 61 is formed on half light nickel dam 62, and husky fourth nickel dam 64 is formed on high-sulfur nickel dam 61; With functional layer 4, it is formed on the husky fourth nickel dam 64 of basal layer 6, wherein functional layer 4 comprises low potential nickel dam 141 and micropore nickel dam 142, wherein for high-sulfur nickel dam and tiny crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, tiny crack nickel dam be formed on high-sulfur nickel dam low potential nickel dam 141; Also can be that tiny crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on tiny crack nickel dam), micropore nickel dam 142 is formed on low potential nickel dam 141; With ornament layer 802, it is formed on micropore nickel dam 142, and wherein ornament layer is the white chromium coating of trivalent.
Constructive embodiment 5
As shown in Figure 5, the super anti-corrosion nickel plating-chromium parts of multilayer of the present embodiment, these parts comprise: base material 1 (ABS material); Pre-treatment coating 2 comprises electroless nickel layer 809, bottoming nickel dam 808 and copper plate 3, and electroless nickel layer 809 is deposited on whole base material 1, and bottoming nickel dam 808 is deposited in electroless nickel layer 809, and bottoming nickel dam 808 is formed copper plate 3; With basal layer 6, it is formed on copper plate 3, and wherein basal layer 6 comprises half light nickel dam 62, full light nickel dam 63 and Sha Ding nickel dam 64, half light nickel dam 62 and is formed on copper plate 3, full light nickel dam 63 is formed on half light nickel dam 62, and husky fourth nickel dam 64 is formed on full light nickel dam 63; With functional layer 4, it is formed on the husky fourth nickel dam 64 of basal layer 6, wherein functional layer 4 comprises low potential nickel dam 141 and micropore nickel dam 142, wherein for high-sulfur nickel dam and tiny crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, tiny crack nickel dam be formed on high-sulfur nickel dam low potential nickel dam 141; Also can be that tiny crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on tiny crack nickel dam), micropore nickel dam 142 is formed on low potential nickel dam 141; With ornament layer 802, it is formed on micropore nickel dam 142, and wherein ornament layer is the white chromium coating of trivalent.
Unique difference of constructive embodiment 6-10 and constructive embodiment 1-5 is only: low potential nickel dam 141 is tiny crack nickel dam.
Unique difference of constructive embodiment 11-15 and constructive embodiment 1-5 is only: low potential nickel dam 141 is high-sulfur nickel dam.
Unique difference of constructive embodiment 16-30 and constructive embodiment 1-15 is only: ornament layer 802 is sexavalent chrome coating.
Unique difference of constructive embodiment 31-45 and constructive embodiment 1-15 is only: ornament layer 802 is trivalent black chromium plating.
Unique difference of constructive embodiment 46-90 and constructive embodiment 1-45 is only: pre-treatment coating 2 comprises bottoming nickel dam 808 and copper plate 3, and bottoming nickel dam 808 is deposited on whole base material 1, and bottoming nickel dam 808 is formed copper plate 3.
Unique difference of constructive embodiment 91-135 and constructive embodiment 1-45 is only: pre-treatment coating 2 comprises electroless nickel layer 809 and copper plate 3, and electroless nickel layer 809 is deposited on whole base material 1, and electroless nickel layer 809 is formed copper plate 3.
Unique difference of constructive embodiment 136-180 and constructive embodiment 1-45 is only: there is not pre-treatment coating 2, directly on base material 1, is formed with copper plate 3.
Unique difference of constructive embodiment 181-360 and constructive embodiment 1-180 is only: base material 1 is pp material.
