CN104772946A - Nickel-chromium plating part and manufacturing method thereof - Google Patents
Nickel-chromium plating part and manufacturing method thereof Download PDFInfo
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- CN104772946A CN104772946A CN201510105136.3A CN201510105136A CN104772946A CN 104772946 A CN104772946 A CN 104772946A CN 201510105136 A CN201510105136 A CN 201510105136A CN 104772946 A CN104772946 A CN 104772946A
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Abstract
The invention discloses a nickel-chromium plating part and a manufacturing method thereof. The 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 a kind of workpiece and the manufacture method thereof with surface plating structure, particularly a kind of nickel plating-chromium parts and manufacture method thereof.
In the application, electrical potential difference is the difference of the standard electrode 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 electrodeposited coating of crackle or hole (comprising Cr VI and trivalent chromium coating) completely, expose after aerial chromium electrodeposited 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 electrodeposited coating in extreme environment, occur a large amount of irregular corrosion, even the corrosion of nickel dam large 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 micro-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 micro-crack nickel dam, product surface sends out mist, and 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: nickel 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 corrosion resistance that improve working of plastics 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 electrodeposited 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 automobile component (grid, panel, door handle) afterwards service 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: nickel 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 of the example described in patent document is actual is restricted to Cr VI plating, does not refer to trivalent chromium plating.
Summary of the invention
For solving the problem, the invention discloses a kind of nickel plating-chromium parts, 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 corrosion resistance of the functional layer comprising microporous nickel, product can be made to reach superelevation corrosion resistance and structural stability, even if after electronegative potential nickel dam is corroded, micropore nickel dam can play the effect of supporting and delaying to corrode equally.
Nickel plating disclosed by the invention-chromium part components, these parts comprise:
Base material;
Pretreatment coating, its deposition over the whole substrate, pretreatment 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 electronegative potential nickel dam and is formed at the micropore nickel dam on electronegative potential nickel dam; With
Decorative layer, it is formed on micropore nickel dam, and described decorative layer is the arbitrary of trivalent chromium coating or Cr VI coating.
The one of nickel plating disclosed by the invention-chromium part components is improved, and decorative layer is trivalent chromium coating, and trivalent chromium coating is the trivalent chromium coating of the white chrome plating of trivalent or trivalent black chromium plating or other kind.When decorative layer is trivalent chromium coating, passivating film can also be contained at trivalent chromium coating surface.
The one of nickel plating disclosed by the invention-chromium part components is improved, and the potential difference of micropore nickel dam and electronegative potential nickel dam is 10-120mv.
The one of nickel plating disclosed by the invention-chromium part components is improved, electronegative potential nickel dam include one deck in high-sulfur nickel dam, micro-crack nickel dam or two-layer between compound.Preferred further, the potential difference between micropore nickel dam and electronegative potential nickel dam is 20-100mv.
The one of nickel plating disclosed by the invention-chromium part components is improved, and when electronegative potential nickel dam employing micro-crack nickel and high-sulfur nickel composite deposite, between micro-crack and high-sulfur nickel, potential difference is in 10-80mv.
The manufacture method of nickel plating disclosed by the invention-chromium parts comprises the steps:
Pretreatment is carried out on the surface of base material;
Pretreatment coating is deposited over the whole substrate, and copper plate is formed on pretreatment coating; With
Basal layer is formed on copper plate; With
Electronegative potential nickel dam in functional layer is formed on basal layer; With
Micropore nickel dam in functional layer is formed on electronegative potential nickel dam; Potential difference between described micropore nickel dam and electronegative potential nickel dam is within the scope of 10-120mv; With
Be formed at by decorative layer on micropore nickel dam, described decorative layer is the arbitrary of trivalent chromium coating or Cr VI coating.
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 electronegative potential nickel dam Indirect Electro is plated on copper plate, can also electroplate other coating, be totally referred to as basal layer between electronegative 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 nickel plating-chromium parts, and it comprises following: matrix; Pretreatment 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 pretreatment 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; Electronegative potential nickel coating, it is formed on basic coating, microporous layers, and it is formed with on electronegative potential nickel dam, and the electrical potential difference wherein between electronegative potential nickel coating and microporous nickel coating is in the scope of 10mV to 120mV; With decorative layer (can be chrome plating, as trivalent chromium coating or Cr VI coating arbitrary), it be formed on microporous nickel coating, and has the one of at least any of microcellular structure and micro-cracked structure.
