CN204589342U - Nickel plating parts - Google Patents
Nickel plating parts Download PDFInfo
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- CN204589342U CN204589342U CN201520138411.7U CN201520138411U CN204589342U CN 204589342 U CN204589342 U CN 204589342U CN 201520138411 U CN201520138411 U CN 201520138411U CN 204589342 U CN204589342 U CN 204589342U
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Abstract
Nickel plating parts disclosed in the utility model, wherein nickel plating parts comprise base material; Pre-treatment coating, its deposition over the whole substrate, pre-treatment coating is formed with copper plate; And functional layer, it is formed on copper plate, and wherein functional layer comprises low potential nickel dam and is formed at the micropore nickel dam on low potential nickel dam.The utility model by the micropore nickel dam that jointly arranges on plating piece top layer and low potential nickel dam, thus greatly improves erosion resistance and the stability of coating, and can also have good bright planarization, coating is in conjunction with effective simultaneously.
Description
Technical field
The utility model relates to a kind of workpiece and the electroplating technology thereof with electroplating surface Rotating fields, particularly a kind of nickel plating parts.
In the application, potential difference is the difference of the normal 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 electrolytic coating of crackle or hole (comprising sexavalent chrome and trivalent chromium coating) completely, expose after aerial chromium electrolytic coating is passivated, its current potential than nickel just, when running into 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 big 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 tiny 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 tiny crack coordinates with trivalent chromium, there is the problems such as appearance poor, cause the product for high corrosion resistant requirement to there is inapplicability.Simultaneously in part prior art, disclose and change microporous nickel technique to reach noble potential characteristic, thus meet the requirement of trivalent chromium corrosion resistance nature, but this this Technology cannot realize and sexavalent chrome, 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 metallic 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 erosion resistance that improve plastic component to a certain extent in this technical scheme, but the resistance to corrosion of this technique still cannot reach containing deicer salts (CaCl
2) requirement of corrosive environment.And about introducing the technique of micro-crack nickel, as Chinese patent application (publication number: CN101705508A) relates to a kind of electroplate liquid for micro-crack nickel plating and application thereof, this micro-crack nickel electroplate liquid mainly composed as follows: nickelous chloride: 180 ~ 260 grams per liters, acetic acid: 20 ~ 60 milliliters/liter, ELPELYT MR:80 ~ 120 milliliter/liter, 62A:1 ~ 5 milliliter/liter, the evaluation physical constraints of the example described in patent documentation is sexavalent chrome plating, 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 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 solidity to corrosion of the functional layer comprising microporous nickel, product can be made to reach superelevation solidity to corrosion and structural stability, even if after low potential nickel dam is corroded, micropore nickel dam can play the effect of supporting and delaying to corrode equally.
Nickel plating parts disclosed in the utility model, 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.
(pre-treatment coating can comprise the arbitrary or two-layer compound in electroless nickel layer or bottoming nickel dam to pre-treatment 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, pre-treatment coating is formed with copper plate; With
Functional layer, it is formed on copper plate, and wherein functional layer comprises low potential nickel dam and is formed at the micropore nickel dam on low potential nickel dam.
The one of nickel plating parts disclosed in the utility model is improved, and the potential difference of micropore nickel dam and low potential nickel dam is 10-120mv.
The one of nickel plating parts disclosed in the utility model is improved, low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between compound.Preferred further, the potential difference between micropore nickel dam and low potential nickel dam is 20-100mv.
When low potential nickel dam adopts the composite deposite of tiny crack nickel dam and high-sulfur nickel dam, between tiny crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mv.Here when corroding arrival low potential nickel dam, because the current potential of tiny crack nickel dam is higher than the current potential of high-sulfur nickel dam, now high-sulfur nickel dam is preferentially corroded by as anodic coating again, extends the corrosion of tiny crack nickel dam, thus improves corrosion-resistant degree further.