Unique difference of constructive embodiment 361-540 and constructive embodiment 1-180 is only: base material 1 is nylon material;
Unique difference of constructive embodiment 541-720 and constructive embodiment 1-180 is only: base material 1 is pc material;
Unique difference of constructive embodiment 721-900 and constructive embodiment 1-180 is only: base material 1 is pet material;
Unique difference of constructive embodiment 901-1080 and constructive embodiment 1-180 is only: base material 1 is bakelite material;
Unique difference of constructive embodiment 1081-1260 and constructive embodiment 1-180 is only: base material 1 is cast iron (including, without being limited to grey cast iron, white cast iron, spheroidal graphite cast iron, vermicular cast iron, malleable iron and cast alloy iron etc.) material;
Unique difference of constructive embodiment 1261-1440 and constructive embodiment 1-180 is only: base material 1 is steel (comprising various ordinary steel, stainless steel etc.) and aluminum alloy material, magnesium alloy material;
Here in all constructive embodiment, potential difference between micropore nickel dam 142 and low potential nickel dam 141 is within the scope of 10-120mv, described low potential nickel dam 141 include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between composite deposite, potential difference between described micropore nickel dam 142 and low potential nickel dam 141 is within the scope of 20-100mv, when low potential nickel dam 141 adopts the composite deposite of tiny crack nickel dam and high-sulfur nickel dam, between tiny crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mv.
Different potential difference schematic diagram can be formed by constructive embodiment 1-15 as shown in Figure 11-Figure 20.
Base material 1 material adopted in technical solution of the present invention can also may be used for being coated with on its surface the material of copper, nickel, chromium coating for other.
In the embodiment of the present invention, the solvent of solution is water (including, without being limited to distilled water, deionized water, low-hardness water etc.) unless otherwise indicated, and concentration is all with the solution measures of unit volume or quality.
The base material of following examples part preferably adopts ABS material.
Preparation embodiment 1-5
The manufacture method of the nickel plating parts of an embodiment of the present invention is as follows, the surface of base material is carried out pre-treatment (pre-treatment in turn includes the following steps: surperficial degrease, surface hydrophilic process, surface coarsening process, surperficial neutralizing treatment, preimpregnation, surface activation process, surperficial dispergation process); By pre-treatment coating (comprising chemical sinking nickel and bottoming nickel) deposition over the whole substrate, the electroless nickel layer outwards formed in turn by substrate surface and bottoming nickel dam, and copper plate is formed on pre-treatment coating (bottoming nickel dam is outer); Be formed on copper plate with by basal layer, basal layer is here half light nickel dam, high-sulfur nickel dam and Sha Ding nickel dam, and half light nickel dam is formed on copper plate, and high-sulfur nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on high-sulfur nickel dam; Be formed on the full light nickel dam of basal layer with by the low potential layer in functional layer, low potential nickel dam is high-sulfur nickel dam here; With the micropore nickel dam in functional layer is formed on high-sulfur nickel dam; With ornament layer is formed on micropore nickel dam, ornament layer is here the white layers of chrome of trivalent.
Potential difference between micropore nickel dam from high-sulfur nickel dam (low potential nickel dam) is respectively 10,20,30,40,50,60,70,80,90,100,110, other arbitrary value (embodiment 1-5 can select different numerical value in 10-120 to be the potential difference in corresponding embodiment between micropore nickel dam and low potential nickel dam respectively, and the potential difference in each embodiment between micropore nickel dam with low potential nickel dam also can be identical) within the scope of the arbitrary or 10-120 of 120mv.Micropore nickel dam is plate the nickel dam of one deck uniformly and containing numerous non-conductive particle and conductive particle at product surface, and make ABS substrate workpiece surface have high Corrosion Protection, high rigidity, high-wearing feature like this, binding force of cladding material is good, luminance brightness advantages of higher.
On above-mentioned part, nickel electric plating method comprises the steps:
(1) surperficial degrease: by ABS substrate at sodium hydroxide NaOH, sodium carbonate Na
2cO
3, water glass Na
2siO
3with clean in the mixing solutions of tensio-active agent.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table one.Tensio-active agent is that conventional surfactants is as sodium laurylsulfonate, sodium stearyl sulfonate etc.
