CN110117803B - Potassium chloride cyanide-free cadmium titanium alloy plating solution, preparation method and electroplating process thereof - Google Patents
Potassium chloride cyanide-free cadmium titanium alloy plating solution, preparation method and electroplating process thereof Download PDFInfo
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Abstract
The invention discloses a potassium chloride cyanide-free cadmium titanium alloy plating solution, a preparation method and an electroplating process thereof, wherein the plating solution comprises the following components: 20-35 g/L of cadmium chloride, 80-140 g/L of a coordination agent, 120-200 g/L of potassium chloride, 1-5 g/L of sodium fluoride, 2-5 mL/L of a titanium salt supply agent, 1-3 mL/L of a brightening agent, 20-40 mL/L of an auxiliary agent and 5-15 mL/L of a displacement agent; the electroplating operation conditions are as follows: the pH value of the plating solution is 6.5-7.5, the temperature of the plating bath is 20-35 ℃, and the cathode current density is 0.5-2A/dm2The area ratio of the cathode to the anode is 2: 1-3. The invention has the advantages of stable plating solution, convenient maintenance, small hydrogen brittleness of the process, excellent corrosion resistance of the cadmium-titanium alloy plating layer and better market prospect.
Description
Technical Field
The invention relates to the field of electroplating, in particular to the technical field of electroplating of potassium chloride cyanide-free cadmium titanium alloy.
Background
With the development of high-altitude and high-speed airplanes, the aviation industry adopts a large amount of high-strength structural materials, but the fatal weakness of the materials is high hydrogen embrittlement sensitivity and the tendency of stress corrosion cracking. Therefore, avoiding hydrogen embrittlement is a problem that must be adequately addressed during processing and use of high strength structural materials. In order to prevent hydrogen embrittlement in the electroplating process, baking is required to be carried out for more than 20 hours at 200 ℃ after electroplating for dehydrogenation, and the hydrogen removal effect is improved by using the loose-hole electroplating, but the protective performance of the loose-hole electroplated layer is poor and the use requirement cannot be met. In the early 60 s of the last century, people such as Koji Ta-kata of Japan invented a cyaniding cadmium-titanium alloy plating process, and proved that a cadmium-titanium alloy plating layer containing 0.1% -0.7% of titanium had excellent corrosion resistance and low hydrogen brittleness, and could be used as a protective layer for high-strength structural steel. This process was introduced in the united states and used as a protective layer for certain aircraft high strength steel structural members. However, this electroplating solution is prepared by dissolving pertitanate with hydrogen peroxide and then adding it into alkaline cyaniding cadmium plating solution containing no brightener, and the titanium salt is very unstable in the plating solution and is easy to hydrolyze and precipitate, so that it needs to be circularly filtered, and its operation and technological control are complex. With the increasing awareness of environmental protection, governments in various countries are strictly restricting or eliminating the use of cyanide electroplating processes at the present stage.
In 1970, cyanogen-free cadmium-titanium alloy electroplating solution was developed and used for dissolving TiOCi in hydrochloric acid2Then added into the ammonium salt cyanide-free cadmium plating solution, and the electroplating solution can be usedObtaining the cadmium-titanium alloy plating layer containing 0.1 to 0.7 percent of titanium. The ammonium salt cyanide-free cadmium-titanium alloy plating solution adopts EDTA and nitrilotriacetic acid as coordination agents, which brings great difficulty to the treatment of electroplating wastewater. The plating solution adopts thiourea and gum arabic as brightening agents, the thiourea is more mixed in the plating layer, so that the corrosion resistance of the plating layer is reduced, the gum arabic decomposition products have adverse effects on the plating layer, and the stability of the plating solution is not high.
The electroplated cadmium-titanium alloy has the characteristic of low hydrogen brittleness, and is particularly suitable for a protective layer of high-strength structural steel for the aviation industry. At present, the corrosion resistance protection of high-strength structural steel at important parts such as aircraft landing gears and the like at home and abroad adopts the cadmium-titanium alloy electroplating technology, the American Boeing company adopts the cyanide cadmium-titanium alloy electroplating technology, and China adopts the cyanide-free cadmium-titanium alloy electroplating technology.
Disclosure of Invention
Therefore, the cyanide-free cadmium titanium alloy plating solution, the preparation method thereof and the electroplating process need to be provided, so as to solve the problems that the quality of the existing cyanide-free cadmium titanium alloy plating solution and plating layer is not stable enough and the electroplating wastewater treatment is difficult.
In order to achieve the purpose, the invention provides the following technical scheme:
the potassium chloride cyanide-free cadmium titanium alloy plating solution comprises the following components in concentration: 20-35 g/L of cadmium chloride, 80-140 g/L of a coordination agent, 120-200 g/L of potassium chloride, 1-5 g/L of sodium fluoride, 2-5 mL/L of a titanium salt supply agent, 1-3 mL/L of a brightening agent, 20-40 mL/L of an auxiliary agent and 5-15 mL/L of a displacement agent;
the displacement agent comprises a water-soluble propargylamide polymer, sodium dimethylbenzenesulfonate and polyoxyethylene ether phosphate.
Furthermore, the mass concentration of the water-soluble propargylamide polymer in the displacement agent is 5-15 g/L, the mass concentration of the sodium dimethylbenzenesulfonate is 30-100 g/L, and the product type is 50-150 mL/L of the PE 600 polyoxyethylene ether phosphate.
Further, the water-soluble propargylamide polymer comprises a propargylamide polymer containing a glucose side group and/or a propargylamide polymer containing a lactose side group, and the molecular weight of the water-soluble propargylamide polymer is 10000-15000.
Furthermore, the titanium salt replenishing agent is a potassium fluotitanate aqueous solution with the mass concentration of 1.5-2.5 g/L.
Further, the complexing agent comprises A, B, C components, wherein the component A comprises nitrilotriacetic acid, the component B comprises any one or two of citric acid, tartaric acid, gluconic acid and malic acid, the component C comprises any one or two of malonic acid, maleic acid, fumaric acid and oxalic acid, and the A, B, C components are uniformly mixed to obtain the complexing agent;
the brightener comprises D, E, F three components, wherein the component D comprises alpha-vinyl-N-propyl sulfonic pyridine inner salt (CAS NO.6613-64-5), the component E comprises any one or two of 3-methoxy-4-hydroxybenzaldehyde, 3, 4-dimethoxybenzaldehyde and 4-methoxybenzaldehyde, and the component F comprises any one or two of propargyl alcohol ethoxy ether, propargyl alcohol propoxy ether, N-diethyl propargyl amine, N-diethyl propargyl amine formate and N, N-diethyl propargyl amine sulfate;
the auxiliary agent comprises water-soluble polyacrylamide with the model number of IC113, 2-ethylhexyl sulfate sodium salt, N, N, N-tri (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine, a component G and a condensation compound consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, wherein the component G is consistent with the component F in the brightener.
Further, the ratio of the component A, the component B and the component C in the complexing agent is as follows: 300-400 g: 350-450 g: 250-350 g, and all the components are added into a container to be stirred and mixed to form a complexing agent;
the preparation proportion of the brightener is as follows: adding 300mL of isopropanol into 400mL of water, uniformly mixing, dissolving D, E and F components into a mixed solution of isopropanol and water according to 50-60 g, 35-45 g and 70-90 g respectively, and adding water to 1000 mL;
the preparation proportion of the auxiliary agent is as follows: 60-70G of water-soluble polyacrylamide with the type of IC113, 30-40G of condensation compound consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, 50-60G of 2-ethylhexyl sulfate sodium salt, 15-25G N, N, N-tris (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine and 40-50G G components are added into 700G of water, stirred to be dissolved, and then water is added to 1000mL, wherein the component G is consistent with the component F in the brightener.
The preparation method of the potassium chloride cyanide-free cadmium titanium alloy plating solution comprises the following steps:
(1) preparing a complexing agent: the proportion of the component A, the component B and the component C is as follows: 300-400 g: 350-450 g: 250-350 g, and all the components are added into a container and stirred and mixed;
preparing a displacement agent: adding 5-15 g of water-soluble propargylamide polymer, 30-100 g of sodium dimethyl benzenesulfonate and 50-150 mL of polyoxyethylene ether phosphate with the product model of PE 600 into 500mL of water, uniformly stirring, and adding water to 1000 mL;
preparing a brightening agent: adding 300mL of isopropanol into 400mL of water, uniformly mixing, dissolving D, E and F components into a mixed solution of isopropanol and water according to 50-60 g, 35-45 g and 70-90 g respectively, and adding water to 1000 mL;
preparing an auxiliary agent: adding 60-70G of water-soluble polyacrylamide with the type of IC113, 30-40G of condensation compound consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, 50-60G of 2-ethylhexyl sulfate sodium salt, 15-25G N, N, N-tris (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine and 40-50G G (the component G is consistent with the component F in the brightener) into 700G of water, stirring to dissolve the water, and supplementing the water to 1000 mL;
(2) adding water of 4/5 aqueduct volume into a plating bath, adding sodium hydroxide, potassium chloride, sodium fluoride and a complexing agent, wherein the mass ratio of the sodium hydroxide to the complexing agent is 1: 2, generating corresponding salt by the sodium hydroxide and the organic acid complexing agent, and stirring to dissolve the substances;
(3) adding cadmium chloride, stirring to dissolve the cadmium chloride, and filtering the plating solution;
(4) at 0.05-0.1A/dm2Electrolyzing for 1-8 h under the cathode current density;
(5) then adding a titanium salt supply agent, and uniformly stirring;
(6) sequentially adding a brightening agent, an auxiliary agent and a displacement agent, adjusting the pH value of the plating solution to 6.5-7.5 by using dilute hydrochloric acid with the volume ratio of 1: 1 or sodium hydroxide solution with the mass fraction of 10%, adding water to the specified volume, and uniformly stirring;
the concentration of cadmium chloride in the finally obtained plating solution reaches 20-35 g/L, the concentration of a coordination agent reaches 80-140 g/L, the concentration of potassium chloride reaches 120-200 g/L, the concentration of sodium fluoride reaches 1-5 g/L, the concentration of a titanium salt supply agent reaches 2-5 mL/L, the concentration of a brightening agent reaches 1-3 mL/L, the concentration of an auxiliary agent reaches 20-40 mL/L, and the concentration of a displacement agent reaches 5-15 mL/L.
The electroplating process of the potassium chloride cyanide-free cadmium titanium alloy plating solution comprises the following steps:
(1) pre-treating a workpiece to be plated;
(2) preparing a potassium chloride cyanide-free cadmium titanium alloy plating solution;
(3) electroplating, wherein the pH value of the electroplating solution is 6.5-7.5 during electroplating, the temperature of the electroplating bath is 20-35 ℃, and the anode adopts a cadmium anode plate with the cadmium content of more than or equal to 99.97%;
when the rack plating process is adopted, the cathode current density is 0.5-2A/dm2The area ratio of the anode to the cathode is 2: 1-3;
when the barrel plating process is adopted, the voltage of a plating bath is 5-10V, and the rotating speed of a barrel is 4-8 r/min;
(4) hydrogen removal: removing hydrogen from the plated part at 200 ℃ for 12 h;
(5) chromate low-chromium color passivation: the cadmium-titanium alloy coating is subjected to '2% nitric acid light extraction → water washing → chromate low-chromium color passivation → water washing → drying' to prepare the chromate low-chromium color passivation layer.
Preferably, when the content of organic impurities in the plating tank is too high, treating the organic impurities by using activated carbon, adding 2-4 g/L of activated carbon powder into the plating solution, stirring for 60-120 min, and filtering the plating solution after 2-8 h; after the filter element is cleaned, 0.5-1 mL/L brightener is added into the plating solution.
Preferably, when the plating bath is polluted by harmful metal impurities, the plating bath is treated by an electrolytic method, an iron cathode plate is hung in the plating bath, and the area ratio of the cathode to the anode is 2: 1 and is 0.05-0.1A/dm2Electrolyzing for 1-2 h under the cathode current density; then 1-3 mL/L of titanium salt replenishing agent is supplemented.
Compared with the prior art, the invention has the following beneficial effects:
(1) the cadmium-titanium alloy plated part prepared by the potassium chloride cyanide-free cadmium-titanium alloy electroplating process is subjected to neutral salt spray test for 2800h according to GB/T10125-1997 salt spray test for artificial atmosphere corrosion test, a cadmium-titanium alloy plating layer does not generate red corrosive substances, and the corrosion resistance of the plating layer is far higher than that of GB/T13322-1991 low-hydrogen brittle cadmium-titanium plating layer for 500h which does not generate red corrosive substances;
(2) the displacement agent can obviously improve the displacement capacity of the plating solution and expand the range of the current density of the plating solution, and the upper limit of the current density of the acid cyanide-free cadmium plating process in the prior art is 1.5A/dm2The upper limit of the current density is 2A/dm2Compared with the orthogenic cyanide-free cadmium plating process, the upper limit of the current density is increased by 33 percent, the deep plating capacity of the plating solution can be improved by plating at higher current density, the problem that the plating layer in a high current density area is rough after a titanium salt replenishing agent is added into the plating solution is avoided, and the production efficiency can be obviously improved in actual production;
(3) the potassium fluotitanate adopted by the invention has better solubility, can be completely dissolved in the plating solution, and the plating solution does not generate titanium salt hydrolysis precipitate; TiOCi used by adopting traditional cadmium-titanium alloy electroplating process2The potassium chloride cyanide-free cadmium titanium alloy can not be effectively dissolved in the potassium chloride cyanide-free cadmium titanium alloy plating solution;
(4) the invention adopts sodium fluoride as the coordination agent of titanium salt, increases the stability of hexafluoro titanium complex ions, and prevents the hexafluoro titanium complex ions from generating precipitates due to hydrolysis reaction in plating solution;
(5) the invention adopts the modern electroplating additive intermediate to prepare the brightener and the auxiliary agent, reduces the inclusion amount of organic matters in the plating layer, and improves the flexibility and the corrosion resistance of the plating layer compared with the traditional cadmium-titanium alloy electroplating process;
(6) according to the invention, a strong coordination agent (such as EDTA disodium salt) is not adopted to coordinate cadmium ions, so that the difficulty in cadmium plating wastewater treatment is reduced, and the wastewater treatment result meets the requirements of GB 21900-.
Detailed Description
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
Example 1:
the components and concentrations of the potassium chloride cyanide-free cadmium titanium alloy plating solution of the embodiment are as follows:
30g/L of cadmium chloride, 150g/L of potassium chloride, 130g/L of coordination agent, 3g/L of sodium fluoride, 5mL/L of titanium salt supply agent, 2mL/L of brightening agent, 30mL/L of auxiliary agent and 10mL/L of displacement agent;
the dislocation agent contains water-soluble propargylamide polymer with the mass concentration of 8-12 g/L, sodium dimethylbenzenesulfonate with the mass concentration of 50-80 g/L and polyethylene oxide ether phosphate with the product type of PE 600 of 80-120 mL/L. Adding 8-12 g of water-soluble propargylamide polymer, 80-120 mL of polyoxyethylene ether phosphate with the mass concentration of 50-80 g of sodium dimethylbenzenesulfonate and the product model of PE 600 into 500mL of water, stirring uniformly, and adding water to 1000 mL.
The complexing agent consists of A, B, C components, wherein the component A is nitrilotriacetic acid, the component B is one or two of citric acid, tartaric acid, gluconic acid and malic acid, the component C is one or two of malonic acid, maleic acid, fumaric acid and oxalic acid, and the complexing agent is prepared according to the following proportion: A. 300-400 g; B. 350-450 g; C. 250-350 g, and adding into a container, stirring and mixing uniformly.
The brightener consists of D, E, F three components, wherein the component D is alpha-vinyl-N-propyl sulfonic pyridine inner salt (CAS NO.6613-64-5), the component E is composed of any one or two of 3-methoxy-4-hydroxybenzaldehyde, 3, 4-dimethoxybenzaldehyde and 4-methoxybenzaldehyde, and the component F is composed of any one or two of propargyl alcohol ethoxy ether, propargyl alcohol propoxy ether, N-diethyl propargyl amine, N-diethyl propargyl amine formate and N, N-diethyl propargyl amine sulfate. The brightener is prepared by the following steps: adding 300mL of isopropanol into 400mL of water, uniformly mixing, dissolving D, E and F components into the mixed solution of isopropanol and water according to 50-60 g, 35-45 g and 70-90 g respectively, and adding water to 1000 mL.
The adjuvant is prepared by the following method: 60-70G of water-soluble polyacrylamide with the type of IC113, 30-40G of condensation compound consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, 50-60G of 2-ethylhexyl sulfate sodium salt, 15-25G N, N, N-tris (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine and 40-50G G components (the component G is consistent with the component F in the brightener) are added into 700G of water, stirred to be dissolved, and then the water is added to 1000 mL.
The titanium salt replenishing agent is an aqueous solution of potassium fluotitanate, 2g of potassium fluotitanate is dissolved in 800mL of water, and water is added to the solution until the volume is 1000 mL.
The potassium chloride cyanide-free cadmium titanium alloy plating solution is prepared by the following method:
(1) adding 4/5 volume of water into the plating bath, sequentially adding sodium hydroxide, potassium chloride, sodium fluoride and complexing agent at a mass ratio of 1: 2, and stirring to dissolve the above substances;
(2) then adding cadmium chloride, stirring until the cadmium chloride is dissolved, and filtering the plating solution;
(3) at 0.07A/dm2Electrolyzing for 1-8 h under the cathode current density;
(4) then adding a titanium salt supply agent, and uniformly stirring;
(5) adding brightener, adjuvant and displacement agent sequentially, adjusting pH of the plating solution to 7 with dilute hydrochloric acid at volume ratio of 1: 1 or 10% sodium hydroxide solution, adding water to specified volume, and stirring.
Finally, the concentration of potassium chloride in the plating solution reaches 150g/L, the concentration of sodium fluoride reaches 3g/L, the concentration of a coordination agent reaches 130g/L, the concentration of a titanium salt replenishing agent reaches 4mL/L, the concentration of cadmium chloride reaches 30g/L, the concentration of a brightening agent reaches 2mL/L, the concentration of an auxiliary agent reaches 30mL/L, and the concentration of a displacement agent reaches 10 mL/L.
The operation of the embodiment is divided into the following steps:
(1) pretreatment: the method comprises the following steps of performing alkaline chemical degreasing → water washing → alkaline anode electrolytic degreasing → water washing → activation → water washing on a workpiece to be plated (high-strength steel part).
(2) Electroplating a cadmium-titanium alloy plating layer: after the pretreatment of the plated workpiece, the electroplating of potassium chloride cyanide-free cadmium-titanium alloy → water washing → drying is carried out to prepare the cadmium-titanium alloy plating layer. The operating conditions during electroplating were as follows:
the pH value of the plating solution is 6.5-7.5, the temperature of the plating bath is 25 ℃, and the cathode current density is 1.5A/dm2The area ratio of the cathode to the anode is 1: 1, and the anode is a cadmium plate with the cadmium content being more than or equal to 99.97 percent.
(3) Hydrogen removal: the plated piece is dehydrogenated for 12h at 200 ℃.
(4) Chromate low-chromium color passivation: the cadmium-titanium alloy coating is subjected to '2% nitric acid light extraction → water washing → chromate low-chromium color passivation → water washing → drying' to prepare the chromate low-chromium color passivation layer.
When the content of organic impurities in the plating tank is too high, treating the organic impurities with activated carbon, adding 2-4 g/L of activated carbon powder into the plating solution, stirring for 60-120 min, and filtering the plating solution after 2-8 h; after the filter element is cleaned, 0.5-1 mL/L brightener is added into the plating solution.
When the plating bath is polluted by harmful metal impurities, treating the metal by an electrolysis method, hanging an iron cathode plate in the plating bath, wherein the area ratio of a cathode to an anode is 2: 1 and is 0.05-0.1A/dm2Electrolyzing for 1-2 h under the cathode current density; then 1-3 mL/L of titanium salt replenishing agent is supplemented.
Corrosion resistance of the plating layer:
the plating piece prepared by the process is subjected to neutral salt spray test for 3000 hours according to GB/T10125-1997 salt spray test for artificial atmosphere corrosion test, and the cadmium-titanium alloy plating layer does not generate red corrosive substances. The corrosion resistance of the cadmium-titanium alloy plating layer prepared by the embodiment is far higher than that of GB/T13322-.
Deep plating capacity of the plating solution:
electroplating thin-wall iron pipe with inner diameter of 10mm in the above-mentioned plating solution, making anode be perpendicular to liquid level, making inner hole direction of iron pipe be parallel to anode, soaking the iron pipe in the plating solution for 100mm, calculating according to external surface area, and calculating according to 2A/dm2The current density is plated for 40min, and then the sample is passivated in a low-chromium passivation solution for 10s, washed and dried. The sample is longitudinally cut, the length of the inner hole coating is measured to be 98mm, the ratio of the coating length to the hole diameter is measured to be 9.8, and the plating solution has good deep plating capacity.
Coating binding force:
the coating binding force was determined by thermal shock test according to JB 2111-1977 "method for testing the binding strength of Metal coatings". The cadmium-plated part prepared by the process is placed in a heating furnace to be heated to 190 ℃, taken out and placed in water at room temperature to be cooled suddenly, the plating layer does not foam or fall off, and the cadmium-titanium alloy plating layer has good bonding force.
The mass fraction test result of the titanium in the coating is as follows:
the prepared potassium chloride cyanide-free cadmium titanium alloy plating solution is subjected to a 267mL Hell bath test and is plated for 40min at a current of 0.5A. The mass fraction of titanium in the coating was measured by an X-Strata 980 type X-ray fluorescence coating measuring instrument, and the results are shown in Table 1. The mass fraction of the titanium in the plating layer meets the requirement of the GB/T13322-1991 'Metal covering layer low hydrogen embrittlement cadmium titanium electroplating layer' standard
TABLE 1 Mass fraction of titanium in cadmium titanium alloy coating
Electroplating wastewater treatment:
the cadmium ions in the cadmium-titanium alloy electroplating wastewater are precipitated by using sodium dimethyldithiocarbamate, and the mass concentration of the treated cadmium ions is less than 0.01mg/L, so that the cadmium ions meet the requirements of GB 21900-.
Example 2:
the components and concentrations of the potassium chloride cyanide-free cadmium titanium alloy barrel plating solution of the embodiment are as follows:
25g/L of cadmium chloride, 180g/L of potassium chloride, 100g/L of coordination agent, 1g/L of sodium fluoride, 2mL/L of titanium salt supply agent, 2mL/L of brightening agent, 30mL/L of auxiliary agent and 5mL/L of displacement agent;
the dislocation agent contains water-soluble propargylamide polymer with the mass concentration of 5-10 g/L, sodium dimethylbenzenesulfonate with the mass concentration of 70-100 g/L and polyethylene oxide ether phosphate with the product type of PE 600 of 100-150 mL/L. Adding 5-10 g of water-soluble propargylamide polymer, 100-150 mL of polyoxyethylene ether phosphate with the mass concentration of 70-100 g of sodium dimethylbenzenesulfonate and the product type of PE 600 into 500mL of water, stirring uniformly, and adding water to 1000 mL.
The preparation method of the complexing agent, the brightening agent, the auxiliary agent and the titanium salt replenishing agent is the same as that of example 1.
The potassium chloride cyanide-free cadmium titanium alloy plating solution is prepared by the following method:
(1) adding 4/5 volume of water into the plating bath, sequentially adding sodium hydroxide, potassium chloride, sodium fluoride and complexing agent at a mass ratio of 1: 2, and stirring to dissolve the above substances;
(2) then adding cadmium chloride, stirring until the cadmium chloride is dissolved, and filtering the plating solution;
(3) at 0.08A/dm2Electrolyzing for 1-8 h under the cathode current density;
(4) then adding a titanium salt supply agent, and uniformly stirring;
(5) adding brightener, adjuvant and displacement agent sequentially, adjusting pH of the plating solution to 7.5 with dilute hydrochloric acid at volume ratio of 1: 1 or 10% sodium hydroxide solution, adding water to specified volume, and stirring.
Finally, the concentration of potassium chloride in the plating solution reaches 180g/L, 100g/L of coordination agent, 25g/L of cadmium chloride, 1g/L of sodium fluoride, 2mL/L of titanium salt supply agent, 2mL/L of brightening agent, 30mL/L of auxiliary agent and 5mL/L of displacement agent.
The operation of the embodiment is divided into the following steps:
(1) pretreatment: the method comprises the following steps of performing alkaline chemical degreasing → water washing → ultrasonic chemical degreasing → water washing → activation → water washing on a workpiece to be plated (high-strength steel part).
(2) Rolling and plating a cadmium-titanium alloy plating layer: after the pretreatment of the plated workpiece, performing barrel plating of potassium chloride cyanide-free cadmium-titanium alloy → water washing → drying to prepare the cadmium-titanium alloy plating layer. The operating conditions during electroplating were as follows:
the pH value of the plating solution is 7.5, the temperature of the plating bath is 30 ℃, the voltage of the plating bath is 6V, the rotating speed of the rotary drum is 6r/min, and the anode is a cadmium plate with the cadmium content being more than or equal to 99.97 percent.
(3) Hydrogen removal: the plated piece is dehydrogenated for 12h at 200 ℃.
(4) Chromate low-chromium color passivation: the cadmium-titanium alloy coating is subjected to '2% nitric acid light extraction → water washing → chromate low-chromium color passivation → water washing → drying' to prepare the chromate low-chromium color passivation layer.
When the content of organic impurities in the plating tank is too high, treating the organic impurities with activated carbon, adding 2-4 g/L of activated carbon powder into the plating solution, stirring for 60-120 min, and filtering the plating solution after 2-8 h; after the filter element is cleaned, 0.5-1 mL/L brightener is added into the plating solution.
When the plating bath is polluted by harmful metal impurities, treating the metal by an electrolysis method, hanging an iron cathode plate in the plating bath, wherein the area ratio of a cathode to an anode is 2: 1 and is 0.05-0.1A/dm2Electrolyzing for 1-2 h under the cathode current density; then 1-3 mL/L of titanium salt replenishing agent is supplemented.
Corrosion resistance of the plating layer:
the plating piece prepared by the process is subjected to neutral salt spray test for 2800h according to GB/T10125-1997 salt spray test for artificial atmosphere corrosion test, and the cadmium-titanium alloy plating layer has no red corrosive and excellent corrosion resistance.
Coating binding force:
the coating binding force was determined by thermal shock test according to JB 2111-1977 "method for testing the binding strength of Metal coatings". The cadmium-plated part prepared by the process is placed in a heating furnace to be heated to 190 ℃, taken out and placed in water at room temperature to be cooled suddenly, the plating layer does not foam or fall off, and the binding force of the cadmium-plated layer is good.
The plating solution deep plating ability, the test result of the mass fraction of titanium in the plating layer and the treatment result of the electroplating wastewater are the same as those of example 1.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The potassium chloride cyanide-free cadmium titanium alloy plating solution is characterized by comprising the following components in percentage by weight: 20-35 g/L of cadmium chloride, 80-140 g/L of a coordination agent, 120-200 g/L of potassium chloride, 1-5 g/L of sodium fluoride, 2-5 mL/L of a titanium salt supply agent, 1-3 mL/L of a brightening agent, 20-40 mL/L of an auxiliary agent and 5-15 mL/L of a displacement agent;
the pH of the plating solution is = 6.5-7.5;
the displacement agent comprises a water-soluble propargylamide polymer, sodium dimethylbenzenesulfonate and polyoxyethylene ether phosphate;
the mass concentration of the water-soluble propargylamide polymer in the dislocation agent is 5-15 g/L, the mass concentration of the sodium dimethylbenzenesulfonate is 30-100 g/L, and the mass concentration of the polyoxyethylene ether phosphate is 50-150 mL/L;
the water-soluble propargylamide polymer comprises a propargylamide polymer containing a glucose side group and/or a propargylamide polymer containing a lactose side group, and the molecular weight of the water-soluble propargylamide polymer is 10000-15000;
the titanium salt replenishing agent is a potassium fluotitanate water solution with the mass concentration of 1.5-2.5 g/L;
the complexing agent comprises A, B, C components, wherein the component A comprises nitrilotriacetic acid, the component B comprises any one or two of citric acid, tartaric acid, gluconic acid and malic acid, the component C comprises any one or two of malonic acid, maleic acid, fumaric acid and oxalic acid, and the A, B, C components are uniformly mixed to obtain the complexing agent;
the brightener comprises D, E, F three components, wherein the component D comprises alpha-vinyl-N-propyl sulfonic pyridine inner salt, the component E comprises any one or two of 3-methoxy-4-hydroxybenzaldehyde, 3, 4-dimethoxybenzaldehyde and 4-methoxybenzaldehyde, and the component F comprises any one or two of propargyl alcohol ethoxy ether, propargyl alcohol propoxy ether, N-diethyl propargylamine, N-diethyl propargylamine formate and N, N-diethyl propargylamine sulfate;
the auxiliary agent comprises water-soluble polyacrylamide, 2-ethylhexyl sulfate sodium salt, N, N, N-tri (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine, a G component and a condensate consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, wherein the G component is consistent with the F component in the brightening agent;
the ratio of the component A, the component B and the component C in the complexing agent is as follows: 300-400 g: 350-450 g: 250-350 g, and all the components are added into a container to be stirred and mixed to form a complexing agent;
the preparation proportion of the brightener is as follows: adding 300mL of isopropanol into 400mL of water, uniformly mixing, dissolving D, E and F components into a mixed solution of isopropanol and water according to 50-60 g, 35-45 g and 70-90 g respectively, and adding water to 1000 mL;
the preparation proportion of the auxiliary agent is as follows: 60-70G of water-soluble polyacrylamide, 30-40G of a condensation compound consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, 50-60G of 2-ethylhexyl sulfate sodium salt, 15-25G N, N, N-tris (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine and 40-50G G components are added into 700G of water, stirred to be dissolved, and then added with water to 1000mL, wherein the G component is consistent with the F component in the brightener.
2. The method for preparing the potassium chloride cyanide-free cadmium titanium alloy plating solution according to claim 1, which is characterized in that:
the method comprises the following steps:
(1) preparing a complexing agent: the proportion of the component A, the component B and the component C is as follows: 300-400 g: 350-450 g: 250-350 g, and all the components are added into a container and stirred and mixed;
preparing a displacement agent: adding 5-15 g of water-soluble propargylamide polymer, 30-100 g of sodium dimethyl benzene sulfonate and 50-150 mL of polyoxyethylene ether phosphate into 500mL of water, uniformly stirring, and adding water to 1000 mL;
preparing a brightening agent: adding 300mL of isopropanol into 400mL of water, uniformly mixing, dissolving D, E and F components into a mixed solution of isopropanol and water according to 50-60 g, 35-45 g and 70-90 g respectively, and adding water to 1000 mL;
preparing an auxiliary agent: 60-70G of water-soluble polyacrylamide, 30-40G of a condensation compound consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, 50-60G of 2-ethylhexyl sulfate sodium salt, 15-25G N, N, N-tris (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine and 40-50G G components, wherein the G component is consistent with the F component in the brightener, added into 700G of water, stirred to be dissolved, and then added with water to 1000 mL;
(2) adding 4/5 volume of water into the plating bath, adding sodium hydroxide, potassium chloride, sodium fluoride and complexing agent at a mass ratio of 1: 2, and stirring to dissolve the sodium hydroxide and organic acid complexing agent;
(3) adding cadmium chloride, stirring to dissolve the cadmium chloride, and filtering the plating solution;
(4) at 0.05-0.1A/dm2Electrolyzing for 1-8 h under the cathode current density;
(5) then adding a titanium salt supply agent, and uniformly stirring;
(6) sequentially adding a brightening agent, an auxiliary agent and a displacement agent, adjusting the pH value of the plating solution to 6.5-7.5 by using dilute hydrochloric acid with the volume ratio of 1: 1 or sodium hydroxide solution with the mass fraction of 10%, adding water to the specified volume, and uniformly stirring;
the concentration of cadmium chloride in the finally obtained plating solution reaches 20-35 g/L, the concentration of a coordination agent reaches 80-140 g/L, the concentration of potassium chloride reaches 120-200 g/L, the concentration of sodium fluoride reaches 1-5 g/L, the concentration of a titanium salt supply agent reaches 2-5 mL/L, the concentration of a brightening agent reaches 1-3 mL/L, the concentration of an auxiliary agent reaches 20-40 mL/L, and the concentration of a displacement agent reaches 5-15 mL/L.
3. The process of claim 1, wherein the plating solution comprises the following steps:
the method comprises the following steps:
(1) pre-treating a workpiece to be plated;
(2) preparing a potassium chloride cyanide-free cadmium titanium alloy plating solution;
(3) electroplating, wherein the pH value of the electroplating solution is 6.5-7.5 during electroplating, the temperature of the electroplating bath is 20-35 ℃, and the anode adopts a cadmium anode plate with the cadmium content of more than or equal to 99.97%;
when the rack plating process is adopted, the cathode current density is 0.5-2A/dm2The area ratio of the anode to the cathode is 2: 1-3;
when the barrel plating process is adopted, the voltage of a plating bath is 5-10V, and the rotating speed of a barrel is 4-8 r/min;
(4) hydrogen removal: removing hydrogen from the plated part at 200 ℃ for 12 h;
(5) chromate low-chromium color passivation: and (3) carrying out 2% nitric acid light extraction on the cadmium-titanium alloy coating → water washing → chromate low-chromium color passivation → water washing → drying to prepare the chromate low-chromium color passivation layer.
4. The process of claim 3 wherein the plating solution of potassium chloride cyanide-free cadmium titanium alloy is prepared by:
when the content of organic impurities in the plating tank is too high, treating the organic impurities with activated carbon, adding 2-4 g/L of activated carbon powder into the plating solution, stirring for 60-120 min, and filtering the plating solution after 2-8 h; after the filter element is cleaned, 0.5-1 mL/L brightener is added into the plating solution.
5. The process of claim 3 wherein the plating solution of potassium chloride cyanide-free cadmium titanium alloy is prepared by:
when the plating bath is polluted by harmful metal impurities, treating the metal by an electrolysis method, hanging an iron cathode plate in the plating bath, wherein the area ratio of a cathode to an anode is 2: 1 and is 0.05-0.1A/dm2Electrolyzing for 1-2 h under the cathode current density; then 1-3 mL/L of titanium salt replenishing agent is supplemented.
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