Disclosed in the utility model, the manufacture method of nickel plating parts comprises the steps:
Pre-treatment is carried out on the surface of base material;
Pre-treatment coating is deposited over the whole substrate, and copper plate is formed on pre-treatment coating; With
Low potential nickel dam in functional layer is formed on copper plate; With
Micropore nickel dam in functional layer is formed on low potential nickel dam; Potential difference between micropore nickel dam and low potential nickel dam is within the scope of 10-120mv.Potential difference controlled, within the scope of this, in electroplating process, not easily to occur bubbling, coating structure is more stable firmly simultaneously, separation not easily occurs and peels off.Here low potential nickel dam coordinate with copper plate for by low potential nickel dam Direct Electroplating on copper plate, centre undopes other coating.
First aspect of the present utility model provides nickel plating parts, and it comprises following: base material; Pre-treatment 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 pre-treatment coating; Functional layer, it is formed on copper plate, and wherein functional layer comprises low potential nickel dam and is formed at the micropore nickel dam on low potential nickel dam, is formed on copper plate by the low potential nickel dam in functional layer; With the micropore nickel dam in functional layer is formed on low potential nickel dam; Potential difference wherein between micropore nickel dam and low potential nickel dam is within the scope of 10-120mv.
Can re-plating (can be chromium coating at ornament layer outside functional layer of the present utility model, chromium coating as white in trivalent or trivalent black chromium plating or sexavalent chrome coating arbitrary), it is formed on microporous nickel coating, and there is the one of at least any of microvoid structure and micro-cracked structure, low potential nickel dam has two kinds of modes when coordinating with copper plate, one be by low potential nickel dam Direct Electroplating on copper plate, centre undopes other coating, another kind of mode can also be plated on copper plate by Indirect Electro by low potential nickel dam, that is other coating can also be electroplated between low potential nickel dam and copper plate, totally be referred to as basic coating, here basic coating can electroplate full light nickel, half light nickel, corresponding coating such as husky fourth nickel or high-sulfur nickel etc.
Second aspect of the present utility model provides the manufacture method of nickel plating parts, and it comprises the following steps: pre-treatment is carried out on the surface of base material; Pre-treatment coating is deposited over the whole substrate, and copper plate is formed on pre-treatment coating; With the low potential nickel dam in functional layer is formed on copper plate; With the micropore nickel dam in functional layer is formed on low potential nickel dam; Potential difference between described micropore nickel dam and low potential nickel dam is within the scope of 10-120mv.
The one of the manufacture method of nickel plating parts disclosed in the utility model is improved, low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between compound.
The one of the manufacture method of nickel plating parts disclosed in the utility model 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 nickelous chloride 50-60g/L, boric acid 40-50g/L, nickel envelope brightening agent 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) company limited is hereinafter referred to as wheat dolantin, NIMAC 14INDEX 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 dispersion agent of wheat dolantin), nickel envelope particle dispersants 0.5-3ml/L, wetting agent 1-5ml/L.When micropore nickel dam is coated with, service temperature controls between 50 ~ 60 DEG C, pH value controls between 3.8 ~ 4.6, and current density is 2 ~ 5ASD, and the operating time controls between 2 ~ 8min, make nickel deposition on plated item by the mode of direct current electrolysis, microporous nickel layer thickness is not less than 1.5 microns.
The one of the manufacture method of nickel plating parts disclosed in the utility model is improved, in plating tiny crack nickel dam operation in aforementioned plating low potential nickel dam operation, tiny crack nickel dam adopts the plating of plating micro-crack nickel plating solution to form, plating micro-crack nickel plating solution comprises composition and concentration is (in unit volume plating solution addition): moisture nickelous chloride 180 ~ 260g/L, acetic acid 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 tiny 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 deposition at 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 parts disclosed in the utility model is improved, in plating high-sulfur nickel dam operation in aforementioned plating low 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 nickelous 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 deposition at 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 neutralizing treatment operation, surperficial preimpregnation, surface activation process operation and surperficial dispergation treatment process comprising ABS resin at interior non-metal kind base material pretreatment process in early stage; Metal species base material then can carry out follow-uply being coated with work after surperficial grease treatment process carries out oil removing, the corresponding operation of the non-metallic base being suitable for following statement equally in earlier stage in pretreatment process.
In above-mentioned manufacture method, non-metal kind base material pretreatment process in early stage is specially and base material blank is cleaned degrease in sodium hydroxide, sodium carbonate and water glass mixing solutions, immerse after degrease in chromic trioxide and sulfuric acid mixture liquid and carry out surface coarsening process, then put into hydrochloric acid soln and carry out surface neutralization, adopt colloidal palladium solution to carry out surface activation process after neutralization, then in sulphuric acid soln, carry out surperficial dispergation process.
As preferably, the mixing solutions of surperficial grease treatment process comprises composition and concentration is: the concentration of sodium hydroxide is 20-50g/L, and the concentration of sodium carbonate is 10-40g/L, and the concentration of water glass is 10-40g/L, tensio-active agent 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 sulphuric acid soln concentration of surface hydrophilic operation is 20-100g/L, whole agent 0.5-2ml/L.
As preferably, the mixed solution of surface coarsening treatment process comprises composition and concentration is: the concentration of chromic trioxide is 330-480g/L, and the concentration of sulfuric acid is 330-480g/L.
Here chromic trioxide is the main salt in plating solution, chromium metal and production chromium sesquioxide hydrate 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 trioxide to plating solution has considerable influence, if chromic trioxide content is high, then covering power is strong, crystallization is careful, if but chromic trioxide too high levels, the hardness of coating then can be made to decline, in addition, chromic trioxide and sulfuric acid can at corrosion substrate surface to form micro-roughened surface at substrate surface as etching reagent, " snap close effect " required during to guarantee electroless plating, the bonding force 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 harmful 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 colloidal palladium solution of surface activation process comprises composition and concentration is: the concentration of Palladous chloride is the concentration 1-6g/L of 20-60ppm, tin protochloride, hydrochloric acid 180-280ml/L.
Here in colloidal palladium solution, Palladous chloride is covered in substrate surface, for follow-up chemical nickel provides catalytic center, the tin ion of tin protochloride then can be deposited on around palladium ion with chemical combination group too, avoid palladium ion be oxidized in water or in air and come off, the life cycle of colloidal palladium solution can be increased.
As preferably, the sulphuric acid soln concentration of surperficial dispergation treatment process is 40-100g/L.
Surface dispergation process refers to and utilizes sulfuric acid to remove in colloidal palladium solution the tin protochloride be coated on around palladous oxide, is come out by palladium metal particle, makes subsequent chemistry sink nickel technique more smooth and easy.
As preferably, the electroless nickel layer plating solution of electroless nickel layer operation comprises composition and concentration is: the concentration of single nickel salt is 15-40g/L, and the concentration of sodium hypophosphite is 20-50g/L, the concentration of Trisodium Citrate 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 palladium metal that substrate surface has catalytic activity, and be convenient to the various metal of follow-up plating, in chemical sinking nickel process, single nickel salt provides nickel element; Inferior sodium phosphate is strong reductant, and the nickel element in single nickel salt is reduced into metallic nickel by it; Trisodium Citrate is buffer reagent, and it makes the reaction of inferior sodium phosphate reduced nickel element more mild, in the utility model, adopts Trisodium Citrate as buffer reagent.
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 nickelous 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 base material simultaneously, base material 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 electroconductibility of coating further.In this step, aqueous sulfuric acid nickel, moisture nickelous 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 sulfate 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 sulfate to improve luminance brightness and the planarization of substrate surface, and can also improve the toughness of coating entirety.This is because copper coating compares nickel coating and other metal plating, its ductility is better, and after therefore plating sour layers of copper, toughness and the Surface flat of overall coating are improved.
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 low potential nickel dam adopt independent tiny crack nickel dam or for high-sulfur nickel dam and tiny crack nickel dam composition compound nickel dam; the anticorrosion effect that the utility model reaches best can be made; here tiny crack nickel dam in functional layer, micropore nickel dam or both combine the reason that can play protection against corrosion and protection base material and be; on workpiece, coated metal/substrate metal extremely easily forms corrosion cell; when anode and cathode current potential is determined, its erosion rate controlled by the ratio of coated metal (negative electrode) 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, erosion rate just becomes very large, easily inwardly forms pitting, but when metal coating surface exists more potential hot spot, cathode/anode ratio is less, corrosion current is assigned to everywhere, and the electric current originally in hot spot significantly reduces, and erosion rate also reduces greatly.Meanwhile, due to the segmentation between micropore or crackle, coating negative electrode is formed discontinuous, the coating after divided becomes small area by big area, further limit so again cathode/anode ratio.But along with time the passing of asking; when coating surface be subject to extraneous factor impact start to occur large mode-Ⅲ crack time; the potential corrosion cell of tiny crack, microvoid structure will be initiated; thus it is subject to the effect of hot spot to protection; thus just can play double-core and reduce the effect of corrosion electric current density, thus the corrosion-resistant degree of significant increase.
The anticorrosive mechanism of low potential nickel
The first step: when piece surface removes corrosive medium, because ornament 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 low potential nickel dam, because microporous nickel current potential is higher than low potential nickel current potential, now low potential nickel is preferentially corroded as anodic coating (namely low 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 tiny 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 erosion rate; the corrosion speed 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 low potential nickel dam further to downward-extension, because below low potential nickel dam, the current potential of coating (as copper plate) is higher than low potential nickel equally, low potential nickel has been regarded anodic coating equally, corrosion tendency now to downward-extension is terminated, corrosion position laterally carries out in low 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, for follow-up low 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 low potential nickel dam that obtain, and have high Corrosion Protection, high rigidity, high-wearing feature, binding force of cladding material is good, luminance brightness advantages of higher; Simultaneously there is the micropore nickel dam of noble potential characteristic and there is the MULTI-LAYER NICKEL of low potential characteristic---low potential nickel dam is for functional layer, and with low potential nickel dam for sacrifice layer, micro-electric current of galvanic corrosion can be disperseed with the micropore nickel dam with microvoid structure, delay be corroded generation, formed simultaneously and can also form oxide compound support after oxidation by microvoid structure, after can being subject to comparatively serious corrosion at the low potential nickel dam as sacrifice layer, it is formed and support, reduce part coating damage speed.The low potential nickel dam as sacrifice layer arranged has lower electromotive force; when the generation galvanic corrosion of piece surface coating; low potential nickel dam preferentially corrodes; and when there is micropore nickel dam or tiny crack nickel dam; its micropore or micro-cracked structure can play the micro-electric current of dispersion corrosion equally; when also having a layer structure outside low potential nickel dam, (during as ornament layer or protective layer) can also be supported outboard structure by micropore or micro-cracked structure, the steadiness of strongthener structure simultaneously.The utility model scheme utilizes the pore texture of microporous nickel and micro-crack nickel in addition, while strongthener structural support performance, can also play the effect reducing quality of coating and expend with reduction raw material.Its micro hole structure can also form large-area sull structure when there is oxidation corrosion simultaneously, thus greatly delays the generation of corrosion.
3, in addition, the utility model selects the plating solution little to environmental influence when filling a prescription and choosing as far as possible, make electroplating technology more environmental protection, further, coating combines firmly, is evenly distributed, longer service life, make the finished product no matter can meet the requirement of user in outward appearance or performance, make the technique of the utility model gained have the higher market competitiveness.
4, the utility model also has good process matching, can not only support the use with traditional hexavalent chromium plating, also can use with trivalent chromium process matching, can impel trivalent chromium environment-protective process, the application on high request product simultaneously.
Accompanying drawing explanation
Fig. 1 is the coating structure schematic diagram of the embodiment of the utility model nickel plating 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 the utility model nickel plating parts 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 the utility model nickel plating component corrosion cream.
Fig. 6 the utility model list low potential nickel dam potential difference picture (low potential nickel dam is the arbitrary of high-sulfur nickel dam or tiny crack nickel dam).
Fig. 7 the utility model compound low potential nickel dam potential difference picture (low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam).
Fig. 8 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 layer; 21, vacancy is corroded;
3, copper plate; 31, surface micropore; 32, corrosion hole;
4, functional layer; 141, low potential nickel dam; 142, micropore nickel dam;
801, corrosive medium; 805, erosional surface;
808, bottoming nickel dam; 809, electroless nickel layer; 810, ABS substrate.
Embodiment
Below in conjunction with the drawings and specific embodiments, illustrate the utility model further, following embodiment should be understood and be only not used in restriction scope of the present utility model for illustration of the utility model.
As shown in Figure 1, below the coating structure of the utility model nickel plating parts is described, here the utility model base material can adopt metal, plastics and other can be suitable for the parts of plating.
Constructive embodiment 1
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment layer 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 low potential nickel dam 141 and micropore nickel dam 142, and wherein low potential nickel dam 141 is high-sulfur nickel dam and the micropore nickel dam 142 be formed on high-sulfur nickel dam.
Constructive embodiment 2
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment layer 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 low potential nickel dam 141 and micropore nickel dam 142, and wherein low potential nickel dam 141 is tiny crack nickel dam and the micropore nickel dam 142 be formed on tiny crack nickel dam.
Constructive embodiment 3
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment layer 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 low potential nickel dam 141 and micropore nickel dam 142, and wherein for high-sulfur nickel dam and tiny crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, tiny crack nickel dam be formed on high-sulfur nickel dam low potential nickel dam 141; Also can be that tiny crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on tiny crack nickel dam) and the micropore nickel dam 142 that is formed on low potential nickel dam 141.
Constructive embodiment 4
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment layer 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 low potential nickel dam 141 and micropore nickel dam 142, and wherein low potential nickel dam 141 is tiny crack nickel dam and the micropore nickel dam 142 be formed on tiny crack nickel dam.
Constructive embodiment 5
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pre-treatment coating 2 comprises bottoming nickel dam 808, and bottoming nickel layer deposition, on whole base material 1, bottoming nickel dam 808 is formed with copper plate 3; With functional layer 4, it is formed on copper plate 3, and wherein functional layer 4 comprises low potential nickel dam 141 and the micropore nickel dam 142 be formed on low potential nickel dam 141.
Constructive embodiment 6
The nickel plating parts of the present embodiment, these parts comprise: base material 1 (ABS material); Pretreatment layer 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 low potential nickel dam 141 and micropore nickel dam 142, and wherein for high-sulfur nickel dam and tiny crack nickel dam, (can be that high-sulfur nickel dam is formed on copper plate 3, tiny crack nickel dam be formed on high-sulfur nickel dam low potential nickel dam 141; Also can be that tiny crack nickel dam is formed on copper plate 3, high-sulfur nickel dam be formed on tiny crack nickel dam) and the micropore nickel dam 142 that is formed in functional layer 4.
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 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 iron and cast alloy 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, chromium coating 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 parts of a kind of embodiment of the utility model is as follows, the surface of base material is carried out pre-treatment (pre-treatment in turn includes the following steps: surperficial degrease, surface hydrophilic process, surface coarsening process, surperficial neutralizing treatment, preimpregnation, surface activation process, surperficial dispergation process); Pre-treatment coating (is comprised chemical sinking nickel and bottoming nickel, the selection that whether pre-treatment coating retains and pre-treatment 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 pre-treatment coating (bottoming nickel dam is outer); With the low potential nickel dam in functional layer is formed on copper plate, low potential nickel dam is high-sulfur nickel dam here; Be formed on high-sulfur nickel dam with by the micropore nickel dam in functional layer.
Potential difference between micropore nickel dam from high-sulfur nickel dam (low potential nickel dam) is respectively 10,20,30,40,50,60,70,80,90,100,110, other arbitrary value (embodiment 1-5 can select different numerical value in 10-120 to be the potential difference in corresponding embodiment between micropore nickel dam and low potential nickel dam respectively, and the potential difference in each embodiment between micropore nickel dam with low potential nickel dam also can be identical) within the scope of the arbitrary or 10-120 of 120mv.Micropore nickel dam is plate the nickel dam of one deck uniformly and containing numerous non-conductive particle and conductive particle at product surface, and make ABS substrate workpiece surface have high Corrosion Protection, high rigidity, high-wearing feature like this, binding force of cladding material is good, luminance brightness advantages of higher.
On above-mentioned part, nickel electric plating method comprises the steps:
(1) surperficial degrease: at sodium hydroxide NaOH, sodium carbonate Na
2cO
3, water glass Na
2siO
3with clean in tensio-active agent mixing solutions.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table one: tensio-active agent is that conventional surfactants is as sodium laurylsulfonate, sodium stearyl sulfonate etc.
Table one
(2) surface hydrophilic process: carry out in sulfuric acid and whole agent mixing solutions.In this step, sulfuric acid and whole agent concentration proportioning is in different embodiments in table two:
Table two
(3) surface coarsening process: at chromic trioxide CrO
3with sulfuric acid H
2sO
4carry out in mixed solution.In this step, chromic trioxide CrO
3with sulfuric acid H
2sO
4concentration proportioning is in different embodiments in table three:
Table three
(4) surperficial neutralizing treatment: the base material after surface coarsening process is put into hydrochloric acid and hydrazine hydrate mixing solutions 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 neutralizing treatment carries out in hydrochloric acid soln, in this step, hydrochloric acid soln at the concentration proportioning of different embodiment in table five:
Table five
(6) surface activation process: surface activation process adopts colloidal palladium solution, colloidal palladium Chlorine in Solution palladium PdCl
2, tin protochloride 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 sulphuric acid soln at the concentration proportioning of different embodiment in table seven:
Table seven
(8) chemical sinking nickel: containing hydration nickel sulfate, hydration sodium hypophosphite, Trisodium Citrate C
6h
5na
3o
7, carry out in ammonium chloride and ammoniacal liquor (ammoniacal liquor be used for the PH of regulator solution be 8.6-9.2) mixing solutions.In this step, in mixing solutions, 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 nickelous chloride NiCl
2-6H
2o, boric acid H
3bO
3and carry out in the mixing solutions of wetting agent.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table nine: in table nine, wetting agent is as the happy 62A of think of and the NIMAC 32C WETTER of wheat dolantin.
Table nine
(10) copper plate: at copper sulfate CuSO
4, sulfuric acid H
2sO
4, chlorion, leveling agent, to carry out in walk agent and open cylinder agent mixing solutions.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 (low 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 nickelous chloride NiCl
2-6H
2o and boric acid H
3bO
3mixing solutions.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 brightening agent 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)
Above Embodiment C ASS experiment reach 96-120h and more than, corrod(o)kote paste experiment then reaches stable more than 336h.
Unique difference of embodiment 6-10 and embodiment 1-5 is only, low potential nickel dam includes tiny crack nickel dam.And tiny crack nickel dam plating solution adopts plating solution as shown in following table 13 accordingly.In table ten three, wetting agent is as the happy 62A of think of and the NIMAC 32C WETTER of wheat dolantin.
Table ten three (plating micro-crack nickel)
Preparation embodiment 11-15 is only with unique difference of preparation embodiment 1-5, low potential nickel dam include high-sulfur nickel dam (each embodiment plating solution is accordingly in turn see table ten Suo Shi), tiny crack nickel dam (each embodiment plating solution is accordingly in turn see shown in table ten two) two-layer between compound, now between tiny 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.
Preparation embodiment 16-30 is only with unique difference of preparation embodiment 1-15, and nickel envelope brightening agent 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 dispersion agent 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 pre-treatment coating is electroless nickel layer.
Preparation embodiment 181-270 is only with unique difference of preparation embodiment 1-90, and pre-treatment coating is bottoming nickel dam.
Preparation embodiment 271-360 is only with unique difference of preparation embodiment 1-90, and the pre-treatment 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.