Table one
(2) surface hydrophilic process: carry out in sulfuric acid and whole agent mixing solutions.In this step, sulfuric acid and whole agent concentration proportioning is in different embodiments in table two:
Table two
(3) surface coarsening process: at chromic trioxide CrO after degrease
3with sulfuric acid H
2sO
4carry out in mixed solution.In this step, chromic trioxide CrO
3with sulfuric acid H
2sO
4concentration proportioning is in different embodiments in table three:
Table three
(4) surperficial neutralizing treatment: the mixing solutions ABS substrate after surface coarsening process being put into hydrochloric acid and hydrazine hydrate carries out.In this step, hydrochloric acid and hydrazine hydrate at the concentration proportioning of different embodiment in table four:
Table four
(5) surperficial preimpregnation: the base material after surperficial neutralizing treatment carries out in hydrochloric acid soln, in this step, hydrochloric acid soln at the concentration proportioning of different embodiment in table five:
Table five
(6) surface activation process: adopt colloidal palladium solution to carry out surface activation process, hydrochloric acid, Palladous chloride PdCl in colloidal palladium solution after neutralization
2with tin protochloride SnCl
2at the concentration proportioning of different embodiment in table six:
Table six
(7) surperficial dispergation process: at sulfuric acid H
2sO
4carry out in solution.In this step sulphuric acid soln at the concentration proportioning of different embodiment in table seven:
Table seven
(8) electroless nickel layer is plated: containing single nickel salt, inferior sodium phosphate, Trisodium Citrate C
6h
5na
3o
7, ammonium chloride and ammoniacal liquor (ammoniacal liquor be used for the pH of regulator solution be 8.6-9.2) mixing solutions in carry out.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table eight.
Table eight
(9) bottoming nickel dam is plated: containing aqueous sulfuric acid nickel
2sO
4-6H
2o, moisture nickelous chloride NiCl
2-6H
2o, boric acid H
3bO
3carry out with in the mixing solutions of wetting agent.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table nine.In table nine, wetting agent is as the happy 62A of think of or the NIMAC32C WETTER of wheat dolantin.
Table nine
(10) copper plate: at copper sulfate CuSO
4, sulfuric acid H
2sO
4, chlorion, leveling agent, walk agent and open cylinder agent mixing solutions in carry out.In this step, in mixing solutions each component at the concentration proportioning of different embodiment in table ten.Here leveling agent is the happy 1560 sour copper additives series thought, and the agent that walks is the happy 1561 sour copper additives series thought, and open cylinder agent is the happy 1562 sour copper additives series thought.
Table ten
(11) half light nickel dam is plated: at aqueous sulfuric acid nickel
2sO
4-6H
2o, moisture nickelous chloride NiCl
2-6H
2o and boric acid H
3bO
3, the elementary brightening agent of semi-bright nickel, semi-bright nickel second-class brightener, potential difference adjusting agent and wetting agent mixing solutions in carry out.In this step, in mixing solutions each component at the concentration proportioning of different embodiment respectively in table ten one.Here wetting agent is as the happy 62A of think of or the NIMAC32C WETTER of wheat dolantin, the elementary brightening agent of semi-bright nickel is the happy BTL MU of think of or the NIMAC SF DUCT of wheat dolantin, semi-bright nickel second-class brightener is the happy TL-2 of think of or the NIMAC SF LEVELER of wheat dolantin, and potential difference adjusting agent is the B benefit of happy think of or the NIMAC SF MAINTENANCE of wheat dolantin.
Table ten one
(12) high-sulfur nickel dam is plated: carry out in the mixing solutions of aqueous sulfuric acid nickel, moisture nickelous chloride, boric acid, high sulfur additives and wetting agent.In this step, in mixing solutions each component at the concentration proportioning of different embodiment respectively in table ten two.Here wetting agent is as the happy 62A of think of or the NIMAC32C WETTER of wheat dolantin.
Table ten two
(13) husky fourth nickel dam is plated: carry out in the mixing solutions of aqueous sulfuric acid nickel, moisture nickelous chloride, boric acid, supplementary additive and Sha Ding nickel forming agent.In this step, in mixing solutions each component at the concentration proportioning of different embodiment respectively in table ten three.Here supplementary additive is Elpelyt pearlbrite carrier K4 or the Elpelyt carrier brightener H of happy think of, and husky fourth nickel forming agent is the happy Elpelyt pearlbrite additive K6AL thought.
Table ten three
(14) high-sulfur nickel dam (low potential layer) is plated: carry out in the mixing solutions of aqueous sulfuric acid nickel, moisture nickelous chloride, boric acid, high sulfur additives and wetting agent.In this step, in mixing solutions each component at the concentration proportioning of different embodiment respectively in table ten four.Here wetting agent is as the happy 62A of think of or the NIMAC32C WETTER of wheat dolantin.