A second aspect of the present invention provides the manufacture method of nickel plating-chromium parts, and it comprises the following steps: be formed at by pretreatment coating on whole matrix; Copper plate is formed on pretreatment coating; Basal layer is formed on copper plate; Your electronegative potential nickel coating being formed on basic coating by, be formed at by micropore nickel dam on electronegative potential nickel dam, the electrical potential difference wherein between electronegative potential nickel coating and microporous nickel coating is in the scope of 10mV to 120mV; Decorative layer is formed on micropore nickel dam.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, and decorative layer is trivalent chromium coating, and trivalent chromium coating is the trivalent chromium coating of the white chrome plating of trivalent or trivalent black chromium plating or other kind.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, electronegative potential nickel dam include one deck in high-sulfur nickel dam, micro-crack nickel dam or two-layer between compound.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, 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 nickel chloride 50-60g/L, boric acid 40-50g/L, nickel envelope brightener 6-12ml/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) Co., Ltd is hereinafter referred to as wheat dolantin, NIMAC 14INDEX as happy 63 or the wheat dolantin thought), nickel envelope key light agent 4-7.5ml/L (610CFC thought as happy or the NIMAC 33 of wheat dolantin), nickel envelope particle 0.2-1.5g/L, nickel envelope particle dispersants 0.5-3ml/L, wetting agent 1-5ml/L (ENHANCER thought as happy or the NiMac Hypore XL dispersant of wheat dolantin).When micropore nickel dam is coated with, operating 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 be deposited on plated item by the mode of direct current electrolysis, require that nickel coating thickness is not less than 1.5 microns.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, decorative layer is the white chrome plating of trivalent, the white chrome plating of trivalent adopts the white chromium plating solution plating of plating trivalent to form, and the white chromium plating solution of trivalent comprises composition and concentration is (in unit volume plating solution addition): moisture chromium chloride 90-150g/L, potassium formate 50-100g/L, ammonium bromide 8-25g/L, ammonium chloride 40-60g/L, potassium chloride 40-100g/L, sodium acetate 10-60g/L, boric acid 40-80g/L, wetting agent 0.5-2.5ml/L.Require that chrome plating is not less than 0.1 μm.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, decorative layer is trivalent black chromium plating, trivalent black chromium plating adopts the black chromium plating solution plating of plating trivalent to form, the black chromium plating solution of trivalent comprises composition and concentration is (in unit volume plating solution addition): moisture chromium chloride 150-250g/L, oxalic acid 2-5g/L, ammonium acetate 3-10g/L, ammonium chloride 20-40g/L, boric acid 20-41g/L, additive 0.5-3g/L.Require that chrome plating is not less than 0.1 μm.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, decorative layer is Cr VI coating, Cr VI coating adopts the plating of plating Cr VI plating solution to form, Cr VI plating solution comprises composition and concentration is (in unit volume plating solution addition): chromic anhydride 260-360g/L, sulfuric acid 0.5-3g/L, decorative chromium brightener 1-4g/L, chromium fog inhibitor 0.1-0.4ml/L.Require that chrome plating is not less than 0.1 μm.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, micro-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 nickel 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 NIMAC 32C WETTER of wheat dolantin).When micro-crack nickel dam is coated with, operating 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 be deposited on 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.
The one of the manufacture method of nickel plating disclosed by the invention-chromium parts is improved, 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 nickel 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 NIMAC 32C 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, making nickel be deposited on plated item by the mode of direct current electrolysis plates on basic coating surface, and 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 neutralisation 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 NaOH, sodium carbonate, surfactant and sodium metasilicate mixed solution, immerse after degrease in chromic anhybride and sulfuric acid mixture liquid and carry out surface coarsening process, then put into hydrochloric acid solution and carry out surface neutralization, adopt colloid palladium solution to carry out surface activation process after neutralization, then in sulfuric acid solution, carry out surperficial dispergation process.
As preferably, the mixed solution of surperficial grease treatment process comprises composition and concentration is: the concentration of NaOH is 20-50g/L, and the concentration of sodium carbonate is 10-40g/L, surfactant 1-3g/L, and the concentration of sodium metasilicate 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 sulfuric acid solution concentration of surface hydrophilic operation is 20-100g/L, whole agent 0.5-2ml/L.
As preferably, the mixed liquor of surface coarsening treatment process comprises composition and concentration is: the concentration of chromic anhybride is 330-480g/L, and the concentration of sulfuric acid is 330-480g/L.
As preferably, in surface and the mixed solution 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 colloid palladium solution of surface activation process comprises composition and concentration is: hydrochloric acid 180-280ml/L, and the concentration of palladium bichloride is the concentration 1-6g/L of 20-60ppm, stannous chloride.
Here in colloid palladium solution, palladium bichloride is covered in substrate surface, for follow-up chemical nickel provides catalytic center, the tin ion of stannous chloride 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 colloid palladium solution can be increased.
As preferably, the sulfuric acid solution concentration of surperficial dispergation treatment process is 40-100g/L.
Surface dispergation process refers to and utilizes sulfuric acid to remove in colloid palladium solution the stannous chloride be coated on around palladium oxide, is come out by Metal Palladium particle, makes subsequent chemistry sink nickel technique more smooth and easy.
In above-mentioned manufacture method, pretreatment 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 mixed solution comprises composition and concentration is: the concentration of nickelous sulfate 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 natrium citricum 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 Metal Palladium that substrate surface has catalytic activity, and be convenient to the various metal of follow-up plating, in chemical sinking nickel process, nickelous sulfate provides nickel element; Inferior sodium phosphate is strong reductant, and the nickel element in nickelous sulfate is reduced into metallic nickel by it; Natrium citricum is buffer, and it makes the reaction of inferior sodium phosphate reduced nickel element more mild.