Comprehensive above all embodiments, can find out, the all embodiments of technical solutions of the utility model reach 96-120h and above (prior art then proposes as 40-48h) by CASS experiment, corrod(o)kote paste experiment then reaches stable more than 336h (product that prior art obtains is then unstable, cannot carry out quantization signifying).
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 metallic substance to make at interior material.When selecting other base material except ABS, pre-treatment coating can carry out selection according to the performance of actual material and process requirements has pre-treatment coating or without pre-treatment coating.
As the etch state figure that Fig. 3 nickel plating parts sample that obtain to by the utility model embodiment 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 amount on surface in the nickel plating sample that the utility model obtains, then equally only there is less corrosion hole 32 in section display, be the coating structure that corrosion hole that surface micropore and sacrifice layer produce all does not have to destroy parts, do not affect the use of product and attractive in appearance.
Fig. 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 the utility model embodiment gained after corrod(o)kote paste experiment (336h, 336h, 168h) (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 utility model obtains then is corroded degree, substantially do not have variable color.As can be seen here, the nickel plating parts that unquestionable technical solutions of the utility model obtain have more excellent coating stability and erosion resistance, make nickel plating parts more durable, attractive in appearance.
As can be seen from Fig. 6 and Fig. 7 coating potential ph diagram ph then, in the utility model scheme, no matter low potential nickel dam is simple layer or lamination layer structure, to be when being corroded with low potential nickel dam as sacrifice layer, when low potential nickel dam is the composite bed of high-sulfur nickel dam and tiny crack nickel dam, the height of the current potential of high-sulfur nickel dam and tiny crack nickel dam regulates with actual production technique, can be that high-sulfur nickel dam electromotive force is slightly high, also can be that tiny crack nickel dam electromotive force is slightly high.
As shown in Figure 8, mechanism when the nickel plating parts that the utility model scheme obtains 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, low potential nickel dam 141 and micropore nickel dam 142, corrosive medium 801 disperses corrosion current and enters low potential nickel dam 141 (to reduce the area of actual participation corrosion in the microvoid structure of micropore nickel dam 142, there is less corroded area, form multiple independently hot spot, thus dispersion corrosion current, delay corrosion speed), after corrosion forms erosional surface 805, the copper plate 3 of high potential is run into after erosional surface 805 runs through low potential nickel dam 141, rear termination longitudinally corrosion is that lateral encroaching is until corrode whole low 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 mid point value that the utility model is claimed, equally all in the scope that the utility model is claimed.
Technique means disclosed in the utility model scheme is not limited only to the technique means disclosed in above-mentioned technique means, also comprises the technical scheme be made up of above technical characteristic arbitrary combination.It is more than embodiment 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 (6)
1. nickel plating parts, these parts comprise:
Base material;
Pre-treatment coating, its deposition over the whole substrate, pre-treatment coating is formed with copper plate; With
Functional layer, it is formed on copper plate, and wherein functional layer comprises low potential nickel dam and is formed at the micropore nickel dam on low potential nickel dam.
2. nickel plating parts according to claim 1, is characterized in that: the potential difference between described micropore nickel dam and low potential nickel dam is within the scope of 10-120mv.
3. nickel plating parts according to claim 1 and 2, is characterized in that: described low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between composite deposite.
4. nickel plating parts according to claim 1 and 2, is characterized in that: the potential difference between described micropore nickel dam and low potential nickel dam is within the scope of 20-100mv.
5. nickel plating parts according to claim 3, is characterized in that: the potential difference between described micropore nickel dam and low potential nickel dam is within the scope of 20-100mv.
6. nickel plating parts according to claim 3, is characterized in that: when low potential nickel dam adopts the composite deposite of tiny crack nickel dam and high-sulfur nickel dam, between tiny crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mv.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104746116A (en) * | 2015-03-11 | 2015-07-01 | 嘉兴敏惠汽车零部件有限公司 | Nickel-plated component 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 |
-
2015
- 2015-03-11 CN CN201520138411.7U patent/CN204589342U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104746116A (en) * | 2015-03-11 | 2015-07-01 | 嘉兴敏惠汽车零部件有限公司 | Nickel-plated component 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 |
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