Table ten four
(15) micropore nickel dam is plated: seal in the mixing solutions of particulate vector at aqueous sulfuric acid nickel, moisture nickelous chloride, boric acid, nickel envelope brightening agent, nickel envelope key light agent and nickel and carry out.In this step, in mixing solutions each component at the concentration proportioning of different embodiment respectively in table ten five.Here nickel envelope brightening agent is 63 of happy think of; The agent of nickel envelope key light is the happy 610CFC thought; Nickel envelope particulate vector is the happy ENHANCER thought.
Table ten five
(16) the white layers of chrome of trivalent (ornament layer) is plated: carry out in the mixing solutions of moisture chromium chloride, potassium formiate, brometo de amonio, ammonium chloride, Repone K, sodium acetate, boric acid, wetting agent.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table ten six.Here wetting agent is as the happy 62A of think of or the NIMAC32C WETTER of wheat dolantin.
Table ten six
More than prepare Embodiment C ASS experiment reach 96-120h and more than, the experiment of rotten gypsum then reaches stable more than 336h.
Preparation embodiment 6-10 is only with unique difference of preparation embodiment 1-5, and low potential nickel dam is fine fisssure lamina.Plating tiny crack nickel dam carries out in the mixing solutions of moisture nickelous chloride, acetic acid, PN-1A, PN-2A, wetting agent.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table ten seven.Here wetting agent is as the happy 62A of think of or the NIMAC32C WETTER of wheat dolantin.
Table ten seven
Preparation embodiment 11-15 is only with unique difference of preparation embodiment 1-5, low potential nickel dam include high-sulfur nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten four), tiny crack nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten seven) two-layer between compound.Now between fine fisssure lamina and high-sulfur nickel dam, potential difference is the arbitrary value mv of the arbitrary or 10-80 scope of 10,20,30,40,50,60,70,80.
Preparation embodiment 16-30 is only with unique difference of preparation embodiment 1-15, and ornament layer is sexavalence layers of chrome.Plating sexavalence layers of chrome is carried out in the mixing solutions of chromic anhydride, sulfuric acid, decorative chromium brightening agent and chromium fog inhibitor.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table ten eight.Here decorative chromium brightening agent is the happy 1120F of think of or the 7000C of Japanese chemical metallization.
Table ten eight
Preparation embodiment 31-45 is only with unique difference of preparation embodiment 1-15, and ornament layer is trivalent black chromium coating.Plating trivalent black chromium coating carries out in the mixing solutions of moisture chromium chloride, oxalic acid, ammonium acetate, ammonium chloride, boric acid and additive.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table ten nine.
Table ten nine
Preparation embodiment 46-90 is only with unique difference of preparation embodiment 1-45, and basal layer comprises the half light nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten one) and full light nickel dam that are outwards formed in turn by copper plate surface.Plate full light nickel dam at aqueous sulfuric acid nickel
2sO
4-6H
2o, moisture nickelous chloride NiCl
2-6H
2o, boric acid H
3bO
3, bright nickel softening agent, the agent of bright nickel key light and wetting agent mixing solutions in carry out.In this step, in mixing solutions each component at the concentration proportioning of different embodiment respectively in table two ten.Here wetting agent is the NIMAC32C WETTER as the happy 62A that thinks or wheat dolantin, and bright nickel softening agent is the NIMAC14INDEX of happy 63 or the wheat dolantin thought, and the agent of bright nickel key light is the NiMac Chanllenger Plus of the happy 66E that thinks or wheat dolantin.
Table two ten
Preparation embodiment 91-135 is only with unique difference of preparation embodiment 1-45, and basal layer comprises the half light nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten one) and husky fourth nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten three) that are outwards formed in turn by copper plate surface.
Preparation embodiment 136-180 is only with unique difference of preparation embodiment 1-45, and basal layer comprises the half light nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten one), high-sulfur layer (each embodiment plating solution is accordingly in turn see shown in table ten two) and the full light nickel dam (each embodiment plating solution is accordingly in turn see shown in table two ten) that are outwards formed in turn by copper plate surface.
