CN204625811U - The super anti-corrosion nickel plating-chromium parts of multilayer - Google Patents

Abstract

The utility model discloses a multi-layer super corrosion-resistant nickel-chrome plated part and a manufacturing method thereof, wherein the multi-layer super corrosion-resistant nickel-chrome plated part includes a base material; a pretreatment coating, which is deposited on the entire base material, is A copper-plated layer is formed on the plating layer; and a base layer, which is formed on the copper-plated layer; and a functional layer, which is formed on the base layer, wherein the functional layer includes a low-potential nickel layer and micropores formed on the low-potential nickel layer a nickel layer; and a decorative layer, which is formed on the microporous nickel layer, and the decorative layer is any one of a trivalent chromium plating layer or a hexavalent chromium plating layer. The utility model increases the low-potential nickel coating on the basis of the micropores and chrome-plating process on the surface of the component, thereby improving the corrosion resistance of the product, especially the corrosion resistance of the trivalent chrome-plated product, which can promote a more environmentally friendly trivalent Larger-scale promotion and application of chromium products.

Description

Multilayer Super Corrosion Resistant Nickel-Chrome Plated Components

technical field

The utility model relates to a workpiece with a surface coating structure, in particular to a multi-layer super corrosion-resistant nickel-chromium plated part.

In this application, the potential difference is the difference between the standard potentials measured by taking each of the two adjacent layers as a whole.

Background technique

The European market has increasingly stringent environmental protection requirements, and the main engine manufacturers have higher and higher requirements for electroplating corrosion resistance. At present, trivalent chromium electroplating cannot meet the corrosion requirements of specific environments (at the same time, it can meet the salt spray test 80h and Russia Mud test 336h).

In the electroplating industry, the method of firstly plating double-layer nickel or triple-layer nickel and then chromium plating is generally used to improve the anti-corrosion ability of the workpiece. The layer nickel process includes: semi-bright nickel + light nickel + microporous nickel + crack-free chromium, or semi-bright nickel + light nickel + micro-crack nickel + crack-free chromium, but due to the high stress of the chromium layer itself, it is difficult to obtain in industry A chromium electroplating layer (including hexavalent chromium and trivalent chromium plating) without cracks or pores at all. After the chromium electroplating layer exposed to the air is passivated, its potential is more positive than that of nickel. When it encounters the corrosive medium in the atmosphere At the same time, it will form a corrosion battery with the nickel layer, causing a large number of irregular corrosions in the decorative nickel plating layer in extreme environments, and even large-area corrosion of the nickel layer will cause the chromium layer to fall off. In order to further improve the anti-corrosion ability of the coating, microporous nickel and micro-cracked nickel are applied to the light nickel coating. Micro-cracked nickel is coated with a high-stress special nickel layer on the light nickel layer. Microcracks; while the microporous nickel layer disperses the corrosion current in the multilayer nickel to prevent the formation of deep corrosion points and avoid visible corrosion. Due to the use of micro-cracked nickel layer alone, the surface of the product is foggy and the brightness is poor, and there is no mention of trivalent chromium plating, and due to the use of micro-porous nickel or micro-cracked nickel alone, the improvement of corrosion resistance is limited.

In the prior art, as the Chinese patent application (publication number: CN102766894 A) relates to a kind of electroplating solution and its application for micro-crack nickel electroplating, the main composition of this micro-crack nickel electroplating solution is as follows: Nickel chloride: 180～260 g/l, acetic acid: 20-60 ml/l, ELPELYT MR: 80-120 ml/l, 62A: 1-5 ml/l. The micro-crack nickel plating process on the surface of plastic parts is: A. Metallization of plastic parts, B. Bright copper, C. Semi-bright nickel, D. High sulfur nickel, E. Bright nickel, F. Microporous nickel, G. Washing , H. bright chromium, I. washing, J. drying; although adopting this four-layer nickel-nickel electroplating solution to carry out electroplating on the plastic surface has improved the corrosion resistance of plastic parts to a certain extent in this technical scheme, yet the anticorrosion property of this process The corrosion ability still cannot meet the requirements of the corrosive environment containing deicing salt (CaCl ₂ ), and the high-sulfur nickel electroplating layer has local fogging phenomenon. In addition, due to the insufficient plastic surface treatment in this method, the deep plating ability of the coating layer is poor, and the coating layer is prone to cracking. Brittle, electroplated plastics have a short service life after being used as automotive parts (grilles, trims, door handles). And about the technique of introducing micro-crack nickel, as Chinese patent application (publication number: CN101705508A) relates to a kind of electroplating solution and application thereof for micro-crack nickel electroplating, the main composition of this micro-crack nickel electroplating solution is as follows: nickel chloride: 180-260 g/l, acetic acid: 20-60 ml/l, ELPELYT MR: 80-120 ml/l, 62A: 1-5 ml/l, the evaluation of examples described in the patent literature is actually limited to hexavalent chromium plating , did not talk about trivalent chromium plating.

Contents of the invention

In order to solve the above problems, the utility model discloses a multi-layer super corrosion-resistant nickel-chromium plated part, which ensures the corrosion resistance and electrochemical performance of the multi-layer nickel structure of the functional layer in an organic combination, which not only ensures the microporous nickel layer The bright appearance and the double corrosion resistance of the functional layer containing microporous nickel can make the product achieve ultra-high corrosion resistance and structural stability. Even after the low potential nickel layer is corroded, the microporous nickel layer can also Play a role in supporting and retarding corrosion.

The utility model discloses a multi-layer super corrosion-resistant nickel-chromium plated component, which comprises:

Substrate;

a pretreatment coating deposited over the entire substrate with a copper plating layer formed on the pretreatment coating; and

a base layer formed on the copper plating layer; and

A functional layer formed on the base layer, wherein the functional layer includes a low-potential nickel layer and a microporous nickel layer formed on the low-potential nickel layer; and

A decorative layer is formed on the microporous nickel layer, and the decorative layer is any of a trivalent chromium coating or a hexavalent chromium coating.

As a preference, the potential difference between the microporous nickel layer and the low potential nickel layer is in the range of 10-120mv.

As a preference, the low-potential nickel layer includes a high-sulfur nickel layer, one layer of the micro-cracked nickel layer or a composite coating between the two layers.

As a preference, the potential difference between the microporous nickel layer and the low potential nickel layer is in the range of 20-100mv.

As a preference, when the low-potential nickel layer adopts the composite coating of the micro-cracked nickel layer and the high-sulfur nickel layer, the potential difference between the micro-cracked nickel layer and the high-sulfur nickel layer is within 10-80mv. Here, when the corrosion reaches the low-potential nickel layer, since the potential of the micro-cracked nickel layer is higher than that of the high-sulfur nickel layer, the high-sulfur nickel layer is preferentially corroded as an anodic coating, prolonging the corrosion of the micro-cracked nickel layer, thereby Further improved corrosion resistance.

An improvement of the multi-layer super corrosion-resistant nickel-chromium plated parts disclosed in the utility model, the base layer includes one or more layers of semi-bright nickel layer, high-sulfur nickel layer, full-bright nickel layer, and satin nickel layer .

An improvement of the multi-layer super-corrosion-resistant nickel-chrome plated parts disclosed in the utility model, the base layer is a compound between a semi-gloss nickel layer and a full-gloss nickel layer, wherein the semi-gloss nickel layer is formed on the copper plating layer , the full-bright nickel layer is formed on the semi-bright nickel layer.

An improvement of the multi-layer super-corrosion-resistant nickel-chrome plated parts disclosed in the utility model, the base layer is a compound between a semi-gloss nickel layer and a satin nickel layer, wherein the semi-gloss nickel layer is formed on the copper-plated layer, A satin nickel layer is formed on the semi-gloss nickel layer.

As a preference, the potential difference between any one of the all-bright nickel layer or satin nickel layer and the low-potential nickel layer is in the range of 0-100mv.

As a preference, the potential difference between the semi-bright nickel layer and the full-bright nickel layer, between the semi-bright nickel layer and the satin nickel layer is within the range of 100-200mv.

An improvement of the multi-layer super corrosion-resistant nickel-chrome plating parts disclosed in the utility model, the base layer is a compound between the semi-gloss nickel layer, the high-sulfur nickel layer and the full-bright nickel layer, wherein the semi-gloss nickel layer is formed On the copper plating layer, the high-sulfur nickel layer is formed on the semi-bright nickel layer, and the full-bright nickel layer is formed on the high-sulfur nickel layer.

An improvement of the multi-layer super corrosion-resistant nickel-chromium plating parts disclosed in the utility model, the base layer is a compound between a semi-gloss nickel layer, a high-sulfur nickel layer and a satin nickel layer, wherein the semi-gloss nickel layer is formed on On the copper plating layer, the high-sulfur nickel layer is formed on the semi-bright nickel layer, and the satin nickel layer is formed on the high-sulfur nickel layer.

An improvement of the multi-layer super corrosion-resistant nickel-chromium plated parts disclosed in the utility model, the base layer is a compound between a semi-gloss nickel layer, a full-gloss nickel layer and a satin nickel layer, wherein the semi-gloss nickel layer is formed on On the copper plating layer, the full-bright nickel layer is formed on the semi-bright nickel layer, and the satin nickel layer is formed on the full-bright nickel layer.

The multi-layer super corrosion-resistant nickel-chrome plated part provided by the utility model comprises the following: a substrate; a pretreatment coating (can include any one of the chemical nickel layer and the primer nickel layer or a combination of the two), which is formed on the entire substrate Copper-plated layer, which is formed on the pretreatment coating; base layer (can include any or more composites in full-gloss nickel layer, semi-gloss nickel layer, satin nickel layer, high-sulfur nickel layer), which is formed on the plated layer On the copper layer; a low-potential nickel coating formed on the base coating, a microporous nickel layer formed on the low-potential nickel layer, wherein the potential difference between the low-potential nickel coating and the microporous nickel coating is in the range of 10mV to 120mV and a decorative layer (which may be a chromium coating, such as any of a trivalent chromium coating or a hexavalent chromium coating), which is formed on the microporous nickel coating and has at least any one of a microporous structure and a microcrack structure.

The manufacturing method of the multi-layer super corrosion-resistant nickel-chromium plating parts provided by the utility model comprises the following steps: forming the pretreatment coating on the whole substrate; forming the copper plating layer on the pretreatment coating; forming the base layer on the On the copper plating layer, wherein the base layer includes at least any one of a semi-gloss nickel layer, a high-sulfur nickel layer, a full-gloss nickel layer, and a satin nickel layer; the noble low-potential nickel coating is formed on the base coating, and the microporous nickel A layer is formed on the low-potential nickel layer, wherein the potential difference between the low-potential nickel plating layer and the microporous nickel layer is in the range of 10mV to 120mV; and the decoration layer is formed on the microporous nickel layer.

An improvement of the manufacturing method of the multi-layer super corrosion-resistant nickel-chrome plated parts disclosed by the utility model, the base layer includes a layer of semi-bright nickel layer, high-sulfur nickel layer, full-bright nickel layer, satin nickel layer or multiple layers.

As preferably, the semi-gloss nickel layer is formed by electroplating with a semi-gloss nickel plating solution, and the semi-gloss nickel plating solution includes components and concentrations (addition amount per unit volume of the plating solution): hydrated nickel sulfate 200-300g/L, hydrated chlorine Nickel 35-50g/L, boric acid 35-50g/L, semi-bright nickel primary brightener 3.0-7.0ml/L (convinced Lesi Chemical Trading (Shanghai) Co., Ltd. hereinafter referred to as Lesi, MacDermid Technology (Suzhou) Co., Ltd. is hereinafter referred to as MacDermid, such as BTL MU of Lesi or NIMAC SF DUCT of MacDermid), semi-bright nickel secondary brightener 0.3-1.0ml/L (such as TL-2 of Lesi or NIMAC SF of MacDermid LEVELER), potential difference adjuster 0.8-1.2ml/L (such as Lesi’s B supplement or Macderma’s NIMAC SF MAINTENANCE), wetting agent 2.0-3.0ml/L (such as Lesi’s 62A or Maidermid’s NIMAC 32C WETTER). During semi-bright nickel layer plating, the operating temperature is controlled between 50-60°C, the pH value is controlled between 3.6-4.6, the current density is 2-5ASD, and the operating time is controlled between 12-24min, through direct current electrolysis To deposit nickel on the surface of the copper plating layer of the electroplated part, the thickness of the semi-gloss nickel plating layer is required to be not less than 8 microns.

As preferably, the full-bright nickel layer is formed by electroplating with a full-bright nickel plating solution, and the full-bright nickel plating solution includes components and concentrations (addition amount per unit volume of the plating solution): aqueous nickel sulfate 220-340g/L, aqueous chlorine Nickel 40-50g/L, boric acid 35-40g/L, bright nickel softener 8-12ml/L (such as Lesi's 63 or Macdermid's NIMAC 14 INDEX), bright nickel main light agent 0.5-0.9ml/L (such as Schleich's 66E or MacDermid's NiMac Challenger Plus), wetting agent 2.0-3.0ml/L (such as Schleich's 62A or MacDermid's NIMAC 32C WETTER). During the all-bright nickel layer plating, the operating temperature is controlled between 50-60°C, the pH value is controlled between 3.6-4.6, the current density is 2-5ASD, and the operating time is controlled between 9-20min, through direct current electrolysis To deposit nickel on the semi-gloss nickel-plated surface of the electroplated part, the thickness of the full-bright nickel coating is required to be not less than 5 microns.

As preferably, the high-sulfur nickel layer is formed by electroplating with a high-sulfur nickel plating solution, and the high-sulfur nickel plating solution includes components and concentrations (addition amount per unit volume of the plating solution): the concentration of aqueous nickel sulfate is 250-350g/L , the concentration of aqueous nickel chloride is 35-60g/L, the concentration of boric acid is 35-65g/L, the concentration of high-sulfur additive is 3-10ml/L, and the concentration of wetting agent is 0.5-3ml/L (such as Le Si 62A or MacDermid's NIMAC 32C WETTER).

As preferably, the satin nickel layer is formed by electroplating with satin nickel plating solution, and the satin nickel plating solution includes composition and concentration (addition amount in the unit volume plating solution): the concentration of aqueous nickel sulfate is 250-350g/L , the concentration of aqueous nickel chloride is 35-60g/L, the concentration of boric acid is 35-65g/L, the concentration of auxiliary additives is 5-20ml/L (such as Elpelyt pearlbrite carrier K4 or Elpelyt carrier brightener H of Lesi), The concentration of nickel satin forming agent is 0.1-0.6ml/L (such as Elpelyt pearlbrite additive K6AL from Schleich).

In the above-mentioned manufacturing method, the low-potential nickel layer includes a high-sulfur nickel layer, a layer of micro-cracked nickel layer or a composite between the two layers.

As preferably, the microporous nickel layer is formed by electroplating with a microporous nickel plating solution, and the microporous nickel plating solution includes composition and concentration (addition amount per unit volume of the plating solution): aqueous nickel sulfate 300-350g/L, aqueous chlorine Nickel 50-60g/L, boric acid 40-50g/L, nickel sealing brightener 6-12ml/L (such as Lesi's 63 or Macdermid's NIMAC 14 INDEX), nickel sealing main brightening agent 4-7.5ml/L (such as Schleich's 610CFC or MacDermid's NIMAC 33), nickel-sealed particles 0.2-1.5g/L (such as Schleich's ENHANCER or MacDermid's NiMac Hypore XL dispersant), nickel-sealed particle dispersant 0.5-3ml/L , Wetting agent 1-5ml/L. When the microporous nickel layer is plated, the operating temperature is controlled between 50-60°C, the pH value is controlled between 3.8-4.6, the current density is 2-5ASD, and the operating time is controlled between 2-8min, through direct current electrolysis. To deposit nickel on the electroplated parts, the thickness of the nickel coating is required to be not less than 1.5 microns.

As preferably, the microcrack nickel layer is formed by electroplating with microcrack nickel plating solution, and the microcrack nickel plating solution includes composition and concentration (addition amount per unit volume of plating solution): aqueous nickel chloride: 180-260g/L, Acetic acid: 10-40ml/L, PN-1A: 40-90g/L, PN-2A: 1-5ml/L, wetting agent: 1-5ml/L (such as Schleiser’s 62A or MacDermid’s NIMAC 32C WETTER) . When the micro-cracked nickel layer is plated, the operating temperature is controlled between 25-35°C, the pH value is controlled between 3.6-4.6, the current density is 5-9ASD, and the operating time is controlled between 2-8min, through direct current electrolysis. To deposit nickel on the surface of the light-plated nickel layer of the electroplated part, the thickness of the micro-cracked nickel layer is required to be not less than 1.0 microns.

