CN204585986U - Nickel plating-chromium parts - Google Patents
Nickel plating-chromium parts Download PDFInfo
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- CN204585986U CN204585986U CN201520136337.5U CN201520136337U CN204585986U CN 204585986 U CN204585986 U CN 204585986U CN 201520136337 U CN201520136337 U CN 201520136337U CN 204585986 U CN204585986 U CN 204585986U
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Abstract
Nickel plating disclosed in the utility model-chromium parts, wherein nickel plating-chromium parts comprise base material; Pretreatment coating, over the whole substrate, pretreatment coating is formed copper plate and functional layer, and it is formed on copper plate its deposition, and wherein functional layer comprises electronegative potential nickel dam and is formed at the micropore nickel dam on electronegative potential nickel dam; And decorative layer, it is formed on micropore nickel dam.The utility model is by the micropore, chrome-plated process basis of parts surface setting, increase electronegative potential nickel coating, thus improve the decay resistance of product, the especially decay resistance of trivalent chromium chrome plating product, can impel that the trivalent chromium product of more environmental protection is more massive to be applicable.
Description
Technical field
The utility model relates to a kind of workpiece and the electroplating technology thereof with electroplating surface Rotating fields, particularly nickel plating-chromium parts.
In the application, electrical potential difference is the difference of the standard electrode potential integrally recorded separately with adjacent two layers.
Background technology
More and more tighter to environmental requirement of European market, and each automobile factory is more and more higher to the corrosion proof requirement of plating, the corrosion that current 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 corrosive medium, just corrosion cell is formed with nickel dam, cause the corrosion of nickel dam, excessive corrosion is there will be in extreme environment, the large area of surperficial layers of chrome is caused to come off, affect the quality of product.In order to improve the antiseptic power of coating further, microporous nickel and micro-crack nickel are applied on light nickel coating, its effect is by different plating technologies, product surface is impelled to produce a large amount of micro-cracks or micropore, form a large amount of small etching channels, thus hot spot is divided into the point that naked eyes can not identify, reduce coming off of layers of chrome, to reach the exterior quality improved in use procedure.Owing to being used alone microporous nickel or micro-crack nickel, be limited to corrosion proof raising; And micro-crack coordinates with trivalent chromium, there is the problems such as appearance poor, cause the product for high corrosion resistant requirement to there is unworthiness.Simultaneously in part prior art, disclose and change microporous nickel technique to reach noble potential characteristic, thus meet the requirement of trivalent chromium decay resistance, but this this technology cannot realize and Cr VI, trivalent chromium mixed production, and two kinds of parts all meet the corrosion-resistant requirement of high-quality.
In prior art, as Chinese patent application (publication number: CN 101988211 A) relates to a kind of metal surface multiple layer nickel plating technique with superior antiseptic property, electroplating technology flow process is: 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, I. wash, 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.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, do not refer to trivalent chromium plating, enter checking simultaneously and there is poor corrosion resistance, outward appearance such as not to meet at the phenomenon.
Utility model content
For solving the problem, the utility model 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 in the utility model-chromium parts, these parts comprise:
Base material; Here the utility model base material can adopt metal, plastics and other can be suitable for the parts of plating.
(pretreatment coating can comprise the arbitrary or two-layer compound in electroless nickel layer or bottoming nickel dam to pretreatment coating, on base material, there is not this layer yet, concrete selection is depending on the material of base material, when electroless nickel layer and bottoming nickel dam exist simultaneously, then electroless nickel layer is formed on base material, bottoming nickel dam is formed in electroless nickel layer), its deposition over the whole substrate, pretreatment coating is formed with copper plate; With
Functional layer, it is formed on copper plate, 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.
The one of nickel plating disclosed in the utility model-chromium parts is improved, and decorative layer is the arbitrary of trivalent chromium coating or Cr VI coating, and wherein trivalent chromium coating can be the trivalent chromium coating of the white chrome plating of trivalent or trivalent black chromium plating or other kind.Wherein trivalent chromium coating can also form passivating film.
The one of nickel plating disclosed in the utility model-chromium parts is improved, and the potential difference of micropore nickel dam and electronegative potential nickel dam is 10-120mV.
The one of nickel plating disclosed in the utility model-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.Preferred further, the potential difference between micropore nickel dam and electronegative potential nickel dam is 20-00mV.
When electronegative potential nickel dam adopts the composite deposite of micro-crack nickel dam and high-sulfur nickel dam, between micro-crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mV.Here when corroding arrival electronegative potential nickel dam, because the current potential of micro-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 micro-crack nickel dam, thus improves corrosion-resistant degree further.
The manufacture method of nickel plating disclosed in the utility model-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
Electronegative potential nickel dam in functional layer is formed on copper plate; With
Micropore nickel dam in functional layer is formed on electronegative potential nickel dam; Potential difference between micropore nickel dam and electronegative potential nickel dam is within the scope of 10-120mV;
Decorative layer is formed on micropore nickel dam.Potential difference controlled, within the scope of this, in electroplating process, not easily to occur bubbling, coating structure is more stable firmly simultaneously, separation not easily occurs and peels off.Here electronegative potential nickel dam coordinate with copper plate for by electronegative potential nickel dam Direct Electroplating on copper plate, centre undopes other coating.
The one of the manufacture method of nickel plating disclosed in the utility model-chromium parts is improved, decorative layer is the arbitrary of trivalent chromium coating or Cr VI coating, and wherein trivalent chromium coating can be 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 in the utility model-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.
The one of the manufacture method of nickel plating disclosed in the utility model-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.
The one of the manufacture method of nickel plating disclosed in the utility model-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.
First aspect of the present utility model provides nickel plating parts, and it comprises following: base material; Pretreatment coating (can comprise electroless nickel layer, bottoming nickel dam arbitrary or the two compound), it is formed on whole base material; Copper plate, copper plate is formed on pretreatment coating; Functional layer, it is formed on copper plate, and wherein functional layer comprises electronegative potential nickel dam and is formed at the micropore nickel dam on electronegative potential nickel dam, is formed on copper plate by the electronegative potential nickel dam in functional layer; With the micropore nickel dam in functional layer is formed on electronegative potential nickel dam; Potential difference wherein between micropore nickel dam and electronegative potential nickel dam is within the scope of 10-120mV; With decorative layer (the white chrome plating of trivalent or trivalent black chromium plating or Cr VI coating arbitrary), it is formed on microporous nickel coating, and has the one of at least any of microcellular structure and micro-cracked structure.
Electronegative potential nickel dam has two kinds of modes when coordinating with copper plate, one be by electronegative potential nickel dam Direct Electroplating on copper plate, centre undopes other coating, another kind of mode is plated on copper plate by electronegative potential nickel dam Indirect Electro, that is other coating can also be electroplated between electronegative potential nickel dam and copper plate, totally be referred to as basic coating, basic coating can electroplate the corresponding coating such as full light nickel, half light nickel, husky fourth nickel or high-sulfur nickel here.
Second aspect of the present utility model provides the manufacture method of nickel plating-chromium parts, and it comprises the following 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 the electronegative potential nickel dam in functional layer is formed on copper plate; With the 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; Decorative layer is formed on micropore nickel dam.
The one of the manufacture method of nickel plating disclosed in the utility model-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 in the utility model-chromium parts is improved, in aforementioned plating micropore nickel dam operation, micropore nickel dam adopts the plating of plating microporous nickel plating solution to form, plating microporous nickel plating solution comprises composition and concentration is: 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 14 INDEX as happy 63 and the wheat dolantin thought), nickel envelope key light agent 4-7.5ml/L (610CFC thought as happy and the NIMAC 33 of wheat dolantin), nickel envelope particle 0.2-1.5g/L (ENHANCER thought as happy and the NiMac Hypore XL dispersant of wheat dolantin), nickel envelope particle dispersants 0.5-3ml/L, wetting agent 1-5ml/L.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, microporous nickel layer thickness is not less than 1.5 microns.
The one of the manufacture method of nickel plating disclosed in the utility model-chromium parts is improved, in plating micro-crack nickel dam operation in aforementioned plating electronegative potential nickel dam operation, 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 20 ~ 60ml/L, PN-1A 40 ~ 90g/L, PN-2A 1 ~ 5ml/L, wetting agent 1 ~ 5ml/L.Wetting agent is as the happy 62A of think of and the NIMAC 32C WETTER of wheat dolantin.When micro-crack nickel dam is coated with, technological temperature controls between 25 ~ 35 DEG C, pH is to controlling between 3.6 ~ 4.6, current density is 5 ~ 9ASD, operating time controls between 2 ~ 8min, make nickel be deposited on plated item on the surface by the mode of direct current electrolysis, micro-crack nickel layer thickness is not less than 1.0 microns.
The one of the manufacture method of nickel plating disclosed in the utility model-chromium parts is improved, in plating high-sulfur nickel dam operation in aforementioned plating electronegative potential nickel dam operation, 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.Wetting agent is as the happy 62A of think of and 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, and current density is 2 ~ 6ASD, and the operating time controls between 2 ~ 8min, make nickel be deposited on plated item on the surface 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 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-metallic substrate pretreatment process in early stage is specially and base material blank is cleaned degrease in NaOH, sodium carbonate 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, and the concentration of sodium metasilicate is 10-40g/L, surfactant 1-3g/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.
Here chromic anhybride is the main salt in plating solution, crome metal and production chrome green hyrate etc. is deposited at substrate surface by the mechanism of oxidation-reduction reaction and electron exchange, coating is turned black, the covering power of chromic anhybride to plating solution has considerable influence, if chromic anhybride content is high, then covering power is strong, crystallization is careful, if but chromic anhybride too high levels, the hardness of coating then can be made to decline, in addition, chromic anhybride and sulfuric acid can at corrosion substrate surface to form micro-roughened surface at substrate surface as corrosive agent, " snap close effect " required during to guarantee chemical plating, the adhesion of substrate surface and coating is improved with this.But sulfate radical can reduce the color characteristics of coating, coating is turned to be yellow, in order to can reach corrosion substrate surface and reduce adverse effect simultaneously, need the content of accurately configuration sulfuric acid.
As preferably, in surface and the concentration of hydrochloric acid solution of operation be 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: the concentration of palladium bichloride is the concentration 1-6g/L of 20-60ppm, stannous chloride, hydrochloric acid 180-280ml/L.
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.
As preferably, the electroless nickel layer plating solution of electroless nickel layer operation comprises composition and concentration is: the concentration of nickelous sulfate is 15-40g/L, and the concentration of sodium hypophosphite is 20-50g/L, the concentration of natrium citricum is 10-4g/L, ammonium chloride 10-50g/L, ammoniacal liquor, PH regulates use, PH=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, in the utility model, adopts natrium citricum as buffer.
As preferably, the bottoming nickel plating bath of plating bottoming nickel operation comprises composition and concentration is: the concentration of aqueous sulfuric acid nickel is 180-280g/L, and the concentration of moisture nickel chloride is 35-60g/L, and the concentration of boric acid is 35-60g/L, wetting agent 1-3ml/L.
When electroless nickel layer and bottoming nickel dam exist on matrix simultaneously, matrix in chemical sinking nickel, after making 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.
As preferably, in the copper plate plating solution of copper plate operation, each component and concentration are: the concentration of copper sulphate is 160-260g/L, and the concentration of sulfuric acid is 50-100g/L, chlorion is 40-100ppm, leveling agent 0.2-1ml/L, walk agent 0.2-1ml/L, open cylinder agent 2-10ml/L.
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.
Plating micro-crack nickel refer to substrate surface plate one deck all and the coating containing numerous crackle, corrosion current can 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 substrate surface, corrosion current can be disperseed further, reduce corrosion electric current density, improve coating corrosion stability comprehensively.
In chemical sinking nickel and plating bottoming nickel step, nickel preplating coating mainly helps out, and boric acid can not only play stabilizer function or the main blackening agent for surface of plating solution therebetween, can improve covering power and the covering power of plating solution, improve compactness of electroplating.
Wherein when electronegative potential nickel dam adopt independent micro-crack nickel dam or for high-sulfur nickel dam and micro-crack nickel dam composition compound nickel dam; the anticorrosion effect that the utility model reaches best can be made; here 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; on workpiece, coated metal/substrate 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) surface substrate 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 removes corrosive medium, because decorative layer (such as layers of chrome) exists the passivation layer of highly corrosion resistant, the micropore on layers of chrome surface exists, the nickel dam of corrosion at micropore place is guided to launch, due to the discontinuity of micropore, cause when corroding total amount and being constant, corrosion is separated into numerous regions, therefore corrodes and carries out not affecting under apparent condition.。
Second step: when corroding arrival electronegative potential nickel dam, because microporous nickel current potential is higher than electronegative potential nickel current potential, now electronegative potential nickel is preferentially corroded as anodic coating (namely electronegative potential nickel dam is preferentially as sacrifice layer), and the corrosion in microporous nickel is terminated.Under the effect of a large amount of discontinuous micro-crack, guide corrosion in crackle depth and laterally launch simultaneously; the nickel dam area corroded will increase and discontinuous greatly; when corrosion current is certain; these " micropores " have disperseed corrosion current greatly; again reduce single-point corrosion rate; the corrosion rate delayed, protect the layers of chrome in appearance and adhesion layer micropore nickel dam thereof, product surface corrosion resistance improves further simultaneously.
3rd step: when to corrode in electronegative potential nickel dam further to downward-extension, because below electronegative potential nickel dam, the current potential of coating (as copper plate) is higher than electronegative potential nickel equally, electronegative potential nickel has been regarded anodic coating equally, corrosion now to downward-extension is terminated, corrosion position laterally carries out in electronegative potential nickel, delay so again the time of corroding to base material further, greatly fall at the end speed of corrosion.
Compared with prior art, the utility model has the advantage of:
1, the utility model is by after base material workpiece pretreatment process premenstruum (premenstrua), for follow-up electronegative potential nickel dam and the plating of micropore nickel dam lay the first stone, and process stabilizing, compatibility is reasonable;
2, the utility model substrate surface 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 utility model scheme 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 utility model 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 the utility model gained have the higher market competitiveness.
Accompanying drawing explanation
Fig. 1 is the coating structure schematic diagram of the embodiment of the utility model nickel plating-chromium parts.
Fig. 2 the utility model list 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. 3 the utility model compound electronegative potential nickel dam potential difference picture (electronegative potential nickel dam is the composite bed of high-sulfur nickel dam and micro-crack nickel dam).
Fig. 4 MULTI-LAYER NICKEL corrosion principle of the present utility model figure (taking ABS as part base material).
Reference numerals list:
1, base material; 2, pretreatment coating;
4, functional layer; 141, electronegative potential nickel dam; 142, micropore nickel dam;
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 utility model further, following detailed description of the invention should be understood and be only not used in restriction scope of the present utility model for illustration of the utility model, here the utility model base material can adopt metal, plastics and other can be suitable for the parts of plating.
As shown in Figure 1, below the coating structure of the utility model nickel plating-chromium parts is described.
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 heavy 809 is amassed 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 functional layer 4, it is formed on copper plate 3, 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, is formed at the micropore nickel dam 142 on high-sulfur nickel dam; With the decorative layer 802 (the white chrome plating of trivalent) be formed on micropore nickel dam 142.
Constructive embodiment 2
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 heavy 809 is amassed 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 functional layer 4, it is formed on copper plate 3, 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, is formed at the micropore nickel dam 142 on micro-crack nickel dam; With the decorative layer 802 (trivalent black chromium plating) be formed on micropore nickel dam 142.
Constructive embodiment 3
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 heavy 809 is amassed 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 functional layer 4, it is formed on copper plate 3, 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), be formed at the micropore nickel dam 142 on electronegative potential nickel dam 141; With the decorative layer 802 (Cr VI coating) be formed on micropore nickel dam 142.
Constructive embodiment 4
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 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; With functional layer 4, it is formed on copper plate 3, 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, is formed at the micropore nickel dam 142 on high-sulfur nickel dam; With the decorative layer 802 (Cr VI coating) be formed on micropore nickel dam 142.
Constructive embodiment 5
Nickel plating-chromium the parts of the present embodiment, these parts comprise: base material 1 (ABS material); 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; With functional layer 4, it is formed on copper plate 3, 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, is formed at the micropore nickel dam 142 on micro-crack nickel dam; With the decorative layer 802 (the white chrome plating of trivalent) be formed on micropore nickel dam 142.
Constructive embodiment 6
Nickel plating-chromium the parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment coating 2 comprises copper plate 3, directly on base material 1, is formed with copper plate 3; With functional layer 4, it is formed on copper plate 3, 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), be formed at the micropore nickel dam 142 in functional layer 4; With the decorative layer 802 (trivalent black chromium plating) be formed on micropore nickel dam 142.
Unique difference of constructive embodiment 7-12 and constructive embodiment 1-6 is only: base material 1 is pp material;
Unique difference of constructive embodiment 13-18 and constructive embodiment 1-6 is only: base material 1 is nylon nylon material;
Unique difference of constructive embodiment 19-24 and constructive embodiment 1-6 is only: base material 1 is pc material;
Unique difference of constructive embodiment 25-30 and constructive embodiment 1-6 is only: base material 1 is pet material;
Unique difference of constructive embodiment 31-36 and constructive embodiment 1-6 is only: base material 1 is bakelite material;
Unique difference of constructive embodiment 37-42 and constructive embodiment 1-6 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 43-48 and constructive embodiment 1-6 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 solutions of the utility model can also may be used for being coated with on its surface the material of copper, nickel, chrome plating for other.
In the utility model embodiment, 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-chromium parts of a kind of embodiment of the utility model 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); Pretreatment coating (is comprised chemical sinking nickel and bottoming nickel, the selection that whether pretreatment coating retains and pretreatment coating forms in addition is selected flexibly according to base material material and handicraft product demand) deposition is 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); With the electronegative potential nickel dam in functional layer is formed on copper plate, 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, wherein decorative layer is the white chrome plating 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, electric plating method comprises the steps:
(1) surperficial degrease: at NaOH NaOH, sodium carbonate Na
2cO
3, sodium metasilicate Na
2siO
3with cleaning treatment in surfactant mixed solution.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: at chromic anhybride CrO
3with sulfuric acid H
2sO
4carry out in mixed liquor.In this step, chromic anhybride CrO
3with sulfuric acid H
2sO
4concentration proportioning is in different embodiments in table three:
Table three
(4) surperficial neutralisation treatment: the base material after surface coarsening process is put into hydrochloric acid and hydrazine hydrate mixed solution carries out.In this step, hydrochloric acid and hydrazine hydrate solution 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: surface activation process adopts colloid palladium solution, colloid palladium Chlorine in Solution palladium PdCl
2, stannous chloride SnCl
2with hydrochloric acid at 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) chemical sinking nickel: containing hydration nickel sulfate, hydration sodium hypophosphite, natrium citricum C
6h
5na
3o
7, carry out in ammonium chloride and ammoniacal liquor (ammoniacal liquor is used for regulating the PH of solution to be 8.6-9.2) mixed solution.In this step, in mixed solution, each component concentration proportioning is in different embodiments in table eight:
Table eight
(9) bottoming nickel is plated: containing aqueous sulfuric acid nickel
2sO
4-6H
2o, moisture nickel chloride NiCl
2-6H
2o, boric acid H
3bO
3and carry out 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 and 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, to carry out in walk agent and open cylinder agent mixed solution.Solution respectively forms concentration proportioning in different embodiment in table ten: wherein leveling agent, the agent that walks, open cylinder agent can select the happy 1560 sour copper additives series thought.
Table ten
(11) high-sulfur nickel dam (electronegative potential nickel dam), plating micropore nickel dam is plated successively.Wherein plate in the processing step of microporous nickel, high-sulfur nickel, the main component of plating solution is the same, is aqueous sulfuric acid nickel
2sO
4-6H
2o, moisture nickel chloride NiCl
2-6H
2o and boric acid H
3bO
3mixed solution.Plate microporous nickel and plate the concentration proportioning of high-sulfur in different embodiment respectively in table ten one and table ten two, nickel envelope brightener is 63 of happy think of here; The agent of nickel envelope key light is the happy 610CFC thought; Nickel envelope particulate vector is the happy ENHANCER thought.In table ten one box 12, wetting agent is as the happy 62A of think of and the NIMAC 32C WETTER of wheat dolantin.
Table ten one (plating microporous nickel)
Table ten two (plating high-sulfur nickel)
(12), plating decorative layer, electroplate in plating trivalent white chromium plating solution, solution respectively forms concentration proportioning in different embodiment in table ten three:
Table ten three (the white chromium of plating trivalent)
Above Embodiment C ASS experiment reach 96-120h and more than, corrod kote paste experiment then reaches stable more than 336h.
Unique difference of embodiment 6-10 and embodiment 1-5 is only, electronegative potential nickel dam includes micro-crack nickel dam, and decorative layer is trivalent black chromium plating.And micro-crack nickel dam plating solution adopts plating solution as shown in following table 14 accordingly, and trivalent black chromium plating plating solution adopts plating solution as shown in following table 15 accordingly, and wherein wetting agent is conventional surfactants, as dodecyl sodium sulfate, sodium stearyl sulfonate etc.In table ten four, wetting agent is as the happy 62A of think of and the NIMAC 32C WETTER of wheat dolantin.
Table ten four (plating micro-crack nickel)
Table ten five (the black chromium of plating trivalent)
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 two), micro-crack nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten four) two-layer between compound, now between micro-crack nickel dam 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; Decorative layer is Cr VI coating, and Cr VI coating plating solution adopts plating solution as shown in following table 16 accordingly, and wherein decorative chromium brightener can be as the happy 1120F of think of and the 7000C of Japanese chemical metallization.
Table ten six (plating Cr VI)
Preparation embodiment 16-30 is only with unique difference of preparation embodiment 1-15, and nickel envelope brightener is NIMAC 14 INDEX 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 31-60 is only with unique difference of preparation embodiment 1-30, 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 61-90 is only with unique difference of preparation embodiment 31-60, 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 91-180 is only with unique difference of preparation embodiment 1-90, and pretreatment coating is electroless nickel layer.
Preparation embodiment 181-270 is only with unique difference of preparation embodiment 1-90, and pretreatment coating is bottoming nickel dam.
Preparation embodiment 271-360 is only with unique difference of preparation embodiment 1-90, and the pretreatment coating of substrate surface is empty, 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.
In technical solutions of the utility model, base material can also adopt materials such as including, without being limited to PC, PP, nylon, PET, bakelite and metal material to make 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 can be seen from Fig. 2 and Fig. 3 coating potential diagram then, in the utility model scheme, no matter electronegative potential nickel dam 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 4, the mechanism when nickel plating that the utility model scheme obtains-chromium parts are corroded is: for form electroless nickel layer 809 in ABS substrate 810 layer by layer in figure, bottoming nickel dam 808, copper plate 3, electronegative potential nickel dam 141, micropore nickel dam 142 and decorative layer 802, corrosive medium 801 is on decorative layer 802 (i.e. trivalent chromium coating or Cr VI coating) surface and in the microcellular structure of micropore nickel dam 142 disperse corrosion current and to enter electronegative potential nickel dam 141 (in based on electrochemical corrosion, corrosion rate is with participation electrode area and the directly related reason of corrosion current size, here the area of actual participation corrosion is reduced, thus there is less corroded area, form multiple independently hot spot, thus dispersion corrosion current, delay corrosion rate), after corrosion forms erosional surface 805, the copper plate 3 of high potential is run into after erosional surface 805 runs through electronegative potential nickel dam 141, rear termination longitudinally corrosion is that lateral encroaching is until corrode whole electronegative potential nickel dam 141, just can carry out next step corrosion, until coating structure is destroyed by entirety.
This place embodiment to the non-limit part of the technical scope midrange that the utility model is claimed, equally all in the scope that the utility model is claimed.
Technological means disclosed in the utility model scheme 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.It is more than detailed description of the invention of the present utility model; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the utility model principle; can also make some improvements and modifications, these improvements and modifications are also considered as protection domain of the present utility model.
Claims (7)
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; And functional layer, it is formed on copper plate, and wherein functional layer comprises electronegative potential nickel dam and is formed at the micropore nickel dam on electronegative potential nickel dam; And decorative layer, it is formed on micropore nickel dam.
2. nickel plating according to claim 1-chromium parts, is characterized in that: described decorative layer is the arbitrary of trivalent chromium coating or Cr VI coating.
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 electronegative potential nickel dam adopts the composite deposite of micro-crack nickel dam and high-sulfur nickel dam, between micro-crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mV.
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|---|---|---|---|
| CN201520136337.5U CN204585986U (en) | 2015-03-11 | 2015-03-11 | Nickel plating-chromium parts |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772947A (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 |
| CN104790004A (en) * | 2015-03-11 | 2015-07-22 | 嘉兴敏惠汽车零部件有限公司 | Nickel and/or chromium plated component and manufacturing method thereof |
| CN114686943A (en) * | 2020-12-28 | 2022-07-01 | 复盛应用科技股份有限公司 | Surface treatment method for golf club head |
-
2015
- 2015-03-11 CN CN201520136337.5U patent/CN204585986U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104772947A (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 |
| CN104790004A (en) * | 2015-03-11 | 2015-07-22 | 嘉兴敏惠汽车零部件有限公司 | Nickel and/or chromium plated component and manufacturing method thereof |
| CN114686943A (en) * | 2020-12-28 | 2022-07-01 | 复盛应用科技股份有限公司 | Surface treatment method for golf club head |
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