Preparation embodiment 181-225 is only with unique difference of preparation embodiment 1-45, and basal layer comprises the half light nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten one) outwards formed in turn by copper plate surface, full light nickel dam (each embodiment plating solution is accordingly in turn see shown in table two ten) and husky fourth nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten three).
Preparation embodiment 226-450 is only with unique difference of preparation embodiment 1-225, and nickel envelope brightening agent is the NIMAC14INDEX of wheat dolantin; The agent of nickel envelope key light is the NIMAC33 of wheat dolantin; Nickel envelope particulate vector is the NiMac Hypore XL dispersion agent of wheat dolantin.
Preparation embodiment 451-900 is only with unique difference of preparation embodiment 1-450, plating microporous nickel plating solution also comprises micropore powder particles 0.3-0.8ml/L (can select arbitrary value about the consumption of micropore powder particles in embodiment: 0.3,0.32,0.33,0.34,0.37,0.39,0.4,0.42,0.43,0.44,0.47,0.49,0.5,0.52,0.53,0.54,0.57,0.59,0.6,0.62,0.63,0.64,0.67,0.69,0.7,0.72,0.73,0.74,0.77,0.79,0.8), 618 of happy think of herein; Wetting agent 1.0-3.0ml/L (can select arbitrary value about the consumption of wetting agent in embodiment: 1,1.2,1.3,1.4,1.7,1.9,2,2.2,2.3,2.4,2.7,2.9,3.0), the happy 62A thought herein.
Preparation embodiment 901-1350 is only with unique difference of preparation embodiment 451-900, and in plating microporous nickel plating solution, micropore powder particles is the NiMac Hypore XL pulvis of wheat dolantin; Wetting agent is the NIMAC32C WETTER of wheat dolantin.
Preparation embodiment 1351-2700 is only with unique difference of preparation embodiment 1-1350, and pre-treatment coating is electroless nickel layer (each embodiment plating solution is accordingly in turn see table eight Suo Shi).
Preparation embodiment 2701-4050 is only with unique difference of preparation embodiment 1-1350, and pre-treatment coating is bottoming nickel dam (each embodiment plating solution is accordingly in turn see table nine Suo Shi).
Preparation embodiment 4051-5400 is only with unique difference of preparation embodiment 1-1350, and substrate surface does not exist pre-treatment coating, and copper plate is directly formed at substrate surface.
More than prepare PN-1A, PN-2A in embodiment and be Atotech (China) Chemical Co., Ltd. commercially available prod.
Comprehensive above all embodiments, can find out, the all embodiments of technical solution of the present invention reach 96-120h and above (prior art then proposes as 40-48h) by CASS experiment, rotten gypsum experiment then reaches stable more than 336h (product that prior art obtains is then unstable, cannot carry out quantization signifying).
In technical solution of the present invention, base material can also adopt and include, without being limited to that the material such as PC, PP, nylon, PET, bakelite and cast iron, steel, aluminium alloy, magnesium alloy makes at interior material.When selecting other base material except ABS, pre-treatment coating can carry out selection according to the performance of actual material and process requirements has pre-treatment coating or without pre-treatment coating.
As the etch state figure that Fig. 7 nickel plating parts sample that obtain to by one embodiment of the invention obtains after 72h CASS tests, with the nickel plating parts sample etch state figure that (under equal experiment condition) obtains after 72h CASS tests that Fig. 6 is prior art, can intuitively arrive through contrast, the corrosion vacancy 21 that existing sample produces after there is a large amount of plating exfoliations and corrosion after the test, seriously have impact on the quality of product coating.Fig. 7 then can find out, then only there is the surface micropore 31 of some amount on surface in the nickel plating sample that the present invention obtains, then equally only there is less corrosion hole 32 in section display, be the coating structure that corrosion hole that surface micropore and sacrifice layer produce all does not have to destroy parts, do not affect the use of product and attractive in appearance.