As preferably, the high-sulfur nickel layer is formed by electroplating with a high-sulfur nickel plating solution, and the high-sulfur nickel plating solution includes components and concentrations (addition amount per unit volume of the plating solution): aqueous nickel sulfate 250-350g/L, aqueous chlorine Nickel 35-60g/L, boric acid 35-65g/L, high-sulfur additive 3-10ml/L, wetting agent 0.5-3ml/L (such as 62A from Lesi or NIMAC 32C WETTER from MacDermid). When the high-sulfur nickel layer is plated, the temperature is controlled between 55-65°C, the pH is controlled between 2.0-3.5, the current density is 2-6ASD, and the operating time is controlled between 2-8min. Nickel is deposited on the surface of the basic coating of electroplated parts, and the thickness of the high-sulfur nickel layer is not less than 1.0 microns.

In the above-mentioned manufacturing method, it also includes the pre-treatment process of the base material, wherein the pre-treatment process of the non-metal base material including ABS resin at least includes the surface oil treatment process, the surface hydrophilic, the surface roughening process, Surface neutralization treatment process, surface pre-dipping, surface activation treatment process and surface debonding treatment process; and metal substrates can be followed by subsequent plating after degreasing in the surface grease treatment process, and the non- The corresponding process in the pre-treatment process of the metal foundation.

In the above-mentioned manufacturing method, the pre-treatment process of the non-metallic substrate is specifically to clean the substrate blank in a mixed solution of sodium hydroxide, sodium carbonate, surfactant and sodium silicate to remove grease, and then immerse the substrate in chromium The surface is roughened in the mixed solution of acid anhydride and sulfuric acid, and then placed in hydrochloric acid solution for surface neutralization. After neutralization, the surface is activated with colloidal palladium solution, and then the surface is degummed in sulfuric acid solution.

As preferably, the composition and concentration included in the mixed solution of the surface oil treatment process are: the concentration of sodium hydroxide is 20-50g/L, the concentration of sodium carbonate is 10-40g/L, surfactant 1-3g/L, silicon The concentration of sodium acid is 10-40g/L.

Preferably, the concentration of the sulfuric acid solution in the surface hydrophilic step is 20-100g/L, and the finishing agent is 0.5-2ml/L.

Preferably, the components and concentrations included in the mixed liquid in the surface roughening treatment step are: the concentration of chromic anhydride is 330-480 g/L, and the concentration of sulfuric acid is 330-480 g/L.

Preferably, the components and concentrations included in the mixed solution in the surface neutralization step are: hydrochloric acid 30-100ml/L, hydrazine hydrate 15-60ml/L.

Preferably, the concentration of the hydrochloric acid solution in the surface pre-soaking process is 40-120ml/L.

Preferably, the colloidal palladium solution for surface activation treatment includes components and concentrations: hydrochloric acid 180-280ml/L, palladium chloride concentration 20-60ppm, stannous chloride concentration 1-6g/L.

Preferably, the concentration of the sulfuric acid solution in the surface degumming treatment process is 40-100 g/L.

In the above-mentioned manufacturing method, the pretreatment coating may include any one of the chemical nickel layer or the primer nickel layer or a combination of the two layers. When the chemical nickel layer and the underlying nickel layer exist simultaneously, the chemical nickel layer is formed on the substrate, and the underlying nickel layer is formed on the chemical nickel layer.

As preferably, include composition and concentration in the mixed solution of electroless nickel plating process: the concentration of nickel sulfate is 15-40g/L, the concentration of sodium hypophosphite is 20-50g/L, the concentration of ammonium chloride is 10-50g/L L, the concentration of sodium citrate is 10-40g/L, and ammonia water adjusts the pH value to 8.6-9.2.

As preferably, the composition and concentration included in the mixed solution of the nickel plating process are as follows: the concentration of aqueous nickel sulfate is 180-280g/L, the concentration of aqueous nickel chloride is 35-60g/L, and the concentration of boric acid is 35-60g /L, the concentration of wetting agent is 1-3ml/L (such as 62A of Lesi or NIMAC 32C WETTER of Mai Demei).

When the chemical nickel layer and the bottoming nickel layer exist on the substrate at the same time, the substrate has been covered with a thin conductive nickel layer through the oxidation-reduction reaction in the electroless nickel deposition; In nickel, a layer of nickel is plated on the chemical nickel by electrochemical method to further enhance the conductivity of the coating. In this step, the hydrated nickel sulfate and hydrated nickel chloride provide the nickel ions required for the electrochemical reaction.

In the above-mentioned manufacturing method, each component and concentration in the mixed solution of copper plating layer process are: the concentration of copper sulfate is 160-260g/L, the concentration of sulfuric acid is 50-100g/L, the concentration of chloride ion is 40- 100ppm, the concentration of the leveling agent is 0.2-1ml/L (such as the 1560 acid copper additive series of Lesi), the concentration of the displacer is 0.2-1ml/L (such as the 1561 acid copper additive series of Lesi), open the cylinder The concentration of the additive is 2-10ml/L (such as the 1562 acid copper additive series of Lesi).

In the above manufacturing method, the decorative layer is either hexavalent chromium plating or trivalent chromium plating. The trivalent chromium coating may be trivalent white chromium coating or trivalent black chromium coating or other types of trivalent chromium coating. When the decorative layer is a trivalent chromium coating, a passivation film may also be included on the surface of the trivalent chromium coating.

As preferably, the plating solution of hexavalent chromium plating process includes composition and concentration: the concentration of chromic anhydride is 260-360g/L, the concentration of sulfuric acid is 0.5-3g/L, the concentration of decorative chrome brightener is 2.0-3.0ml/ L (such as Lesi's 1120F or Nippon Metal Chemical's 7000C), chromium mist inhibitor 0.1-0.4ml/L. It is required that the chromium plating layer is not less than 0.1μm.

As preferably, the plating solution of trivalent white chromium plating process comprises composition and concentration: the concentration of aqueous chromium chloride is 90-150g/L, the concentration of potassium formate is 50-100g/L, and the concentration of ammonium bromide is 8-150g/L. 25g/L, the concentration of ammonium chloride is 40-60g/L, the concentration of potassium chloride is 40-100g/L, the concentration of sodium acetate is 10-60g/L, and the concentration of boric acid is 40-80g/L. The concentration of the wet agent is 0.5-2.5ml/L. It is required that the chromium plating layer is not less than 0.1μm.

Preferably, the plating solution of the trivalent black chromium plating process includes components and concentrations: the concentration of aqueous chromium chloride is 150-250g/L, the concentration of oxalic acid is 2-5g/L, and the concentration of ammonium acetate is 3-10g/L. L, the concentration of ammonium chloride is 20-40g/L, the concentration of boric acid is 20-41g/L, and the concentration of additives is 0.5-3g/L. It is required that the chromium plating layer is not less than 0.1μm.

Nickel plating with microcracks refers to plating a uniform coating containing countless cracks on the surface of the substrate, which can disperse the corrosion current and reduce the corrosion current density. Microporous nickel plating refers to plating a layer of uniform coating containing countless non-conductive particles on the plastic surface, which can further disperse the corrosion current, reduce the corrosion current density, and comprehensively improve the corrosion resistance of the coating.

In the steps of semi-bright nickel plating and full-bright nickel plating, boric acid is used as a stabilizer instead of sodium citrate in electroless nickel plating, because more attention is paid to the quality of the coating during the steps of semi-bright nickel plating and full-bright nickel plating. Deep plating ability and denseness of coating.

The reason why the microcracked nickel layer, microporous nickel layer or the combination of the two in the functional layer can prevent corrosion and protect the substrate is that the plating metal/substrate metal on the workpiece is extremely easy to form a corrosion cell. The corrosion rate is controlled by the ratio of the exposed area of the substrate metal (anode) to the surface of the coating metal (cathode). When there is only one corrosion point, the cathode/anode ratio is the largest at this time, the corrosion current is concentrated at this point, the corrosion rate becomes very large, and it is easy to form pitting corrosion inward, but when there are more potential corrosion points on the surface of the metal coating At the corrosion point, the cathode/anode ratio is small, the corrosion current is distributed everywhere, the current on the original corrosion point is significantly reduced, and the corrosion rate is also greatly reduced. At the same time, due to the division between micropores or cracks, the cathode of the coating is discontinuous, and the divided coating changes from a large area to a small area, which further limits the cathode/anode ratio. However, as time goes by, when the surface of the coating is affected by external factors and large cracks begin to appear, the potential corrosion cells of micro-cracks and micro-porous structures will be triggered, thereby protecting the corrosion points, so that it can be It plays the role of dual core to reduce the corrosion current density, thus greatly improving the corrosion resistance.

Anticorrosion Mechanism of Low Potential Nickel

Step 1: When there is a corrosive medium on the surface of the part, the exposed nickel layer at the micropores is first corroded as an anodic coating. The size of the corrosion current is determined by the surface area of the coating. Under the action of a large number of discontinuous micropores, it is corroded. The area of the nickel layer will be greatly increased and discontinuous. Under the condition of a certain corrosion current, these "micropores" greatly disperse the corrosion current, reduce the corrosion rate, and delay the corrosion rate.

Step 2: When the corrosion reaches the low-potential nickel layer, because the potential of the microporous nickel is lower than the potential of the nickel, the potential of the nickel is high. At this time, the low-potential nickel is preferentially corroded as an anodic coating (that is, the low-potential layer is preferentially used as a sacrificial layer), and the micropore Corrosion in nickel is stopped. Under the action of a large number of discontinuous microcracks, the area of the corroded nickel layer will be greatly increased and discontinuous. Under the condition of a certain corrosion current, these "micropores" greatly disperse the corrosion current and reduce the corrosion rate again. Delayed corrosion rate.

The third step: When the corrosion extends further down in the low-potential nickel until the base coating (including the coating below the low-potential nickel), since the potential of the base coating is also higher than that of the low-potential nickel, the low-potential nickel is also regarded as an anodic coating. At this time, the corrosion extending downward is terminated in the base coating, and the corrosion direction is carried out laterally in the low-potential nickel, which further delays the time for corrosion to the substrate and greatly reduces the corrosion rate.

Compared with the prior art, the utility model has the advantages that: the microporous nickel layer and the low-potential nickel layer obtained by electroplating the substrate surface of the utility model have high anti-corrosion performance, high hardness, high wear resistance, and coating bonding force Good, high brightness and other advantages; at the same time, the microporous nickel layer with high potential characteristics and the multilayer nickel with low potential characteristics—the low potential nickel layer are used as the functional layer, and the low potential nickel layer is used as the sacrificial layer to have micro The microporous nickel layer with a porous structure can disperse the microcurrent of electrochemical corrosion, delay the occurrence of corrosion, and at the same time form oxides to support the formation of oxides after oxidation through the microporous structure, which can be used as a sacrificial layer. After more serious corrosion, it forms a support to reduce the damage speed of the coating of the part. The low-potential nickel layer set as a sacrificial layer has a lower potential. When electrochemical corrosion occurs on the surface coating of the part, the low-potential nickel layer corrodes preferentially, and when there is a microporous nickel layer or a microcracked nickel layer, its micropores Or the micro-crack structure can also disperse the corrosion micro-current, and at the same time, when there is an outer layer structure outside the low-potential nickel layer (such as a decorative layer or a protective layer), the outer structure can also be supported by the micro-pore or micro-crack structure. Enhance the stability of the material structure. In addition, the utility model scheme utilizes the pore structure of microporous nickel and microcracked nickel, which can reduce the quality of the coating and reduce the consumption of raw materials while enhancing the structural support performance of the material. At the same time, its microporous structure can also form a large-area oxide film structure when oxidation and corrosion occur, thereby greatly delaying the occurrence of corrosion.

Description of drawings

Fig. 1 is the coating structure schematic diagram of an embodiment of the multilayer super corrosion-resistant nickel-chromium plating part of the present invention (using ABS as the part base material).

Fig. 2 is the coating structure schematic diagram of an embodiment of the multilayer super corrosion-resistant nickel-chromium plating part of the present invention (with ABS as part base material).

3 is a schematic diagram of the coating structure of an embodiment of the multilayer super corrosion-resistant nickel-chromium plated part of the present invention (using ABS as the part base material).

4 is a schematic diagram of the coating structure of an embodiment of the multi-layer super corrosion-resistant nickel-chromium plated part of the present invention (using ABS as the part base material).

5 is a schematic diagram of the coating structure of an embodiment of the multilayer super corrosion-resistant nickel-chrome plated part of the present invention (using ABS as the part base material).

Metallographic diagram after 72 hours of nickel-plated part CASS of Fig. 6 prior art, among Fig. 6 (a) is the front metallographic diagram of sample after experiment, among Fig. 6 (b) is the side (section) metallographic diagram of sample after experiment picture.

Fig. 7 metallographic diagram after 72 hours of nickel-plated part CASS of the utility model, among Fig. 7 (a) is the front metallographic diagram of sample after experiment, among Fig. 7 (a) is the side metallographic diagram of sample after experiment.

Fig. 8 The pictures of the nickel-plated parts of the prior art after the fluorogypsum experiment was carried out for 168 and 336 hours.

Fig. 9 is the pictures after 168 hours and 336 hours of the fluorine gypsum experiment of the nickel-plated part of the utility model.

Fig. 10 is the multilayer nickel corrosion principle diagram of the utility model (using ABS as the part base material).

Fig. 11 potential difference schematic diagram of an embodiment of nickel-plated and/or chromium parts of the utility model (the low-potential nickel layer is any one of high-sulfur nickel layer or micro-crack nickel layer, and the base layer is semi-gloss nickel layer and full-gloss nickel layer Nickel layer composite).

Fig. 12 potential difference schematic diagram of an embodiment of nickel-plated and\or chromium parts of the utility model (the low-potential nickel layer is any one of high-sulfur nickel layer or micro-crack nickel layer, and the base layer is semi-gloss nickel layer and satin Nickel layer composite).

Fig. 13 potential difference schematic diagram of an embodiment of nickel plating and/or chromium parts of the utility model (the low-potential nickel layer is any one of high-sulfur nickel layer or micro-crack nickel layer, and the base layer is semi-gloss nickel layer, high-sulfur nickel layer Nickel layer and full nickel layer composite).

Fig. 14 potential difference schematic diagram of an embodiment of the utility model nickel-plated and/or chromium parts (the low-potential nickel layer is either a high-sulfur nickel layer or a micro-crack nickel layer, and the base layer is a semi-gloss nickel layer, a high-sulfur layer Nickel layer and satin nickel layer composite).

Fig. 15 potential difference schematic diagram of an embodiment of nickel-plated and/or chromium parts of the utility model (the low-potential nickel layer is any of high-sulfur nickel layer or micro-crack nickel layer, and the base layer is semi-gloss nickel layer, full-gloss nickel layer Nickel layer and satin nickel layer composite).

Fig. 16 potential difference schematic diagram of an embodiment of nickel-plated and/or chromium parts of the utility model (the low-potential nickel layer is a composite layer of a high-sulfur nickel layer and a micro-crack nickel layer, and the base layer is a semi-gloss nickel layer and a full-gloss nickel layer Nickel layer composite).

Fig. 17 potential difference schematic diagram of an embodiment of the utility model nickel-plated and/or chromium parts (the low-potential nickel layer is a composite layer of high-sulfur nickel layer and micro-crack nickel layer, and the base layer is a semi-gloss nickel layer and satin Nickel layer composite).

Fig. 18 potential difference schematic diagram of an embodiment of the utility model nickel-plated and/or chromium parts (the low-potential nickel layer is a composite layer of a high-sulfur nickel layer and a micro-crack nickel layer, and the base layer is a semi-gloss nickel layer, a high-sulfur layer Nickel layer and full nickel layer composite).

Fig. 19 potential difference schematic diagram of an embodiment of nickel plating and/or chromium parts of the utility model (the low-potential nickel layer is a composite layer of high-sulfur nickel layer and micro-crack nickel layer, the base layer is a semi-gloss nickel layer, high-sulfur Nickel layer and satin nickel layer composite).

Fig. 20 The potential difference schematic diagram of a kind of embodiment of nickel-plated and/or chromium parts of the utility model (low-potential nickel layer is the composite layer of high-sulfur nickel layer and micro-crack nickel layer, base layer is semi-gloss nickel layer, full-gloss nickel layer Nickel layer and satin nickel layer composite).

List of reference signs: 1. Substrate; 2. Pretreatment coating; 21. Corrosion vacancy; 3. Copper plating layer; 31. Surface micropore; 32. Corrosion hole; 4. Functional layer; 141. Low potential nickel layer; 142. Microporous nickel layer; 6. Base layer; 61. High-sulfur nickel layer; 62. Semi-bright nickel layer; 63. Full-gloss nickel layer; 64. Satin nickel layer; 801. Corrosive medium; 802. Decorative layer; 805, corrosion surface; 808, primer nickel layer; 809, chemical nickel layer; 810, ABS substrate.

Detailed ways

The utility model will be further explained below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the utility model and are not intended to limit the scope of the utility model.

The coating structure of the multi-layer super corrosion-resistant nickel-chrome plated part of the present invention is described below, where the base material of the present invention can be metal, plastic and other parts suitable for electroplating.

Structural Example 1

As shown in Figure 1, the multilayer super corrosion-resistant nickel-chromium plating part of the present embodiment, this part comprises: base material 1 (ABS material); Copper layer 3, chemical nickel layer 809 is deposited on the entire substrate 1, and a bottoming nickel layer 808 is deposited on the chemical nickel layer 809, and a copper plating layer 3 is formed on the bottoming nickel layer 808; and base layer 6, which forms On the copper plating layer 3, wherein the base layer 6 includes a semi-bright nickel layer 62 and a full-bright nickel layer 63, the semi-bright nickel layer 62 is formed on the copper-plated layer 3, and the full-bright nickel layer 63 is formed on the semi-bright nickel layer 62 and a functional layer 4, which is formed on the full light nickel layer 63 of the base layer 6, wherein the functional layer 4 includes a low-potential nickel layer 141 and a microporous nickel layer 142, wherein the low-potential nickel layer 141 is a high-sulfur nickel layer and a microporous nickel layer. Crack nickel layer (can be that high-sulfur nickel layer is formed on copper-plated layer 3, and micro-crack nickel layer is formed on high-sulfur nickel layer; It can also be that micro-crack nickel layer is formed on copper-plate layer 3, and high-sulfur nickel layer forms On the micro-cracked nickel layer), the microporous nickel layer 142 is formed on the low-potential nickel layer 141; and the decoration layer 802, which is formed on the microporous nickel layer 142, wherein the decoration layer is a trivalent white chromium plating layer, here all light The potential difference between the nickel layer 63 and the low-potential nickel layer 141 is in the range of 0-100mv, and the potential difference between the semi-bright nickel layer 62 and the full-bright nickel layer 63 is in the range of 100-200mv.

Structural Example 2

As shown in Figure 2, the multilayer super corrosion-resistant nickel-chromium plating part of the present embodiment, this part comprises: base material 1 (ABS material); Copper layer 3, chemical nickel layer 809 is deposited on the entire substrate 1, and a bottoming nickel layer 808 is deposited on the chemical nickel layer 809, and a copper plating layer 3 is formed on the bottoming nickel layer 808; and base layer 6, which forms On the copper plating layer 3, wherein the base layer 6 includes a semi-bright nickel layer 62 and a satin nickel layer 64, the semi-bright nickel layer 62 is formed on the copper plating layer 3, and the satin nickel layer 64 is formed on the semi-bright nickel layer 62; And the functional layer 4, which is formed on the satin nickel layer 64 of the base layer 6, wherein the functional layer 4 includes a low-potential nickel layer 141 and a microporous nickel layer 142, wherein the low-potential nickel layer 141 is a high-sulfur nickel layer and microcracks Nickel layer (can be that the high-sulfur nickel layer is formed on the copper-plated layer 3, and the micro-crack nickel layer is formed on the high-sulfur nickel layer; it can also be that the micro-crack nickel layer is formed on the copper-plated layer 3, and the high-sulfur nickel layer is formed on the copper-plated layer 3 On the micro-crack nickel layer), the microporous nickel layer 142 is formed on the low-potential nickel layer 141; and the decoration layer 802, which is formed on the microporous nickel layer 142, wherein the decoration layer is a trivalent white chromium plating layer, where satin nickel The potential difference between the layer 64 and the low-potential nickel layer 141 is in the range of 0-100mv, and the potential difference between the semi-bright nickel layer 62 and the full-bright nickel layer 63 is in the range of 100-200mv.

Structural Example 3

As shown in Figure 3, the multilayer super corrosion-resistant nickel-chromium plating part of the present embodiment, this part comprises: base material 1 (ABS material); Copper layer 3, chemical nickel layer 809 is deposited on the entire substrate 1, and a bottoming nickel layer 808 is deposited on the chemical nickel layer 809, and a copper plating layer 3 is formed on the bottoming nickel layer 808; and base layer 6, which forms On the copper-plated layer 3, wherein the base layer 6 includes a semi-bright nickel layer 62, a high-sulfur nickel layer 61 and a full-bright nickel layer 63, the semi-bright nickel layer 62 is formed on the copper-plated layer 3, and the high-sulfur nickel layer 61 is formed on On the semi-bright nickel layer 62, the full-bright nickel layer 63 is formed on the high-sulfur nickel layer 61; and the functional layer 4, which is formed on the full-bright nickel layer 63 of the base layer 6, wherein the functional layer 4 includes a low-potential nickel layer 141 And the microporous nickel layer 142, wherein the low-potential nickel layer 141 is a high-sulfur nickel layer and a micro-crack nickel layer (can be that the high-sulfur nickel layer is formed on the copper-plated layer 3, and the micro-crack nickel layer is formed on the high-sulfur nickel layer; It can also be that the micro-crack nickel layer is formed on the copper-plated layer 3, the high-sulfur nickel layer is formed on the micro-crack nickel layer), the micro-porous nickel layer 142 is formed on the low-potential nickel layer 141; and the decoration layer 802 is formed on the On the microporous nickel layer 142, the decorative layer is a trivalent white chromium plating layer.

Structural Example 4

As shown in Figure 4, the multilayer super corrosion-resistant nickel-chromium plating part of the present embodiment, this part comprises: base material 1 (ABS material); Copper layer 3, chemical nickel layer 809 is deposited on the entire substrate 1, and a bottoming nickel layer 808 is deposited on the chemical nickel layer 809, and a copper plating layer 3 is formed on the bottoming nickel layer 808; and base layer 6, which forms On the copper plating layer 3, the base layer 6 includes a semi-bright nickel layer 62, a high-sulfur nickel layer 61 and a satin nickel layer 64, the semi-bright nickel layer 62 is formed on the copper plating layer 3, and the high-sulfur nickel layer 61 is formed on the semi-gloss nickel layer On the light nickel layer 62, a satin nickel layer 64 is formed on the high-sulfur nickel layer 61; and a functional layer 4, which is formed on the satin nickel layer 64 of the base layer 6, wherein the functional layer 4 includes a low-potential nickel layer 141 and Microporous nickel layer 142, wherein the low-potential nickel layer 141 is a high-sulfur nickel layer and a micro-crack nickel layer (can be that the high-sulfur nickel layer is formed on the copper-plated layer 3, and the micro-crack nickel layer is formed on the high-sulfur nickel layer; also It can be that the micro-crack nickel layer is formed on the copper-plated layer 3, the high-sulfur nickel layer is formed on the micro-crack nickel layer), the micro-porous nickel layer 142 is formed on the low-potential nickel layer 141; and the decoration layer 802 is formed on the micro-crack nickel layer. On the hole nickel layer 142, the decorative layer is a trivalent white chromium plating layer.

Structural Example 5

As shown in Figure 5, the multilayer super corrosion-resistant nickel-chromium plating part of the present embodiment, this part comprises: base material 1 (ABS material); Copper layer 3, chemical nickel layer 809 is deposited on the entire base material 1, and a bottoming nickel layer 808 is deposited on the chemical nickel layer 809, and a copper plating layer 3 is formed on the bottoming nickel layer 808; and a base layer 6, which forms On the copper-plated layer 3, wherein the base layer 6 includes a semi-gloss nickel layer 62, a full-gloss nickel layer 63 and a satin nickel layer 64, the semi-gloss nickel layer 62 is formed on the copper-plate layer 3, and the full-gloss nickel layer 63 is formed on the half-gloss nickel layer On the light nickel layer 62, the satin nickel layer 64 is formed on the full light nickel layer 63; and the functional layer 4, which is formed on the satin nickel layer 64 of the base layer 6, wherein the functional layer 4 includes a low potential nickel layer 141 and Microporous nickel layer 142, wherein the low-potential nickel layer 141 is a high-sulfur nickel layer and a micro-crack nickel layer (can be that the high-sulfur nickel layer is formed on the copper-plated layer 3, and the micro-crack nickel layer is formed on the high-sulfur nickel layer; also It can be that the micro-crack nickel layer is formed on the copper-plated layer 3, the high-sulfur nickel layer is formed on the micro-crack nickel layer), the micro-porous nickel layer 142 is formed on the low-potential nickel layer 141; and the decoration layer 802 is formed on the micro-crack nickel layer. On the hole nickel layer 142, the decorative layer is a trivalent white chromium plating layer.

The only difference between structural examples 6-10 and structural examples 1-5 is that the low-potential nickel layer 141 is a micro-cracked nickel layer.

The only difference between structural examples 11-15 and structural examples 1-5 is that the low-potential nickel layer 141 is a high-sulfur nickel layer.

The only difference between structural examples 16-30 and structural examples 1-15 is that the decoration layer 802 is a hexavalent chromium plating layer.

The only difference between the structural examples 31-45 and the structural examples 1-15 is that the decoration layer 802 is a trivalent black chromium plating layer.

The only difference between Structural Examples 46-90 and Structural Examples 1-45 is that: the pretreatment coating 2 includes a bottoming nickel layer 808 and a copper plating layer 3, and the bottoming nickel layer 808 is deposited on the entire substrate 1. A copper plating layer 3 is formed on the bottom nickel layer 808 .

The only difference between Structural Examples 91-135 and Structural Examples 1-45 is that the pretreatment coating 2 includes the chemical nickel layer 809 and the copper plating layer 3, the chemical nickel layer 809 is deposited on the entire substrate 1, and the chemical nickel layer Copper plating layer 3 is formed on 809 .

The only difference between Structural Examples 136-180 and Structural Examples 1-45 is that there is no pretreatment plating layer 2 , and a copper plating layer 3 is directly formed on the base material 1 .

The only difference between the structural example 181-360 and the structural example 1-180 is that the substrate 1 is made of pp material.

The only difference between structural examples 361-540 and structural examples 1-180 is that the base material 1 is made of nylon;

The only difference between Structural Example 541-720 and Structural Example 1-180 is that the base material 1 is made of pc;

The only difference between Structural Example 721-900 and Structural Example 1-180 is that the substrate 1 is made of pet material;

The only difference between Structural Example 901-1080 and Structural Example 1-180 is that the substrate 1 is bakelite;

The only difference between structural examples 1081-1260 and structural examples 1-180 is that the base material 1 is cast iron (including but not limited to gray cast iron, white cast iron, nodular cast iron, vermicular cast iron, malleable cast iron and alloy cast iron, etc.) material;

The only difference between the structural examples 1261-1440 and the structural examples 1-180 is that the base material 1 is made of steel (including various common steels, stainless steel, etc.), aluminum alloy, and magnesium alloy;

In all structural embodiments here, the potential difference between the microporous nickel layer 142 and the low-potential nickel layer 141 is in the range of 10-120mv, and the low-potential nickel layer 141 includes one of the high-sulfur nickel layer and the micro-crack nickel layer. layer or a composite coating between the two layers, the potential difference between the microporous nickel layer 142 and the low-potential nickel layer 141 is in the range of 20-100mv, when the low-potential nickel layer 141 adopts micro-crack nickel layer and high-sulfur nickel When the composite coating is applied, the potential difference between the micro-cracked nickel layer and the high-sulfur nickel layer is within 10-80mv.

As shown in FIGS. 11-20 , different potential differences can be formed through structural embodiments 1-15.

The material of the base material 1 adopted in the technical solution of the utility model can also be other materials that can be used for plating copper, nickel, and chrome coatings on its surface.

The solvent of the solution in the embodiment of the utility model is water (including but not limited to distilled water, deionized water, low hardness water, etc.) unless otherwise specified, and the concentration is measured by the solution per unit volume or mass.

The base material of the parts in the following examples is preferably made of ABS.

Preparation Examples 1-5

The manufacture method of the nickel-plated parts of an embodiment of the present invention is as follows, the surface of base material is carried out pretreatment (pretreatment comprises the following steps successively: surface degrease, surface hydrophilic treatment, surface roughening treatment, surface neutralization treatment , pre-dipping, surface activation treatment, surface debonding treatment); deposit the pre-treatment coating (including chemical nickel deposition and primer nickel) on the entire substrate, and the chemical nickel layer and primer layer formed from the surface of the substrate in sequence The bottom nickel layer, and the copper plating layer is formed on the pretreatment plating layer (outside the bottom nickel layer); and the base layer is formed on the copper plating layer, where the base layer is a semi-light nickel layer, a high-sulfur nickel layer and satin The nickel layer, the semi-gloss nickel layer is formed on the copper plating layer, the high-sulfur nickel layer is formed on the semi-gloss nickel layer, the satin nickel layer is formed on the high-sulfur nickel layer; and the low potential layer in the functional layer is formed on the base On the all-light nickel layer of the layer, the low-potential nickel layer is a high-sulfur nickel layer here; and the microporous nickel layer in the functional layer is formed on the high-sulfur nickel layer; and the decorative layer is formed on the microporous nickel layer, here The decorative layer is a trivalent white chromium layer.

The potential difference between the microporous nickel layer and the high-sulfur nickel layer (low potential nickel layer) is 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120mv or 10 Other arbitrary values in the range of -120 (embodiments 1-5 can select different numerical values in 10-120 respectively to be the potential difference between the microporous nickel layer and the low-potential nickel layer in the corresponding embodiment, the microporous nickel layer in each embodiment The potential difference with the low-potential nickel layer may also be the same). The microporous nickel layer is a nickel layer that is uniformly plated on the surface of the product and contains countless non-conductive particles and conductive particles, so that the surface of the ABS substrate workpiece has high corrosion resistance, high hardness, high wear resistance, and the coating is combined Good strength, high brightness and other advantages.

The method for nickel electroplating on the above-mentioned parts comprises the steps:

(1) Surface degreasing: Clean the ABS substrate in a mixed solution of sodium hydroxide NaOH, sodium carbonate Na ₂ CO ₃ , sodium silicate Na ₂ SiO ₃ and surfactant. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 1. Surfactants are common surfactants such as sodium dodecylsulfonate, sodium octadecylsulfonate and the like.

Table I

(2) Surface hydrophilic treatment: carried out in a mixed solution of sulfuric acid and finishing agent. In this step, the concentration ratio of sulfuric acid and surface finishing agent in different embodiments is shown in Table 2:

Table II

(3) Surface roughening treatment: after degreasing, carry out in a mixed solution of chromic anhydride CrO ₃ and sulfuric acid H ₂ SO ₄ . In this step, the concentration ratios of chromic anhydride CrO3 and sulfuric _{acid H2SO4} in different embodiments are shown in Table ₃ :

Table three

(4) Surface neutralization treatment: put the ABS substrate after surface roughening treatment into a mixed solution of hydrochloric acid and hydrazine hydrate. In this step, the concentration ratios of hydrochloric acid and hydrazine hydrate in different embodiments are shown in Table 4:

Table four

(5) Surface pre-soaking: the base material after surface neutralization treatment is carried out in hydrochloric acid solution. In this step, the concentration ratio of hydrochloric acid solution in different embodiments is shown in Table 5:

Table five

(6) surface activation treatment: adopt colloidal palladium solution to carry out surface activation treatment after neutralization, hydrochloric acid, palladium chloride PdCl in the colloidal palladium solution ₂ and stannous chloride SnCl ₂ concentration ratios in different embodiments are shown in Table 6:

Table six

(7) Surface degumming treatment: carried out in sulfuric acid H ₂ SO ₄ solution. In this step, the concentration ratio of sulfuric acid solution in different embodiments is shown in Table 7:

Table Seven

(8) Electroless nickel plating layer: mixed with nickel sulfate, sodium hypophosphite, sodium citrate C ₆ H ₅ Na ₃ O ₇ , ammonium chloride and ammonia water (ammonia water is used to adjust the pH of the solution to 8.6-9.2) in solution. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 8.

table eight

(9) Primer nickel plating: carried out in a mixed solution containing aqueous nickel sulfate Ni ₂ SO ₄ -6H ₂ O, aqueous nickel chloride NiCl ₂ --6H ₂ O, boric acid H ₃ BO ₃ and a wetting agent. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 9. The wetting agent in Table 9 is 62A from Rosuria or NIMAC 32C WETTER from MacDermid.

Table nine

(10) Copper plating layer: carried out in a mixed solution of copper sulfate CuSO ₄ , sulfuric acid H ₂ SO ₄ , chloride ions, leveling agent, displacement agent and cylinder opener. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 10. Here the leveling agent is Schleich’s 1560 acid copper additive series, the positioning agent is Schleich’s 1561 acid copper additive series, and the cylinder opener is Schleich’s 1562 acid copper additive series.

table ten

(11) Semi-bright nickel plating layer: in aqueous nickel sulfate Ni ₂ SO ₄ -6H ₂ O, aqueous nickel chloride NiCl ₂ -6H ₂ O and boric acid H ₃ BO ₃ , semi-bright nickel primary brightener, semi-bright nickel secondary It is carried out in the mixed solution of grade brightener, potential difference regulator and wetting agent. In this step, the concentration ratios of the components in the mixed solution in different embodiments are shown in Table 11. The wetting agent here is such as Schleich’s 62A or MacDermid’s NIMAC 32C WETTER, the semi-bright nickel primary brightener is Schleich’s BTL MU or MacDermid’s NIMAC SF DUCT, and the semi-bright nickel secondary brightener is Schleich’s TL- 2 or NIMAC SF LEVELER of Mai Demei, the potential difference regulator is B supplement of Lesi or NIMAC SF MAINTENANCE of Mai Demei.

Table Eleven

(12) High-sulfur nickel plating layer: carried out in a mixed solution of aqueous nickel sulfate, aqueous nickel chloride, boric acid, high-sulfur additives and wetting agents. In this step, the concentration ratios of the components in the mixed solution in different embodiments are shown in Table 12. The wetting agent here is 62A of Rosex or NIMAC 32C WETTER of MacDermid.

Table 12

(13) Sardine nickel plating layer: carried out in a mixed solution of aqueous nickel sulfate, aqueous nickel chloride, boric acid, auxiliary additives and satin nickel forming agent. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 13. Here the auxiliary additive is Elpelyt pearlbrite carrier K4 or Elpelyt carrier brightener H from Schleich, and the nickel satin forming agent is Elpelyt pearlbrite additive K6AL from Schleich.

Table 13

(14) Plating a high-sulfur nickel layer (low potential layer): carried out in a mixed solution of aqueous nickel sulfate, aqueous nickel chloride, boric acid, high-sulfur additives and wetting agents. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 14. The wetting agent here is 62A of Rosex or NIMAC 32C WETTER of MacDermid.

Table Fourteen

(15) Microporous nickel plating layer: carried out in a mixed solution of aqueous nickel sulfate, aqueous nickel chloride, boric acid, nickel sealing brightener, nickel sealing main brightening agent and nickel sealing particle carrier. In this step, the concentration ratios of the components in the mixed solution in different embodiments are shown in Table 15. Here, the nickel sealing brightener is Schleich's 63; the nickel sealing main brightener is Schleich's 610CFC; the nickel sealing particle carrier is Schleich's ENHANCER.

Table 15

(16) Trivalent white chromium plating layer (decorative layer): carried out in a mixed solution containing chromium chloride, potassium formate, ammonium bromide, ammonium chloride, potassium chloride, sodium acetate, boric acid, and wetting agent. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 16. The wetting agent here is 62A of Rosex or NIMAC 32C WETTER of MacDermid.

Table 16

The CASS experiment of the above preparation examples reaches 96-120h and above, and the fluorogypsum experiment reaches a stability of more than 336h.

The only difference between Preparation Examples 6-10 and Preparation Examples 1-5 is that the low-potential nickel layer is a microcrack layer. The microcracked nickel layer is plated in a mixed solution of aqueous nickel chloride, acetic acid, PN-1A, PN-2A, and a wetting agent. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 17. The wetting agent here is 62A of Rosex or NIMAC 32C WETTER of MacDermid.

Table 17

The only difference between Preparation Examples 11-15 and Preparation Examples 1-5 is that the low-potential nickel layer includes a high-sulfur nickel layer (each embodiment plating solution is shown in Table 14 in sequence), micro-cracked nickel layer (each embodiment plating solution is shown in Table 17 in sequence correspondingly) compound between two layers. At this time, the potential difference between the microcrack layer and the high-sulfur nickel layer is any one of 10, 20, 30, 40, 50, 60, 70, 80 or any value in the range of 10-80 mv.

The only difference between Preparation Examples 16-30 and Preparation Examples 1-15 is that the decoration layer is a hexavalent chromium layer. The hexavalent chromium plating layer is carried out in a mixed solution of chromic anhydride, sulfuric acid, decorative chrome brightener and chromium mist inhibitor. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 18. The decorative chrome brightener here is 1120F from Schleich or 7000C from Nippon Metal Chemical Industry.

Table 18

The only difference between Preparation Examples 31-45 and Preparation Examples 1-15 is that the decorative layer is a trivalent black chromium layer. The trivalent black chromium plating layer is carried out in a mixed solution containing chromium chloride, oxalic acid, ammonium acetate, ammonium chloride, boric acid and additives. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 19.

Table nineteen

The only difference between Preparation Examples 46-90 and Preparation Examples 1-45 is that the base layer includes a semi-gloss nickel layer formed sequentially outwards from the surface of the copper plating layer (see Table 10 for each embodiment plating solution correspondingly in sequence) 1) and full-gloss nickel layer. The full-bright nickel layer is coated with aqueous nickel sulfate Ni ₂ SO ₄ -6H ₂ O, aqueous nickel chloride NiCl ₂ -6H ₂ O, boric acid H ₃ BO ₃ , bright nickel softener, bright nickel main light agent and wetting agent in a mixed solution. In this step, the concentration ratio of each component in the mixed solution in different embodiments is shown in Table 20. The wetting agent here is 62A of Rusys or NIMAC 32C WETTER of MacDermid, the softener of bright nickel is 63 of Nias or NIMAC 14 INDEX of Macdermid, and the main brightening agent of bright nickel is 66E of NiMac or NiMac Chanllenger of Macdermid Plus.

Table twenty

The only difference between Preparation Examples 91-135 and Preparation Examples 1-45 is that the base layer includes a semi-gloss nickel layer formed sequentially outwards from the surface of the copper-plated layer (each embodiment plating solution is correspondingly referred to in Table 10 in sequence) 1) and satin nickel layer (each embodiment plating solution is correspondingly shown in Table 13 in sequence).

The only difference between Preparation Examples 136-180 and Preparation Examples 1-45 is that the base layer includes a semi-gloss nickel layer formed outwards from the surface of the copper-plated layer (each embodiment plating solution is correspondingly referred to in Table 10 in sequence) 1), high-sulfur layer (each embodiment plating solution is correspondingly shown in Table 12) and all-bright nickel layer (each embodiment plating solution is correspondingly shown in Table 20).

The only difference between the preparation examples 181-225 and the preparation examples 1-45 is that the base layer includes a semi-gloss nickel layer formed sequentially outwards from the surface of the copper plating layer (each embodiment plating solution is correspondingly referred to in the table sequentially) Shown in eleven), full light nickel layer (each embodiment plating solution is correspondingly shown in Table 20 in sequence) and satin nickel layer (each embodiment plating solution is correspondingly shown in Table 13 in sequence).

The only difference between Preparation Example 226-450 and Preparation Example 1-225 is that the nickel sealing brightener is Macdermid’s NIMAC 14 INDEX; the nickel sealing main brightening agent is Macdermid’s NIMAC 33; the nickel sealing particle carrier is Macdermid Midea NiMac Hypore XL dispersant.

The only difference between Preparation Example 451-900 and Preparation Example 1-450 is that the microporous nickel plating solution also includes microporous powder particles 0.3-0.8ml/L (in this embodiment about microporous powder particles The dosage can choose any value: 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), Lesi's 618; wetting agent 1.0-3.0ml/L (you can choose any value for the amount of wetting agent in the examples here : 1, 1.2, 1.3, 1.4, 1.7, 1.9, 2, 2.2, 2.3, 2.4, 2.7, 2.9, 3.0), Lesi’s 62A.

The only difference between Preparation Example 901-1350 and Preparation Example 451-900 is that the microporous powder particles in the microporous nickel plating bath are NiMac Hypore XL powder from MacDermid; the wetting agent is NIMAC 32C WETTER from MacDermid.

The only difference between Preparation Example 1351-2700 and Preparation Example 1-1350 is that the pretreatment coating is an electroless nickel layer (see Table 8 for the corresponding plating solutions of each example).

The only difference between Preparation Examples 2701-4050 and Preparation Examples 1-1350 is that the pretreatment coating is a primer nickel layer (refer to Table 9 for the corresponding plating solutions of each embodiment).

The only difference between Preparation Examples 4051-5400 and Preparation Examples 1-1350 is that there is no pretreatment coating on the surface of the substrate, and the copper plating layer is directly formed on the surface of the substrate.

In the above preparation examples, PN-1A and PN-2A are commercially available products from Atotech (China) Chemical Co., Ltd.

Based on all the above embodiments, it can be seen that all the embodiments of the technical solution of the present invention reach 96-120h and above through the CASS experiment (the prior art then proposes to be 40-48h), and the fluorogypsum experiment then reaches a stability of more than 336h (the existing The product obtained by the technology is unstable and cannot be quantified).

In the technical solution of the utility model, the base material can also be made of materials including but not limited to PC, PP, nylon, PET, bakelite, cast iron, steel, aluminum alloy, magnesium alloy and the like. When selecting other substrates except ABS, the pretreatment coating can be selected according to the actual material performance and process requirements with pretreatment coating or without pretreatment coating.

Fig. 7 is the corrosion state figure obtained after the nickel-plated part sample obtained by an embodiment of the utility model through the 72h CASS experiment, and Fig. 6 is after the nickel-plated part sample of the prior art through the 72h CASS experiment (under the same experimental conditions ) obtained by comparing the corrosion state diagram, it can be seen intuitively that the existing samples have a large number of coating peelings after the experiment and corrosion vacancies 21 after corrosion, which seriously affects the quality of the product coating. As can be seen from Fig. 7, the nickel-plated sample obtained by the utility model only has a certain number of surface micropores 31 on the surface, while the cross-section shows that there are only small corrosion holes 32, no matter the surface micropores and the sacrificial layer. The resulting corrosion holes are not able to damage the coating structure of the components, and do not affect the use and appearance of the product.

Fig. 8 and Fig. 9 are respectively the sample surface corrosion state figure (in the figure) of the nickel-plated part sample of the prior art and the nickel-plated part sample gained by an embodiment of the utility model through the fluorogypsum experiment (336h, 336h, 168h) The inside of the circle is divided into experimental areas), as can be seen from the figure, the surface of the nickel-plated parts sample of the prior art is corroded to varying degrees, while the sample obtained by the utility model is corroded very slightly, and basically does not have discoloration. It can be seen that there is no doubt that the nickel-plated part obtained by the technical solution of the utility model has better plating stability and corrosion resistance, making the nickel-plated part more durable and beautiful.

As shown in Figure 10, the mechanism when the nickel-plated parts obtained by the utility model scheme is corroded is: in the figure, the chemical nickel layer 809, the nickel layer 808, and the copper-plated layer 3 are formed layer by layer on the ABS base material 810. , base layer 6 , low potential nickel layer 141 , microporous nickel layer 142 and decoration layer 802 . The corrosion medium 801 disperses the corrosion current in the microporous structure of the microporous nickel layer 142 and enters the low potential nickel layer 141 (reduces the area actually involved in corrosion, has a smaller corrosion area, forms a plurality of independent corrosion points, thereby disperses corrosion current, slowing down the corrosion rate), after corrosion forms the corrosion surface 805, when the corrosion surface 805 penetrates the low-potential nickel layer 141 and encounters the high-potential base layer 6 and the copper plating layer 3, the vertical corrosion is stopped, and the horizontal corrosion becomes until the After the entire low-potential nickel layer 141 has been corroded, the next step of corrosion will be carried out until the coating structure is destroyed as a whole.

As can be seen from the coating potential diagrams in Figures 11 to 20, in this embodiment, no matter whether the low-potential nickel layer is a single layer or a composite layer structure, the low-potential nickel layer is used as a sacrificial layer when being corroded, and the low-potential nickel layer is used as a sacrificial layer. When the nickel layer is a composite layer of the high-sulfur nickel layer and the micro-cracked nickel layer, the potential of the high-sulfur nickel layer and the micro-cracked nickel layer is adjusted with the actual production process, and the potential of the high-sulfur nickel layer can be slightly higher, or it can be The potential of the micro-cracked nickel layer is slightly higher. When the low-potential nickel layer is completely corroded, the base layer will be corroded first in accordance with the priority order of electric corrosion to reduce the damage to the surface structure.

The embodiment here does not exhaust the mid-point value of the technical scope claimed by the utility model, and all of them are also within the scope of the utility model.

The technical means disclosed in the solution of the utility model are not limited to the technical means disclosed in the above technical means, but also include technical solutions composed of any combination of the above technical features. The above are the specific embodiments of the present utility model, and it should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present utility model, some improvements and modifications can also be made, and these improvements and modifications are also considered It is the protection scope of the utility model.

Claims (11)

1. the super anti-corrosion nickel plating-chromium parts of multilayer, these parts comprise:

Base material;

Pre-treatment coating, its deposition over the whole substrate, pre-treatment coating is formed with copper plate; With

Basal layer, it is formed on copper plate; With

Functional layer, it is formed on basal layer, and wherein functional layer comprises low potential nickel dam and is formed at the micropore nickel dam on low potential nickel dam; With

Ornament layer, it is formed on micropore nickel dam, and described ornament layer is the arbitrary of trivalent chromium coating or sexavalent chrome coating.

2. the super anti-corrosion nickel plating-chromium parts of multilayer 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. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 2, is characterized in that: described low potential nickel dam include one deck in high-sulfur nickel dam, tiny crack nickel dam or two-layer between composite deposite.

4. the super anti-corrosion nickel plating-chromium parts of the multilayer according to Claims 2 or 3, is characterized in that: the potential difference between described micropore nickel dam and low potential nickel dam is within the scope of 20-100mv.

5. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 3, is characterized in that: when low potential nickel dam adopts the composite deposite of tiny crack nickel dam and high-sulfur nickel dam, between tiny crack nickel dam and high-sulfur nickel dam, potential difference is in 10-80mv.

6. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 1, is characterized in that: described basal layer comprise in half light nickel dam, high-sulfur nickel dam, full light nickel dam, husky fourth nickel dam one or more layers.

7. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, is characterized in that: described basal layer is the compound between half light nickel dam and full light nickel dam, and wherein, half light nickel dam is formed on copper plate, and full light nickel dam is formed on half light nickel dam.

8. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, it is characterized in that: described basal layer is the compound between half light nickel dam and Sha Ding nickel dam, wherein, half light nickel dam is formed on copper plate, and husky fourth nickel dam is formed on half light nickel dam.

9. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, it is characterized in that: described basal layer is half light nickel dam, high-sulfur nickel dam and the compound entirely between light nickel dam, wherein, half light nickel dam is formed on copper plate, high-sulfur nickel dam is formed on half light nickel dam, and full light nickel dam is formed on high-sulfur nickel dam.

10. the super anti-corrosion nickel plating-chromium parts of multilayer according to claim 6, it is characterized in that: described basal layer is half light nickel dam, compound between high-sulfur nickel dam and Sha Ding nickel dam, wherein, half light nickel dam is formed on copper plate, high-sulfur nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on high-sulfur nickel dam.

The super anti-corrosion nickel plating-chromium parts of 11. multilayer according to claim 6, it is characterized in that: described basal layer is half light nickel dam, full compound between light nickel dam and Sha Ding nickel dam, wherein, half light nickel dam is formed on copper plate, full light nickel dam is formed on half light nickel dam, and husky fourth nickel dam is formed on full light nickel dam.