As preferably, the mixed solution 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 nickel 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 NIMAC 32C 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 electric conductivity of coating further.In this step, aqueous sulfuric acid nickel, moisture nickel chloride provide nickel ion needed for electrochemical reaction.
In above-mentioned manufacture method, in the mixed solution of copper plate operation, each component and concentration are: the concentration of copper sulphate 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 sulphate to improve 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 coats of metal, 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, basal layer can comprise the compound of the arbitrary or multilayer in half light nickel dam, full light nickel dam, husky fourth nickel dam, high-sulfur nickel dam.
As preferably, plating each component and concentration in the mixed solution of half light nickel operation is: aqueous sulfuric acid nickel 200-300g/L, moisture nickel chloride 35-50g/L, boric acid 35-50g/L, the elementary brightener 3.0-7.0ml/L of semi-bright nickel (the BTL MU thought as happy or the 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 NIMAC 32C WETTER of wheat dolantin).When half light nickel dam is coated with, operating 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 be deposited on 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 column structure, can improve the corrosion resistance of coating.
As preferably, plating each component and concentration in the mixed solution of full light nickel operation is: aqueous sulfuric acid nickel 220-340g/L, moisture nickel chloride 40-50g/L, boric acid 35-40g/L, bright nickel softening agent 8-12ml/L (the NIMAC 14INDEX 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 NIMAC 32C WETTER of wheat dolantin).When full light nickel dam is coated with, operating 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, make nickel be deposited on plated item by the mode of direct current electrolysis to plate on half light nickel surface, 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 layer structure, can improve the brightness of coating.
As preferably, plating each component and concentration in the mixed solution of husky fourth nickel operation is: the concentration of aqueous sulfuric acid nickel is 250-350g/L, the concentration of moisture nickel chloride is 35-60g/L, the concentration of boric acid is 35-65g/L, the concentration of auxiliary additive is 5-20ml/L (the Elpelyt pearlbrite carrier K4 thought as happy or Elpelyt carrier brightener H), and the concentration of husky fourth nickel forming agent is 0.1-0.6ml/L (as the happy Elpelyt pearlbrite additive K6AL thought).
As preferably, in the mixed solution of plating high-sulfur nickel operation, each component and concentration are: the concentration of aqueous sulfuric acid nickel is 250-350g/L, the concentration of moisture nickel 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 NIMAC 32C WETTER of wheat dolantin).
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, stabilizing agent all have employed boric acid but not natrium citricum 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.
Micro-crack nickel dam in functional layer, micropore nickel dam or both combine the reason that can play anticorrosion 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 corrosion 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, corrosion 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 corrosion 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 size by large 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 micro-crack, microcellular 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 electronegative 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 corrosion rate, the corrosion rate delayed.
Second step: when corroding arrival electronegative potential nickel dam, comparatively electronegative potential nickel current potential is high due to microporous nickel current potential, and now electronegative potential nickel is preferentially corroded as anodic coating (namely electronegative potential layer is preferentially as sacrifice layer), and the corrosion in microporous nickel is terminated.Under the effect of a large amount of discontinuous micro-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 corrosion rate, the corrosion rate delayed.
3rd step: to corrode in electronegative potential nickel further to downward-extension until basic coating (comprising the following coating of electronegative potential nickel) time, because the current potential of basic coating is higher than electronegative potential nickel equally, electronegative potential nickel has been regarded anodic coating equally, corrosion now to downward-extension is terminated at basic coating, corrosion position laterally carries out in electronegative 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 (premenstrua), and for follow-up electronegative 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 electronegative potential nickel dam that obtain, and have high Corrosion Protection, high rigidity, high-wearing feature, binding force of cladding material is good, brightness advantages of higher; Simultaneously there is the micropore nickel dam of high potential characteristic and there is the MULTI-LAYER NICKEL of electronegative potential characteristic---electronegative potential nickel dam is for functional layer, and with electronegative potential nickel dam for sacrifice layer, micro-electric current of electrochemical corrosion can be disperseed with the micropore nickel dam with microcellular structure, delay be corroded generation, formed simultaneously and can also form oxide support after oxidation by microcellular structure, after can being subject to comparatively serious corrosion at the electronegative potential nickel dam as sacrifice layer, it is formed and support, reduce part coating damage speed.The electronegative potential nickel dam as sacrifice layer arranged has lower electromotive force; when the generation electrochemical corrosion of piece surface coating; electronegative potential nickel dam preferentially corrodes; and when there is micropore nickel dam or micro-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 electronegative potential nickel dam, (during as decorative layer or protective layer) can also be supported outboard structure by micropore or micro-cracked structure, the steadiness of reinforcing material structure simultaneously.The present invention program utilizes the pore structure of microporous nickel and micro-crack nickel in addition, while reinforcing material 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 oxide etch simultaneously, thus greatly delays the generation of corrosion.
3, in addition, the present invention selects the plating solution little to ambient influnence 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 final products 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 of the embodiment of nickel plating of the present invention-chromium parts.
The nickel plating parts CASS of Fig. 2 prior art metallograph after 72 hours, in Fig. 2, (a) is the front metallograph of sample after experiment, and in Fig. 2, (b) be side (section) metallograph of experiment sample afterwards.
Fig. 3 nickel plating parts of the present invention CASS metallograph after 72 hours, in Fig. 3, (a) is the front metallograph of sample after experiment, and in Fig. 3, (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. 4 prior art.
The picture carried out after 168 and 336 hours tested by Fig. 5 nickel plating component corrosion of the present invention cream.
Fig. 6 list of the present invention electronegative potential nickel dam potential difference picture (electronegative potential nickel dam is the arbitrary of high-sulfur nickel dam or micro-crack nickel dam).
Fig. 7 compound electronegative potential of the present invention nickel dam potential difference picture (electronegative potential nickel dam is the composite bed of high-sulfur nickel dam and micro-crack nickel dam).
Fig. 8 MULTI-LAYER NICKEL corrosion principle of the present invention figure (taking ABS as part base material).
Reference numerals list:
1, base material; 2, pretreatment coating; 21, vacancy is corroded;
3, copper plate; 31, surface micropore; 32, etch pit;
4, functional layer; 141, electronegative potential nickel dam; 142, micropore nickel dam;
6, basal layer; 801, corrosive medium; 802, decorative layer;
805, erosional surface; 808, bottoming nickel dam; 809, electroless nickel layer;
810, ABS substrate.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, illustrate the present invention further, following detailed description of the invention should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
As shown in Figure 1, below the coating structure of nickel plating of the present invention-chromium parts 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
Nickel plating-chromium the parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment 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; With functional layer 4, it is formed on basal layer 6, and wherein functional layer 4 comprises electronegative potential nickel dam 141 and micropore nickel dam 142, and wherein electronegative potential nickel dam 141 is high-sulfur nickel dam, and micropore nickel dam 142 is formed on electronegative potential nickel dam 141; With decorative layer 802, it is formed on micropore nickel dam 142, and wherein decorative layer is the white layers of chrome of trivalent.
Constructive embodiment 2
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment 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; With functional layer 4, it is formed on basal layer 6, and wherein functional layer 4 comprises electronegative potential nickel dam 141 and micropore nickel dam 142, and wherein electronegative potential nickel dam 141 is micro-crack nickel dam, and micropore nickel dam 142 is formed on electronegative potential nickel dam 141; With decorative layer 802, it is formed on micropore nickel dam 142, and wherein decorative layer is the white layers of chrome of trivalent.
Constructive embodiment 3
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Basal layer 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; With functional layer 4, it is formed on basal layer 6, wherein functional layer 4 comprises electronegative potential nickel dam 141 and micropore nickel dam 142, and wherein for high-sulfur nickel dam and micro-crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, micro-crack nickel dam be formed on high-sulfur nickel dam electronegative potential nickel dam 141; Also can be that micro-crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on micro-crack nickel dam), micropore nickel dam 142 is formed on electronegative potential nickel dam 141; With decorative layer 802, it is formed on micropore nickel dam 142, and wherein decorative layer is the white layers of chrome of trivalent.
Unique difference of constructive embodiment 4-6 and constructive embodiment 1-3 is only: pretreatment 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 7-9 and constructive embodiment 1-3 is only: pretreatment 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 10-12 and constructive embodiment 1-3 is only: there is not pretreatment coating 2, directly on base material 1, is formed with copper plate 3.
Unique difference of constructive embodiment 13-24 and constructive embodiment 1-12 is only: decorative layer 802 is sexavalence layers of chrome.
Unique difference of constructive embodiment 25-36 and constructive embodiment 1-12 is only: decorative layer 802 is trivalent black chromium coating.
Unique difference of constructive embodiment 37-72 and constructive embodiment 1-36 is only: base material 1 is pp material.
Unique difference of constructive embodiment 73-108 and constructive embodiment 1-36 is only: base material 1 is nylon material;
Unique difference of constructive embodiment 109-144 and constructive embodiment 1-36 is only: base material 1 is pc material;
Unique difference of constructive embodiment 145-180 and constructive embodiment 1-36 is only: base material 1 is pet material;
Unique difference of constructive embodiment 181-216 and constructive embodiment 1-36 is only: base material 1 is bakelite material;
Unique difference of constructive embodiment 217-252 and constructive embodiment 1-36 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 cast iron and alloy cast iron etc.) material;
Unique difference of constructive embodiment 253-288 and constructive embodiment 1-36 is only: base material 1 is steel (comprising various ordinary steel, stainless steel etc.) and aluminum alloy material, magnesium alloy material;
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, chrome plating 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 pretreatment (pretreatment in turn includes the following steps: surperficial degrease, surface hydrophilic process, surface coarsening process, surperficial neutralisation treatment, preimpregnation, surface activation process, surperficial dispergation process); By pretreatment 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 pretreatment coating (bottoming nickel dam is outer); Be formed on copper plate with by basal layer, basal layer is here half light nickel dam, full light nickel dam and Sha Ding nickel dam, and half light nickel dam is formed on copper plate, and full light nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on full light nickel dam; Be formed on the full light nickel dam of basal layer with by the electronegative potential layer in functional layer, electronegative 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 decorative layer is formed on micropore nickel dam, decorative layer is here the white layers of chrome of trivalent.
Potential difference between micropore nickel dam from high-sulfur nickel dam (electronegative 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 electronegative potential nickel dam respectively, and the potential difference in each embodiment between micropore nickel dam with electronegative 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 surface of the work have high Corrosion Protection, high rigidity, high-wearing feature like this, binding force of cladding material is good, brightness advantages of higher.
On above-mentioned part, nickel electric plating method comprises the steps:
(1) surperficial degrease: by ABS substrate at NaOH NaOH, sodium carbonate Na
2cO
3, sodium metasilicate Na
2siO
3with cleaning treatment in the mixed solution of surfactant.In this step, in mixed solution, each component concentration proportioning is in different embodiments in table one.Surfactant is that conventional surfactants is as dodecyl sodium sulfate, sodium stearyl sulfonate etc.
Table one
(2) surface hydrophilic process: carry out in sulfuric acid and whole agent mixed solution.In this step, sulfuric acid and whole agent concentration proportioning is in different embodiments in table two:
Table two
(3) surface coarsening process: carry out in chromic anhybride CrO3 and sulfuric acid H2SO4 mixed liquor after degrease.In this step, chromic anhybride CrO3 and sulfuric acid H2SO4 concentration proportioning are in different embodiments in table three:
Table three
(4) surperficial neutralisation treatment: the mixed solution 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 neutralisation treatment carries out in hydrochloric acid solution, in this step, hydrochloric acid solution at the concentration proportioning of different embodiment in table five:
Table five
(6) surface activation process: adopt colloid palladium solution to carry out surface activation process, hydrochloric acid, palladium bichloride PdCl in colloid palladium solution after neutralization
2with stannous chloride 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 sulfuric acid solution at the concentration proportioning of different embodiment in table seven:
Table seven
(8) electroless nickel layer is plated: containing nickelous sulfate, inferior sodium phosphate, natrium citricum C
6h
5na
3o
7, ammonium chloride and ammoniacal liquor (ammoniacal liquor is used for regulating the pH of solution to be 8.6-9.2) mixed solution in carry out.In this step, in mixed solution, 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 nickel chloride NiCl
2-6H
2o, boric acid H
3bO
3carry out with in the mixed solution of wetting agent.In this step, in mixed solution, 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 NIMAC 32C WETTER of wheat dolantin.
Table nine
(10) copper plate: at copper sulphate CuSO
4, sulfuric acid H
2sO
4, chlorion, leveling agent, walk agent and open cylinder agent mixed solution in carry out.In this step, in mixed solution 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 nickel chloride NiCl
2-6H
2o and boric acid H
3bO
3, the elementary brightener of semi-bright nickel, semi-bright nickel second-class brightener, potential difference adjusting agent and wetting agent mixed solution in carry out.In this step, in mixed solution 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 NIMAC 32C WETTER of wheat dolantin, the elementary brightener 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) full light nickel dam is plated: at aqueous sulfuric acid nickel
2sO
4-6H
2o, moisture nickel chloride NiCl
2-6H
2o, boric acid H
3bO
3, bright nickel softening agent, the agent of bright nickel key light and wetting agent mixed solution in carry out.In this step, in mixed solution each component at the concentration proportioning of different embodiment respectively in table ten two.Here wetting agent is the NIMAC 32C WETTER as the happy 62A that thinks or wheat dolantin, and bright nickel softening agent is the NIMAC 14INDEX 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 ten two
(13) husky fourth nickel dam is plated: carry out in the mixed solution of aqueous sulfuric acid nickel, moisture nickel chloride, boric acid, auxiliary additive and Sha Ding nickel forming agent.In this step, in mixed solution each component at the concentration proportioning of different embodiment respectively in table ten three.Here auxiliary 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 (electronegative potential layer) is plated: carry out in the mixed solution of aqueous sulfuric acid nickel, moisture nickel chloride, boric acid, high sulfur additives and wetting agent.In this step, in mixed solution 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 NIMAC 32C WETTER of wheat dolantin.
Table ten four
(15) micropore nickel dam is plated: seal in the mixed solution of particulate vector at aqueous sulfuric acid nickel, moisture nickel chloride, boric acid, nickel envelope brightener, nickel envelope key light agent and nickel and carry out.In this step, in mixed solution each component at the concentration proportioning of different embodiment respectively in table ten five.Here nickel envelope brightener 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 (decorative layer) is plated: carry out in the mixed solution of moisture chromium chloride, potassium formate, ammonium bromide, ammonium chloride, potassium chloride, sodium acetate, boric acid, wetting agent.In this step, in mixed solution, 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 NIMAC 32C 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 electronegative potential nickel dam is fine fisssure lamina.Plating micro-crack nickel dam carries out in the mixed solution of moisture nickel chloride, acetic acid, PN-1A, PN-2A, wetting agent.In this step, in mixed solution, 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 NIMAC 32C WETTER of wheat dolantin.
Table ten seven
Preparation embodiment 11-15 is only with unique difference of preparation embodiment 1-5, electronegative potential nickel dam include high-sulfur nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten four), micro-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 decorative layer is sexavalence layers of chrome.Plating sexavalence layers of chrome is carried out in the mixed solution of chromic anhydride, sulfuric acid, decorative chromium brightener and chromium fog inhibitor.In this step, in mixed solution, each component concentration proportioning is in different embodiments in table ten eight.Here decorative chromium brightener 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 decorative layer is trivalent black chromium coating.Plating trivalent black chromium coating carries out in the mixed solution of moisture chromium chloride, oxalic acid, ammonium acetate, ammonium chloride, boric acid and additive.In this step, in mixed solution, 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), high-sulfur nickel dam and the Sha Ding 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.Plating high-sulfur nickel dam carries out in the mixed solution of aqueous sulfuric acid nickel, moisture nickel chloride, boric acid, high sulfur additives and wetting agent.In this step, in mixed solution each component at the concentration proportioning of different embodiment respectively in table two ten.Here wetting agent is as the happy 62A of think of or the NIMAC 32C WETTER of 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 full light nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten two) 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) 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 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), high-sulfur layer (each embodiment plating solution is accordingly in turn see shown in table two ten) and the full light nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten two) that are outwards formed in turn by copper plate surface.
Preparation embodiment 226-450 is only with unique difference of preparation embodiment 1-225, and nickel envelope brightener is the NIMAC 14INDEX of wheat dolantin; The agent of nickel envelope key light is the NIMAC 33 of wheat dolantin; Nickel envelope particulate vector is the NiMac Hypore XL dispersant 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 NIMAC 32C WETTER of wheat dolantin.
Preparation embodiment 1351-2700 is only with unique difference of preparation embodiment 1-1350, and pretreatment 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 pretreatment 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 pretreatment 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, pretreatment coating can carry out selection according to the performance of actual material and process requirements has pretreatment coating or without pretreatment coating.
As the etch state figure that Fig. 3 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. 2 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. 3 then can find out, then only there is the surface micropore 31 of some on surface in the nickel plating sample that the present invention obtains, then equally only there is less etch pit 32 in section display, be the coating structure that etch pit 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. 4 and Fig. 5 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 corrosion resistance, make nickel plating parts more durable, attractive in appearance.
As can be seen from Fig. 6 and Fig. 7 coating potential diagram then, in the present invention program, no matter electronegative potential layer is simple layer or lamination layer structure, to be when being corroded with electronegative potential nickel dam as sacrifice layer, when electronegative potential nickel dam is the composite bed of high-sulfur nickel dam and micro-crack nickel dam, the height of the current potential of high-sulfur nickel dam and micro-crack nickel dam regulates with actual production technique, can be that high-sulfur nickel dam electromotive force is slightly high, also can be that micro-crack nickel dam electromotive force is slightly high.
As shown in Figure 8, 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, electronegative potential nickel dam 141, micropore nickel dam 142 and decorative layer 802 in ABS substrate 810 layer by layer in figure.Corrosive medium 801 disperses corrosion current and enters electronegative potential nickel dam 141 (to reduce the area of actual participation corrosion in the microcellular structure of micropore nickel dam 142, there is less corroded area, form multiple independently hot spot, thus dispersion corrosion current, delay corrosion rate), after corrosion forms erosional surface 805, after erosional surface 805 runs through electronegative 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 electronegative potential nickel dam 141, just can carry out next step corrosion, until coating structure is destroyed by entirety.
The non-limit part of technical scope midrange that this place embodiment is protected application claims, equally all in the scope of protection of present invention.
Technological means disclosed in the present invention program is not limited only to the technological means disclosed in above-mentioned technological means, also comprises the technical scheme be made up of above technical characteristic.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 (16)
1. nickel plating-chromium parts, these parts comprise:
Base material;
Pretreatment coating, its deposition over the whole substrate, pretreatment 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 electronegative potential nickel dam and is formed at the micropore nickel dam on electronegative potential nickel dam; With
Decorative layer, it is formed on micropore nickel dam, and described decorative layer is the arbitrary of trivalent chromium coating or Cr VI coating.
2. nickel plating according to claim 1-chromium parts, is characterized in that: described decorative layer is trivalent chromium coating, and described trivalent chromium coating is the white chrome plating of trivalent or trivalent black chromium plating.
3. nickel plating according to claim 1-chromium parts, is characterized in that: the potential difference between described micropore nickel dam and electronegative potential nickel dam is within the scope of 10-120mv.
4. the nickel plating according to claim 1 or 3-chromium parts, is characterized in that: described electronegative potential nickel dam include one deck in high-sulfur nickel dam, micro-crack nickel dam or two-layer between compound.
5. the nickel plating according to claim 1 or 3-chromium parts, is characterized in that: the potential difference between described micropore nickel dam and electronegative potential nickel dam is within the scope of 20-100mv.
6. nickel plating according to claim 4-chromium parts, is characterized in that: the potential difference between described micropore nickel dam and electronegative potential nickel dam is within the scope of 20-100mv.
7. nickel plating according to claim 4-chromium parts, is characterized in that: when described electronegative potential nickel dam employing micro-crack and high-sulfur nickel composite deposite, between micro-crack nickel and high-sulfur nickel, potential difference is in 10-80mv.
8. the manufacture method of nickel plating-chromium parts, the method comprises the steps:
Pretreatment is carried out on the surface of base material;
Pretreatment coating is deposited over the whole substrate, and copper plate is formed on pretreatment coating; With
Basal layer is formed on copper plate; With
Electronegative potential nickel dam in functional layer is formed on basal layer; With
Micropore nickel dam in functional layer is formed on electronegative potential nickel dam; Potential difference between described micropore nickel dam and electronegative potential nickel dam is within the scope of 10-120mv; With
Be formed at by decorative layer on micropore nickel dam, described decorative layer is the arbitrary of trivalent chromium coating or Cr VI coating.
9. the manufacture method of nickel plating according to claim 8-chromium parts, is characterized in that: described decorative layer is trivalent chromium coating, and described trivalent chromium coating is the white chrome plating of trivalent or trivalent black chromium plating.
10. the manufacture method of nickel plating according to claim 8-chromium parts, is characterized in that: described electronegative potential nickel dam include one deck in high-sulfur nickel dam, micro-crack nickel dam or two-layer between compound.
The manufacture method of 11. nickel plating according to claim 8-chromium parts, it is characterized in that: described micropore nickel dam adopts the plating of plating microporous nickel plating solution to form, described plating microporous nickel plating solution comprises composition and concentration is (in unit volume plating solution addition): aqueous sulfuric acid nickel 300-350g/L, moisture nickel chloride 50-60g/L, boric acid 40-50g/L, nickel envelope brightener 6-12ml/L, nickel envelope key light agent 4-7.5ml/L, nickel envelope particle 0.2-1.5g/L, nickel envelope particle dispersants 0.5-3ml/L, wetting agent 1-5ml/L.
The manufacture method of 12. nickel plating according to claim 9-chromium parts, it is characterized in that: described decorative layer is the white chrome plating of trivalent, the white chrome plating of described trivalent adopts the white chromium plating solution plating of plating trivalent to form, and described trivalent white chromium plating solution comprises composition and concentration is: moisture chromium chloride 90-150g/L, potassium formate 50-100g/L, ammonium bromide 8-25g/L, ammonium chloride 40-60g/L, potassium chloride 40-100g/L, sodium acetate 10-60g/L, boric acid 40-80g/L, wetting agent 0.5-2.5ml/L.
The manufacture method of 13. nickel plating according to claim 9-chromium parts, it is characterized in that: described decorative layer is trivalent black chromium plating, described trivalent black chromium plating adopts the black chromium plating solution plating of plating trivalent to form, described trivalent black chromium plating solution comprises composition and concentration is: moisture chromium chloride 150-250g/L, oxalic acid 2-5g/L, ammonium acetate 3-10g/L, ammonium chloride 20-40g/L, boric acid 20-41g/L, additive 0.5-3g/L.
The manufacture method of 14. nickel plating according to claim 8-chromium parts, it is characterized in that: described decorative layer is Cr VI coating, described Cr VI coating adopts the plating of plating Cr VI plating solution to form, described Cr VI plating solution comprises composition and concentration is: chromic anhydride 260-360g/L, sulfuric acid 0.5-3g/L, decorative chromium brightener 1-4g/L, chromium fog inhibitor 0.1-0.4ml/L.
The manufacture method of 15. nickel plating according to claim 10-chromium parts, it is characterized in that: described micro-crack nickel dam adopts the plating of plating micro-crack nickel plating solution to form, described plating micro-crack nickel plating solution comprises composition and concentration is: moisture nickel chloride: 180-260g/L, acetic acid: 10-40ml/L, PN-1A:40-90g/L, PN-2A:1-5ml/L, wetting agent: 1-5ml/L.
16. the manufacture method of nickel plating according to claim 10-chromium parts, it is characterized in that: described high-sulfur nickel dam adopts the plating of plating high-sulfur nickel plating bath to form, described plating high-sulfur nickel plating bath comprises composition and concentration is: aqueous sulfuric acid nickel 250-350g/L, moisture nickel chloride 35-60g/L, boric acid 35-65g/L, high sulfur additives 3-10ml/L, wetting agent 0.5-3ml/L.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104775143A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Multilayer ultra corrosion resistant nickel-chromium plating part and manufacturing method thereof |
| CN105696041A (en) * | 2016-04-08 | 2016-06-22 | 苏州市美能五金镀饰有限公司 | Hardware chromium plating technology |
| CN106521591A (en) * | 2016-11-10 | 2017-03-22 | 无锡市明盛强力风机有限公司 | Nickel plating method for plastic for automobiles |
| CN107313101A (en) * | 2017-06-08 | 2017-11-03 | 华南理工大学 | A kind of preparation method of environmentally friendly nickel envelope chromium-free deactivation layer |
| CN108425917A (en) * | 2018-03-30 | 2018-08-21 | 芜湖强振汽车紧固件有限公司 | A kind of automobile-used fastener constructions improving antiseptic property |
| CN110219028A (en) * | 2019-06-27 | 2019-09-10 | 九牧厨卫股份有限公司 | A kind of high blackness dumb light metal black composite deposite and preparation method thereof |
| CN111020647A (en) * | 2019-12-20 | 2020-04-17 | 常州极太汽车配件有限公司 | Composition for surface treatment of aluminum flexible connection |
| CN111910230A (en) * | 2020-07-15 | 2020-11-10 | 九牧厨卫股份有限公司 | Antibacterial black chromium surface coating and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171468A (en) * | 1991-12-16 | 1993-07-09 | Ebara Yuujiraito Kk | Nickel-chromium-plated product |
| EP1167584A1 (en) * | 2000-06-29 | 2002-01-02 | Lacks Enterprises, Inc. | Decorative chrome electroplate on plastics |
| JP2007039772A (en) * | 2005-08-05 | 2007-02-15 | Kakihara Kogyo Kk | Method for forming copper-free plated film on resin |
| 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 |
| CN104775143A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Multilayer ultra corrosion resistant nickel-chromium plating part and manufacturing method thereof |
| CN204640958U (en) * | 2015-03-11 | 2015-09-16 | 嘉兴敏惠汽车零部件有限公司 | Nickel plating-chromium parts |
-
2015
- 2015-03-11 CN CN201510105136.3A patent/CN104772946B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05171468A (en) * | 1991-12-16 | 1993-07-09 | Ebara Yuujiraito Kk | Nickel-chromium-plated product |
| EP1167584A1 (en) * | 2000-06-29 | 2002-01-02 | Lacks Enterprises, Inc. | Decorative chrome electroplate on plastics |
| JP2007039772A (en) * | 2005-08-05 | 2007-02-15 | Kakihara Kogyo Kk | Method for forming copper-free plated film on resin |
| 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 |
| CN104775143A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Multilayer ultra corrosion resistant nickel-chromium plating part and manufacturing method thereof |
| CN204640958U (en) * | 2015-03-11 | 2015-09-16 | 嘉兴敏惠汽车零部件有限公司 | Nickel plating-chromium parts |
Cited By (11)
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| CN104775143A (en) * | 2015-03-11 | 2015-07-15 | 嘉兴敏惠汽车零部件有限公司 | Multilayer ultra corrosion resistant nickel-chromium plating part and manufacturing method thereof |
| CN105696041A (en) * | 2016-04-08 | 2016-06-22 | 苏州市美能五金镀饰有限公司 | Hardware chromium plating technology |
| CN106521591A (en) * | 2016-11-10 | 2017-03-22 | 无锡市明盛强力风机有限公司 | Nickel plating method for plastic for automobiles |
| CN107313101A (en) * | 2017-06-08 | 2017-11-03 | 华南理工大学 | A kind of preparation method of environmentally friendly nickel envelope chromium-free deactivation layer |
| CN107313101B (en) * | 2017-06-08 | 2019-06-18 | 华南理工大学 | A kind of preparation method of environmentally friendly nickel envelope-chromium-free deactivation layer |
| CN108425917A (en) * | 2018-03-30 | 2018-08-21 | 芜湖强振汽车紧固件有限公司 | A kind of automobile-used fastener constructions improving antiseptic property |
| CN110219028A (en) * | 2019-06-27 | 2019-09-10 | 九牧厨卫股份有限公司 | A kind of high blackness dumb light metal black composite deposite and preparation method thereof |
| CN110219028B (en) * | 2019-06-27 | 2021-06-25 | 九牧厨卫股份有限公司 | High-blackness matte metal black composite coating and preparation method thereof |
| CN111020647A (en) * | 2019-12-20 | 2020-04-17 | 常州极太汽车配件有限公司 | Composition for surface treatment of aluminum flexible connection |
| CN111910230A (en) * | 2020-07-15 | 2020-11-10 | 九牧厨卫股份有限公司 | Antibacterial black chromium surface coating and preparation method thereof |
| CN111910230B (en) * | 2020-07-15 | 2021-08-06 | 九牧厨卫股份有限公司 | Antibacterial black chromium surface coating and preparation method thereof |
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