Fig. 8 and Fig. 9 is then respectively the nickel plating parts sample of prior art and the sample surfaces etch state figure of the nickel plating parts sample of one embodiment of the invention gained after fluorgypsum experiment (336h, 336h, 118h) (in figure, circle inside is divided into Experimental Area), can find out in figure, the nickel plating parts sample surfaces of prior art is all subject to corrosion in various degree, it is very slight that the sample that the present invention obtains then is corroded degree, substantially do not have variable color.As can be seen here, the nickel plating parts that unquestionable technical solution of the present invention obtains have more excellent coating stability and erosion resistance, make nickel plating parts more durable, attractive in appearance.
As shown in Figure 10, the mechanism when nickel plating parts that the present invention program obtains are corroded is: for form electroless nickel layer 809, bottoming nickel dam 808, copper plate 3, basal layer 6, low potential nickel dam 141, micropore nickel dam 142 and ornament layer 802 in ABS substrate 810 layer by layer in figure.Corrosive medium 801 disperses corrosion current and enters low potential nickel dam 141 (to reduce the area of actual participation corrosion in the microvoid structure of micropore nickel dam 142, there is less corroded area, form multiple independently hot spot, thus dispersion corrosion current, delay corrosion speed), after corrosion forms erosional surface 805, after erosional surface 805 runs through low potential nickel dam 141, run into high potential basal layer 6 and rear termination of copper plate 3 are longitudinally corroded, become lateral encroaching until corroded by whole low potential nickel dam 141, just can carry out next step corrosion, until coating structure is destroyed by entirety.
Coating potential ph diagram ph as Figure 11 to Figure 20 then can be found out, in the present embodiment scheme, no matter low potential nickel dam is simple layer or lamination layer structure, to be when being corroded with low potential nickel dam as sacrifice layer, when low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam, the height of the current potential of high-sulfur nickel dam and tiny crack nickel dam regulates with actual production technique, can be that high-sulfur nickel dam electromotive force is slightly high, also can be that tiny crack nickel dam electromotive force is slightly high.Then preferentially corrode basal layer according to electrocorrosion priority ranking when low potential nickel dam corrodes completely, reduce the destruction to surface structure.
The non-limit part of technical scope mid point value that this place embodiment is protected application claims, equally all in the scope of protection of present invention.
Technique means disclosed in the present invention program is not limited only to the technique means disclosed in above-mentioned technique means, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.Be more than the specific embodiment of the present invention, it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications are also considered as protection scope of the present invention.
Claims (13)
1. the super anti-corrosion nickel plating-chromium parts of multilayer, these parts comprise:
Base material;
Pre-treatment coating, its deposition over the whole substrate, pre-treatment coating is formed with copper plate; With
Basal layer, it is formed on copper plate; With
Functional layer, it is formed on basal layer, and wherein functional layer comprises low potential nickel dam and is formed at the micropore nickel dam on low potential nickel dam; With
Ornament layer, it is formed on micropore nickel dam, and described ornament layer is the arbitrary of trivalent chromium coating or sexavalent chrome coating.
2. nickel plating parts according to claim 1, is characterized in that: the potential difference between described micropore nickel dam and low potential nickel dam is within the scope of 10-120mv.
3. nickel plating parts according to claim 2, is characterized in that: described low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between composite deposite.
4. the nickel plating parts according to Claims 2 or 3, is characterized in that: the potential difference between described micropore nickel dam and low potential nickel dam is within the scope of 20-100mv.
5. nickel plating parts according to claim 3, is characterized in that: when low potential nickel dam adopts the composite deposite of tiny crack nickel dam and high-sulfur nickel dam, between tiny crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mv.
6. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 1, is characterized in that: described basal layer comprise in half light nickel dam, high-sulfur nickel dam, full light nickel dam, husky fourth nickel dam one or more layers.
7. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, is characterized in that: described basal layer is the compound between half light nickel dam and full light nickel dam, and wherein, half light nickel dam is formed on copper plate, and full light nickel dam is formed on half light nickel dam.
8. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, it is characterized in that: described basal layer is the compound between half light nickel dam and Sha Ding nickel dam, wherein, half light nickel dam is formed on copper plate, and husky fourth nickel dam is formed on half light nickel dam.
9. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, it is characterized in that: described basal layer is half light nickel dam, high-sulfur nickel dam and the compound entirely between light nickel dam, wherein, half light nickel dam is formed on copper plate, high-sulfur nickel dam is formed on half light nickel dam, and full light nickel dam is formed on high-sulfur nickel dam.
10. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, it is characterized in that: described basal layer is half light nickel dam, compound between high-sulfur nickel dam and Sha Ding nickel dam, wherein, half light nickel dam is formed on copper plate, high-sulfur nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on high-sulfur nickel dam.
The super anti-corrosion nickel plating-chromium parts of 11. multilayer according to claim 6, it is characterized in that: described basal layer is half light nickel dam, full compound between light nickel dam and Sha Ding nickel dam, wherein, half light nickel dam is formed on copper plate, full light nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on full light nickel dam.
The manufacture method of the super anti-corrosion nickel plating-chromium parts of 12. multilayer, the method comprises the steps:
Pre-treatment is carried out on the surface of base material;
Pre-treatment coating is deposited over the whole substrate, and copper plate is formed on pre-treatment coating; With
Basal layer is formed on copper plate; With
Low potential nickel dam in functional layer is formed on basal layer; With
Micropore nickel dam in functional layer is formed on low potential nickel dam; With
Be formed at by ornament layer on micropore nickel dam, described ornament layer is the arbitrary of trivalent chromium coating or sexavalent chrome coating.
The manufacture method of the super anti-corrosion nickel plating-chromium parts of 13. multilayer according to claim 12, is characterized in that: described basal layer comprise in half light nickel dam, high-sulfur nickel dam, full light nickel dam, husky fourth nickel dam one or more layers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510105201.2A CN104775143B (en) | 2015-03-11 | 2015-03-11 | Multilayer super corrosion resistant nickel-chromium plated component and method of making same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510105201.2A CN104775143B (en) | 2015-03-11 | 2015-03-11 | Multilayer super corrosion resistant nickel-chromium plated component and method of making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104775143A true CN104775143A (en) | 2015-07-15 |
| CN104775143B CN104775143B (en) | 2020-08-18 |
Family
ID=53616900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510105201.2A Active CN104775143B (en) | 2015-03-11 | 2015-03-11 | Multilayer super corrosion resistant nickel-chromium plated component and method of making same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104775143B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772946A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Nickel-chromium plating part and manufacturing method thereof |
| CN109440175A (en) * | 2018-12-17 | 2019-03-08 | 嘉兴敏惠汽车零部件有限公司 | A kind of multi-thread unification novel electroplating production line for car trim |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102317504A (en) * | 2009-02-13 | 2012-01-11 | 日产自动车株式会社 | Chrome-plated part and manufacturing method of the same |
| CN102943292A (en) * | 2012-11-07 | 2013-02-27 | 嘉兴敏惠汽车零部件有限公司 | Method for electroplating micro-crack nickel on plastic surface |
| CN104772946A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Nickel-chromium plating part and manufacturing method thereof |
| CN204589340U (en) * | 2015-03-11 | 2015-08-26 | 嘉兴敏惠汽车零部件有限公司 | A kind of super anti-corrosion nickel plating-chromium parts |
| CN204589341U (en) * | 2015-03-11 | 2015-08-26 | 嘉兴敏惠汽车零部件有限公司 | Nickel plating and or chromium parts |
| CN204625811U (en) * | 2015-03-11 | 2015-09-09 | 嘉兴敏惠汽车零部件有限公司 | The super anti-corrosion nickel plating-chromium parts of multilayer |
| RU2618017C2 (en) * | 2015-03-11 | 2017-05-02 | Цзясин Миньхой Аутомотив Партс Ко., Лтд | Nickel and/or chromium-plated element and method for its production |
| CN104772947B (en) * | 2015-03-11 | 2017-07-11 | 嘉兴敏惠汽车零部件有限公司 | Plate nickel chromium triangle part and its manufacture method |
-
2015
- 2015-03-11 CN CN201510105201.2A patent/CN104775143B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102317504A (en) * | 2009-02-13 | 2012-01-11 | 日产自动车株式会社 | Chrome-plated part and manufacturing method of the same |
| CN102943292A (en) * | 2012-11-07 | 2013-02-27 | 嘉兴敏惠汽车零部件有限公司 | Method for electroplating micro-crack nickel on plastic surface |
| CN104772946A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Nickel-chromium plating part and manufacturing method thereof |
| CN204589340U (en) * | 2015-03-11 | 2015-08-26 | 嘉兴敏惠汽车零部件有限公司 | A kind of super anti-corrosion nickel plating-chromium parts |
| CN204589341U (en) * | 2015-03-11 | 2015-08-26 | 嘉兴敏惠汽车零部件有限公司 | Nickel plating and or chromium parts |
| CN204625811U (en) * | 2015-03-11 | 2015-09-09 | 嘉兴敏惠汽车零部件有限公司 | The super anti-corrosion nickel plating-chromium parts of multilayer |
| RU2618017C2 (en) * | 2015-03-11 | 2017-05-02 | Цзясин Миньхой Аутомотив Партс Ко., Лтд | Nickel and/or chromium-plated element and method for its production |
| JP6134354B2 (en) * | 2015-03-11 | 2017-05-24 | 嘉興敏惠汽車零部件有限公司 | Nickel and / or chrome plated parts |
| CN104772947B (en) * | 2015-03-11 | 2017-07-11 | 嘉兴敏惠汽车零部件有限公司 | Plate nickel chromium triangle part and its manufacture method |
| CN104772946B (en) * | 2015-03-11 | 2018-03-16 | 嘉兴敏惠汽车零部件有限公司 | Plate nickel chromium triangle part and its manufacture method |
| US9976223B2 (en) * | 2015-03-11 | 2018-05-22 | Jiaxing Minhui Automotive Parts Co., Ltd. | Nickel and/or chromium plated member and method for manufacturing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772946A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Nickel-chromium plating part and manufacturing method thereof |
| CN109440175A (en) * | 2018-12-17 | 2019-03-08 | 嘉兴敏惠汽车零部件有限公司 | A kind of multi-thread unification novel electroplating production line for car trim |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104775143B (en) | 2020-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104775142A (en) | Ultra-corrosion-resistant nickel-chromium plating component and manufacturing method thereof | |
| CN104772946B (en) | Plate nickel chromium triangle part and its manufacture method | |
| CN104790004A (en) | Nickel and/or chromium plated component and manufacturing method thereof | |
| CN204589340U (en) | A kind of super anti-corrosion nickel plating-chromium parts | |
| CN204625811U (en) | The super anti-corrosion nickel plating-chromium parts of multilayer | |
| CN102936742B (en) | Method for electroplating black trivalent chromium on surface of plastic for vehicle decorating strip | |
| CN100462479C (en) | Chemical plating method for Mg and its alloy | |
| CN102943292A (en) | Method for electroplating micro-crack nickel on plastic surface | |
| CN102345150B (en) | Magnesium alloy surface treating method and magnesium alloy prepared by same | |
| CN103882492A (en) | Chemical plating posttreatment method of metallic matrix | |
| CN204585986U (en) | Nickel plating-chromium parts | |
| CN103510130A (en) | Trivalent hard chromium electroplating method | |
| CN204589341U (en) | Nickel plating and or chromium parts | |
| US20230398571A1 (en) | Corrosion-resistant magnesium alloy with a multi-level protective coating and preparation process thereof | |
| CN104746116A (en) | Nickel-plated component and manufacturing method thereof | |
| CN104775143A (en) | Multilayer ultra corrosion resistant nickel-chromium plating part and manufacturing method thereof | |
| CN204589342U (en) | Nickel plating parts | |
| CN104772947B (en) | Plate nickel chromium triangle part and its manufacture method | |
| CN204640958U (en) | Nickel plating-chromium parts | |
| Kotomchin et al. | Study of High-Performance Chromium Electrolyte for Restoration of Automobile and Road-Construction Machinery Parts | |
| KR102194114B1 (en) | Functional chromium layer with improved corrosion resistance | |
| CN207918993U (en) | A kind of imitative golden composite plating layer structure of bright Zn-Ni alloy, high tin copper-tin alloy, ormolu | |
| KR100402730B1 (en) | Method process for forming copper and nickel-plated of electrolytic plating in magnesium compound | |
| CN204690105U (en) | The outer covering protection Rotating fields of a kind of car trim | |
| JPH06240490A (en) | Corrosion resistant chromium plating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |