CN105671599A - Sulfate trivalent chromium electroplating solution and preparation method thereof - Google Patents

Sulfate trivalent chromium electroplating solution and preparation method thereof Download PDF

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Publication number
CN105671599A
CN105671599A CN201610219258.XA CN201610219258A CN105671599A CN 105671599 A CN105671599 A CN 105671599A CN 201610219258 A CN201610219258 A CN 201610219258A CN 105671599 A CN105671599 A CN 105671599A
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trivalent chromium
sodium
plating solution
acid
trivalent
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骆祖文
张爱玲
王鲁艳
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DILIGENCE TECHNOLOGY Co Ltd
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DILIGENCE TECHNOLOGY Co Ltd
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Priority to CN201610219258.XA priority Critical patent/CN105671599A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/04Electroplating: Baths therefor from solutions of chromium
    • C25D3/06Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/04Electroplating: Baths therefor from solutions of chromium
    • C25D3/10Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used

Abstract

The invention discloses a sulfate trivalent chromium electroplating solution and a preparation method thereof.The method includes the steps that a tank body is soaked with sulfuric acid with the volume ratio being 1%; pure water is injected into the tank body; conductive salt and buffering salt are added; a trivalent chromium ion solution is added; a brightening agent, a wetting agent and a promoting agent which are of a certain quantity are added, and electrolytic dummy plating can be performed.The sulfate trivalent chromium electroplating solution includes 150-250 g/L conductive salt, 60-120 g/L buffering salt, 5-20 g/L trivalent chromium ions, a 10-20 g/L complexing agent, a 0.1-1 g/L brightening agent, 1-5 g/L C-S compounds, 1-4 g/L saccharin sodium reactant and a 0.1-1 g/L wetting agent.The performance of a sulfate trivalent chromium electroplating technology is improved by means of the sulfate trivalent chromium electroplating solution; an obtained trivalent chromium coating is white, bright and fine, the deposition speed of the coating is high, and the covering capacity and the even-plating capacity are excellent.

Description

A kind of trivalent chromium sulfate plating solution and preparation method thereof
Technical field
The invention belongs to electroplating technology field, particularly relate to a kind of trivalent chromium sulfate plating solution and preparation method thereof.
Background technology
Chromium plating occupies extremely important status in electroplating technology, is listed in one of three big platings. For a long time, chromium plating adopts hexavalent chromium plating liquid. But Cr VI toxicity is about chromic 100 times, and can not degrade, long-term absorption will cause the diseases such as squamous cell carcinoma, sarcoma and adenocarcinoma. Chromic waste water, refuse can not at nature natural degradations as cyanide, and in human body and organism inner accumulated, the incubation period of its harm for a long time, is the extremely strong strong carcinogen of a kind of toxicity, is also serious corrosive medium. Along with the countries in the world growing interest to environmental problem, the reality that traditional hexavalent chromium plating is on the verge of being replaced. researcher both domestic and external has carried out much research for the Cr VI technique replacing high pollution, if stannum-cobalt-zinc is for chromium process, the requirement to outward appearance such as small workpiece can be met, but be difficult to reach the requirement of hardness aspect. And obtain most attention as more environmental protection, the better trivalent chromium plating technique of gained coating. Trivalent chromium plating solution can be divided into chloride type and sulfate type system by system. Chloride type system plating solution contains substantial amounts of chloride ion, poisonous chlorine is discharged during production, environment and equipment there is harm, and the aspect existing defects such as plating solution color and luster and impurity tolerance. sulphate type trivalent chromium plating system is without chloride ion, not producing any toxic gas in electroplating process, and tint is consistent with Cr VI, coating covering power and covering power are superior, tank liquor impurity can pass through cleaner and easily remove, and safeguards more simple. Therefore, sulfate trivalent chromium plating system is increasingly subject to the favor in market. and external, sulfate trivalent chromium electroplating technology is also conducted in-depth research by many experts and company. Trivalent chromium source is set forth by US1591051, it is preferable that chromic sulfate is as chromium source; Thiourea ligand effect etc. has been studied by US4062737; The application in trivalent chromium plating of the C-S key compounds has been carried out research etc. by US4502927. Market also occurs in that some comparatively outstanding trivalent chromium plating products, such as the chloride trivalent chromium plating system of ATOTECH, produces chlorine, and color and luster is partially dark;MACDERMID sulfate trivalent chromium plating system, coating sedimentation rate is relatively slow, and electroplates for a long time, and Deposit appearance turns white, requirement can not be met. domestic also have some producers as above equine skill etc. to develop similar products, there is certain defect problem and can not be popularized in an all-round way.
Summary of the invention
It is an object of the invention to provide a kind of trivalent chromium sulfate plating solution and preparation method thereof, it is intended to solve existing trivalent chromium plating product color partially dark, coating sedimentation rate is relatively slow, and electroplates for a long time, and Deposit appearance turns white, it is impossible to meet the problem required.
The preparation method that the present invention is achieved in that a kind of trivalent chromium sulfate plating solution, the preparation method of described trivalent chromium sulfate plating solution includes:
By the cell body soak with sulphuric acid by 1% volume ratio, clean up;
Inject the pure water of 80% toward cell body, heating is to 55 DEG C;
Adding conducting salt and the buffer salt of requirement, stirring tank liquor guarantees to be completely dissolved;
The trivalent chromic ion solution adding complexation good is a certain amount of;
It is sufficiently mixed uniformly, and regulates pH value to 3.5 with the sodium hydroxide solution of 25%, repeatedly test, until stable;
Add the brightener of given amount, wetting agent and accelerator etc., can electrolysis examination plating.
Further, the preparation method of described saccharin sodium reactant includes: add saccharin sodium solid or solution, under stirring, at system is warming up to 100-120 DEG C, and isothermal reaction 2 hours, obtain colourless namely obtaining product to yellow solution.
Another object of the present invention is to the trivalent chromium sulfate plating solution providing the preparation method of a kind of described trivalent chromium sulfate plating solution to prepare, described trivalent chromium sulfate plating solution solvent is water, consists of: conducting salt 150g/L~250g/L, buffer salt 60g/L~120g/L, trivalent chromic ion 5g/L~20g/L, chelating agent 10g/L~20g/L, brightener 0.1g/L~1g/L, C~S compound 1g/L~5g/L, saccharin sodium reactant 1g/L~4g/L, wetting agent 0.1g/L~1g/L.
Further, described trivalent chromium sulfate plating solution is composed as follows: conducting salt 180g/L~220g/L, buffer salt 80g/L~100g/L, trivalent chromic ion 8g/L~12g/L, chelating agent 14g/L~18g/L, brightener 0.4g/L~0.6g/L, C~S compound 2g/L~3g/L, saccharin sodium reactant 1g/L~4g/L, wetting agent 0.4g/L~0.6g/L.
Further, described conducting salt adopts one or both mixing in sodium sulfate, potassium sulfate, ammonium sulfate.
Further, described buffer salt adopts boric acid.
Further, described trivalent chromic ion adopts chromic sulfate, chromium sulfate basic, chromium carbonate, chromium acetate, chromic formate, one or more mixing of chromic oxide gel.
Further, described chelating agent adopts one or more mixing of malic acid, tartaric acid, citric acid, oxalic acid, 5-sulphosalicylic acid, iminodiacetic acid, aspartic acid, formic acid, acetic acid.
Further, described brightener adopts one or more of the sulfonic compounds such as sodium allylsulfonate, sodium vinyl sulfonate, cyclobutenyl sodium sulfonate, methylpropenyl sodium sulfonate;
Described C-S compound adopts one or more mixing of thiourea, allylthiourea, tolylthiourea, thioacetamide, TETD, thioacetamide, TGA, mercaptopropionic acid.
Further, described wetting agent adopts one or more mixing of 2-ethylhexylsulfate sodium, succinic acid dihexyl sodium sulfonate, sodium lauryl sulphate, 120,000 base benzene sulfonic acid sodium salts, aphthols polyoxyethylene ether, fatty alcohol-polyoxyethylene ether.
Further, described cleaner adopts one or both mixing of SDD, sodium diethyldithiocarbamate.
Trivalent chromium sulfate plating solution provided by the invention and preparation method thereof, in conjunction with external, domestic trivalent chromium plating technological development present situation and at present market present situation on product are studied; Propose new environmental protection sulfate trivalent chromium electroplating technology, particularly select saccharin sodium product in the application of this system, the bigger performance that improve sulfate trivalent chromium electroplating technology; Under its technique, gained trivalent chromium coating is bright, fine and smooth in vain, and coating sedimentation rate is fast, and covering power and covering power are superior, can replace ornamental hexavalent chromium plating technique completely, meet client's Production requirement, meet the requirement of environmental protection. The saccharin sodium product of gained of the present invention, owing to having good dissolubility, its use scope being greatly increased so that sulfate trivalent chromium system is more stable, manipulation scope is more broad; Through overtesting, the deposition efficiency of coating is had obvious effect by the saccharin sodium product of gained of the present invention; Certain density saccharin sodium product, sedimentation rate and the overlay area of coating are significantly widened, and especially the deposition in district in coating are had remarkable result.
Accompanying drawing explanation
Fig. 1 is the preparation method flow chart of the trivalent chromium sulfate plating solution that the embodiment of the present invention provides.
Fig. 2 is the thickness of coating distribution schematic diagram that the embodiment of the present invention provides.
Fig. 3 is the employing electrochemistry linear sweep test schematic diagram that the embodiment of the present invention provides.
Fig. 4 is the sulfate trivalent chromium coating surface morphology schematic diagram that the embodiment of the present invention provides.
Fig. 5 is the Cr VI coating surface morphology schematic diagram that the embodiment of the present invention provides.
Fig. 6 is the chloride trivalent chromium coating surface morphology schematic diagram that the embodiment of the present invention provides.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated. should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Below in conjunction with accompanying drawing, the application principle of the present invention is explained in detail.
The trivalent chromium sulfate plating solution solvent of the embodiment of the present invention is water, consists of: conducting salt 150g/L~250g/L, buffer salt 60g/L~120g/L, trivalent chromic ion 5g/L~20g/L, chelating agent 10g/L~20g/L, brightener 0.1g/L~1g/L, C~S compound 1g/L~5g/L, saccharin sodium reactant 1g/L~4g/L, wetting agent 0.1g/L~1g/L.
The trivalent chromium sulfate plating solution of the embodiment of the present invention preferably constitutes as follows: conducting salt 180g/L~220g/L, buffer salt 80g/L~100g/L, trivalent chromic ion 8g/L~12g/L, chelating agent 14g/L~18g/L, brightener 0.4g/L~0.6g/L, C~S compound 2g/L~3g/L, saccharin sodium reactant 1g/L~4g/L, wetting agent 0.4g/L~0.6g/L.
Conducting salt mentioned by the present invention, has the electric conductivity improving plating solution, improves electroplating efficiency. one or both arbitrary proportions mixing in sodium sulfate, potassium sulfate, ammonium sulfate of the above-mentioned conducting salt mentioned. Conducting salt consumption in trivalent chromium sulfate plating solution is 150-250g/L, it is preferable that consumption is 180-220g/L.
Buffer salt mentioned by the present invention, has the pH value of stable plating solution, in cathode hydrogen evolution, the electroplating process of anode oxygen uptake, maintains trivalent chromic ion in rational pH value range.Buffer salt is preferably boric acid, the consumption 60-120g/L in trivalent chromium sulfate plating solution, it is preferable that consumption is 80-100g/L.
Source of trivalent chromium mentioned by the present invention, it is provided that the trivalent chromic ion required for electroplating process. it is selected from chromic sulfate, chromium sulfate basic, chromium carbonate, chromium acetate, chromic formate, one or more arbitrary proportions mixing in the compound such as chromic oxide gel. Trivalent chromic ion content in trivalent chromium sulfate plating solution is 5-20g/L, it is preferable that content is 8-12g/L.
Chelating agent mentioned by the present invention, as complexation coefficient is too strong, will cause that trivalent chromic ion is difficult to deposit and affect electroplating efficiency; Complexation coefficient is too weak, trivalent chromic ion will be made easily to precipitate out, electroplating process also can produce chromic oxide gel fragment, affecting quality of coating. chelating agent of the present invention and trivalent chromic ion form suitable complexation COEFFICIENT K, provide stable part for trivalent chromic ion. and chelating agent of the present invention is selected from as one or more arbitrary proportions mixing such as malic acid, tartaric acid, citric acid, oxalic acid, 5-sulphosalicylic acid, iminodiacetic acid, aspartic acid, formic acid, acetic acid. Chelating agent consumption in trivalent chromium sulfate plating solution is 10-20g/L, it is preferable that consumption is 14-18g/L.
Brightener mentioned by the present invention, has the effect of brightness and the refinement degree improving coating. It is selected from one or more arbitrary proportions mixing composition of the sulfonic compounds such as sodium allylsulfonate, sodium vinyl sulfonate, cyclobutenyl sodium sulfonate, methylpropenyl sodium sulfonate. Brightener consumption in trivalent chromium sulfate plating solution is 0.1-1g/L, it is preferable that consumption is 0.4-0.6g/L.
C-S compound mentioned by the present invention, tool is significantly improved the sedimentation rate of coating, promotes effect of chromic electroplating efficiency. The C-S compound being selected from has one or more arbitrary proportions mixing such as thiourea, allylthiourea, tolylthiourea, thioacetamide, TETD, thioacetamide, TGA, mercaptopropionic acid. C-S compound consumption in trivalent chromium sulfate plating solution is 1-5g/L, it is preferable that consumption is 2-3g/L.
Wetting agent mentioned by the present invention safeguards that the surface tension of tank liquor is below 40 MNs/m. This wetting agent mentioned by invention is selected from one or more arbitrary proportions mixing such as 2-ethylhexylsulfate sodium, succinic acid dihexyl sodium sulfonate, sodium lauryl sulphate, 120,000 base benzene sulfonic acid sodium salts, aphthols polyoxyethylene ether, fatty alcohol-polyoxyethylene ether. Wetting agent consumption in trivalent chromium sulfate plating solution is 0.1-1g/L, it is preferable that consumption is 0.4-0.6g/L.
Cleaner mentioned by the present invention has the effect settling the foreign ions such as copper, zinc, nickel, ferrum significantly, and is dispelled by filtration. One or both arbitrary proportions mixing that cleaner compounds is SDD, sodium diethyldithiocarbamate that this invention is mentioned. its amount can be added adjustable according to the content of impurity in tank liquor.
Especially, the saccharin sodium product that the present invention mentions has the effects such as the covering power improving coating and deposition efficiency in sulfate trivalent chromium bath solution. The saccharin sodium product that the present invention mentions consumption in trivalent chromium sulfate plating solution is 1-4g/L, it is preferable that consumption is 2-3g/L.
PH value range of the invention process is 3.2-3.8, and preferred pH value is 3.5.
Temperature range of the invention process is 15-60 DEG C, and preferred temperature is 55 DEG C.
Cathode-current density of the invention process ranges for 7-15 ampere every square decimeter, and preferred current density range is 12 amperes every square decimeter.
The invention process adopts slight air stirring or movable cathode mode to electroplate.
As it is shown in figure 1, the preparation method of the trivalent chromium sulfate plating solution of the embodiment of the present invention comprises the following steps:
S101: by the cell body soak with sulphuric acid by 1% volume ratio, clean up;
S102: inject the pure water of about 80% toward cell body, heating is to 55 DEG C;
S103: adding conducting salt and the buffer salt of requirement, stirring tank liquor guarantees to be completely dissolved;
S104: the trivalent chromic ion solution adding complexation good is a certain amount of;
S105: be sufficiently mixed uniformly, and regulate pH value to 3.5 with the sodium hydroxide solution of 25%, repeatedly test, until stable;
S106: add the brightener of given amount, wetting agent and accelerator etc., can electrolysis examination plating.
Below the operation principle of the present invention is described in detail.
Conductive compositions and buffer salt are made conducting salt by the present invention, prior to chelating agent and trivalent chromic ion complexation is formed chromium solution, wetting agent and cleaner is separately formed respectively; And brightener, C-S key compound and saccharin sodium product are intersected composite, make brightener and accelerator, regulator etc. so that more convenient in manipulation, system is more stable. It is desirable to provide a kind of sulphate type trivalent chromium electroplating technology, this technique comprises conducting salt, buffer salt, source of trivalent chromium, chelating agent, brightener, C-S compound, cleaner, wetting agent etc. Especially, the present invention provides the preparation of the product of a kind of saccharin sodium and the application in this system. The synthesis of the saccharin sodium product that the present invention mentions, it is necessary to certain medium and the reaction condition being suitable for. The medium that the present invention mentions refers to the aqueous environment of certain ph, and the aqueous environment of this certain ph refers to strong alkaline aqueous solution, it is necessary to adding suitable compound provides. Required compound is selected from one or more arbitrary proportions mixing of sodium hydroxide, potassium hydroxide, sodium sulfide, ammonia, hydrazine hydrate, N-Methyl pyrrolidone, 2-Pyrrolidone etc. Desired substance reaches certain basicity, and alkali condition is more strong, and reaction more easily carries out. The saccharin sodium product of the present invention, it is necessary to produce at a certain temperature and obtain. Intensification is conducive to reacting to carry out, and at a lower temperature, reaction can not occur. Selectable temperature range is 90-150 DEG C, and more excellent is selected at 100-120 DEG C. The saccharin sodium product of the present invention, by, in the aqueous solution in the certain ph configured, adding saccharin sodium solid or its solution, under stirring, at system is warming up to 100-120 DEG C, isothermal reaction about 2 hours, obtain colourless namely obtaining product to yellow solution. The product of gained can pass through to add the amount of saccharin sodium, controls the concentration of product. The saccharin sodium product of the present invention, it is possible to be tracked detection control by proton nmr spectra and react to obtain degree. By product is adjusted to acidity, saccharin sodium whether complete reaction can also be checked. Owing to saccharin sodium is when pH value is less than 4, namely there will be a large amount of precipitation, and this product when highly acid (pH value is less than 1) all without there being any precipitation, by this phenomenon can to react degree judges. The saccharin sodium product of gained of the present invention, owing to having good dissolubility, its use scope being greatly increased so that sulfate trivalent chromium system is more stable, manipulation scope is more broad.Through overtesting, the deposition efficiency of coating is had obvious effect by the saccharin sodium product of gained of the present invention. Certain density saccharin sodium product, sedimentation rate and the overlay area of coating are significantly widened, and especially the deposition in district in coating are had remarkable result.
Below in conjunction with detailed description of the invention, the application principle of the present invention is further described. (for 1L electroplate liquid)
Embodiment 1
Sodium sulfate 200g/L boric acid 90g/L, chromium sulfate basic 60g/L, malic acid 15g/L, formic acid 1g/L, thiourea 0.005g/L, saccharin sodium product 3g/L, sodium allylsulfonate 0.5g/L, succinic acid dihexyl sodium sulfonate 0.5g/L, all the other be water.
Embodiment 2
Potassium sulfate 210g/L, boric acid 100g/L, chromium sulfate basic 60g/L, malic acid 15g/L, formic acid 1g/L, thiourea 0.005g/L, saccharin sodium 3g/L, sodium allylsulfonate 0.5g/L, succinic acid dihexyl sodium sulfonate 0.5g/L, all the other be water.
Embodiment 3
Sodium sulfate 50g/L, potassium sulfate 150g/L, boric acid 90g/L, chromium sulfate basic 60g/L, malic acid 15g/L, formic acid 1g/L, allylthiourea 0.006g/L, saccharin sodium product 3g/L, sodium vinyl sulfonate 0.5g/L, succinic acid dihexyl sodium sulfonate 0.5g/L, all the other be water.
Embodiment 4
Sodium sulfate 50g/L, potassium sulfate 150g/L, ammonium sulfate 30g/L, boric acid 90g/L, chromium sulfate basic 60g/L, citric acid 15g/L, formic acid 1g/L, allylthiourea 0.006g/L, saccharin sodium product 3g/L, sodium vinyl sulfonate 0.5g/L, diethylhexyl sodium sulfate 0.5g/L, all the other be water.
Embodiment 5
Potassium sulfate 150g/L, ammonium sulfate 50g/L, boric acid 90g/L, chromic oxide gel 25g/L, citric acid 5g/L, malic acid 10g/L, formic acid 1g/L, allylthiourea 0.008g/L, saccharin sodium product 4g/L, sodium vinyl sulfonate 0.5g/L, diethylhexyl sodium sulfate 08g/L, all the other be water.
Below in conjunction with performance test, the application effect of the present invention is described in detail.
1, the outward appearance test of coating
By patent sulfate trivalent chromium bath solution technique, gained coating carries out colorimetric card appearance luster contrast. and tint presents the blue and white outward appearance consistent with Cr VI coating, light is fine and smooth. and the obfuscation of chloride type trivalent chromium Deposit appearance is black, it is impossible to fully meet customer demand.
2, sedimentation rate test
By patent sulfate trivalent chromium bath solution technique, adopt square groove, temperature 55 DEG C, electric current density 7 amperes every square decimeter, plating 7 minutes, obtain coating test piece. Adopt Germany's FISCHERX-RayXDLM-C4 calibrator, test piece is taken 5 test thickness of coating, is calculated averaging, show that sedimentation rate is 0.06um/min. Taking market sulfuric acid type trivalent chromium plating tank liquor on year-on-year basis to test, its sedimentation rate is 0.045um/min. This Product Process has more apparent advantage in plating speed.
3, current efficiency test
The current efficiency of test plating solution adopts " the copper test coulometer method of plating solution current efficiency ". and market sulfuric acid type trivalent chromium plating process current efficiency is 7.28%. And present invention process current efficiency can reach 8.93%. The energy can be saved in actual use, reduce cost, improve production efficiency and economic benefit.
3, thickness distribution
By patent sulfate trivalent chromium bath solution technique, adopting HULL groove, temperature 55 DEG C, 5A7min electroplates, and obtains coating test piece. Each 1cm access point testing, adopts Germany's FISCHERX-RayXDLM-C4 calibrator, tests thickness of coating.Result is as shown in Figure 2. As seen from the figure, the distribution of this process thickness first rises, after the trend that slightly decreases, present downward trend with chloride type trivalent chromium plating technological coating thickness and exist and be clearly distinguished from. The distribution of this " parabola " shape makes middle electric current density district have higher deposit thickness, and whole thickness of coating more uniformly spreads.
4, covering power test
By patent sulfate trivalent chromium bath solution technique, adopting HULL groove, temperature 55 DEG C, 5A7min electroplates, and obtains coating test piece. Reach 8.8cm by measuring coating overlay area width, and chloride type trivalent chromium plating technique overlay area is 7.3cm. As can be seen here, this technique has more excellent covering power.
5, cathodic polarization aptitude tests
By introducing ligand complex agent and not adding chelating agent, system being contrasted, adopt electrochemistry linear sweep test, result is as shown in Figure 3. Having figure it can be seen that the cathode potential of blank system is-1.35V, and under this technique, the cathode potential of product full constituent system is-1.45V, under the effect of various additives, cathode potential is negative moves, and have dropped 100mV. Therefore, under this technique, the polarizability of plating solution is substantially strengthened, and coating deposition is more orderly, and coating crystallization is more careful.
6, coating microscopic appearance
Fig. 4 is the microscopic appearance under amplifying 30000 times of the trivalent chromium sulfate plating solution coating obtained by the present invention, Fig. 5 is hexavalent chromium plating liquid coating microscopic appearance under amplifying 30000 times, and Fig. 6 is market chloride type trivalent chromium plating solution coating microscopic appearance under amplifying 30000 times. As seen from the figure, this technique trivalent chromium sulfate plating solution coating is microgranule heaped-up, and microgranule is uniformly fine and closely woven, and structure is consistent with Cr VI coating; And chloride type trivalent chromium plating technique gained coating is stratiform accumulation, fine and smooth not smooth, existing defects.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.

Claims (10)

1. the preparation method of a trivalent chromium sulfate plating solution, it is characterised in that the preparation method of described trivalent chromium sulfate plating solution includes:
By the cell body soak with sulphuric acid by 1% volume ratio, clean up;
Inject the pure water of 80% toward cell body, heating is to 55 DEG C;
Adding conducting salt 150g/L~250g/L, buffer salt 60g/L~120g/L, stirring tank liquor dissolves;
Add trivalent chromic ion 5g/L~20g/L that complexation is good;
Mix homogeneously, and regulate pH value to 3.5 with the sodium hydroxide solution of 25%, repeatedly test, until stable;
Add brightener 0.1g/L~1g/L, C~S compound 1g/L~5g/L, saccharin sodium reactant 1g/L~4g/L, wetting agent 0.1g/L~1g/L, can electrolysis examination plating.
2. the preparation method of trivalent chromium sulfate plating solution as claimed in claim 1, it is characterized in that, the preparation method of described saccharin sodium reactant includes: add saccharin sodium solid or solution, under stirring, at system is warming up to 100-120 DEG C, isothermal reaction 2 hours, obtains colourless namely obtaining product to yellow solution.
3. the trivalent chromium sulfate plating solution that prepared by the preparation method of a trivalent chromium sulfate plating solution as claimed in claim 1, it is characterized in that, described trivalent chromium sulfate plating solution solvent is water, consists of: conducting salt 150g/L~250g/L, buffer salt 60g/L~120g/L, trivalent chromic ion 5g/L~20g/L, chelating agent 10g/L~20g/L, brightener 0.1g/L~1g/L, C~S compound 1g/L~5g/L, saccharin sodium reactant 1g/L~4g/L, wetting agent 0.1g/L~1g/L.
4. trivalent chromium sulfate plating solution as claimed in claim 3, it is characterized in that, described trivalent chromium sulfate plating solution is composed as follows: conducting salt 180g/L~220g/L, buffer salt 80g/L~100g/L, trivalent chromic ion 8g/L~12g/L, chelating agent 14g/L~18g/L, brightener 0.4g/L~0.6g/L, C~S compound 2g/L~3g/L, saccharin sodium reactant 1g/L~4g/L, wetting agent 0.4g/L~0.6g/L.
5. the trivalent chromium sulfate plating solution as described in claim 3 or 4, it is characterised in that described conducting salt adopts one or both mixing in sodium sulfate, potassium sulfate, ammonium sulfate.
6. the trivalent chromium sulfate plating solution as described in claim 3 or 4, it is characterised in that described buffer salt adopts boric acid.
7. the trivalent chromium sulfate plating solution as described in claim 3 or 4, it is characterised in that described trivalent chromic ion adopts chromic sulfate, chromium sulfate basic, chromium carbonate, chromium acetate, chromic formate, one or more mixing of chromic oxide gel.
8. the trivalent chromium sulfate plating solution as described in claim 3 or 4, it is characterized in that, described chelating agent adopts one or more mixing of malic acid, tartaric acid, citric acid, oxalic acid, 5-sulphosalicylic acid, iminodiacetic acid, aspartic acid, formic acid, acetic acid.
9. the trivalent chromium sulfate plating solution as described in claim 3 or 4, it is characterised in that described brightener adopt sodium allylsulfonate, sodium vinyl sulfonate, cyclobutenyl sodium sulfonate, methylpropenyl sodium sulfonate one or more;
Described C-S compound adopts one or more mixing of thiourea, allylthiourea, tolylthiourea, thioacetamide, TETD, thioacetamide, TGA, mercaptopropionic acid.
10. the trivalent chromium sulfate plating solution as described in claim 3 or 4, it is characterized in that, described wetting agent adopts one or more mixing of 2-ethylhexylsulfate sodium, succinic acid dihexyl sodium sulfonate, sodium lauryl sulphate, 120,000 base benzene sulfonic acid sodium salts, aphthols polyoxyethylene ether, fatty alcohol-polyoxyethylene ether;
Described cleaner adopts one or both mixing of SDD, sodium diethyldithiocarbamate.
CN201610219258.XA 2016-04-11 2016-04-11 Sulfate trivalent chromium electroplating solution and preparation method thereof Pending CN105671599A (en)

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CN107245737A (en) * 2017-06-17 2017-10-13 无锡市恒利弘实业有限公司 A kind of ionic liquid high pressure CO2The method for electroplating super abrasive chromium in metallic substrate surface under anhydrous electroplate liquid system
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CN108034969A (en) * 2017-12-15 2018-05-15 闽南师范大学 A kind of sulfate trivalent chromium plating chromium plating bath and its application process
CN108950610A (en) * 2018-08-27 2018-12-07 重庆立道新材料科技有限公司 A kind of trivalent chromium chrome plating layer brightening agent and its plating chromium plating bath
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CN106283132A (en) * 2016-08-26 2017-01-04 湖北吉和昌化工科技有限公司 A kind of soft dispersant of subacidity system electroplating bright copper
CN106283132B (en) * 2016-08-26 2018-07-10 湖北吉和昌化工科技有限公司 A kind of soft dispersant of subacidity system electroplating bright copper
CN107245737A (en) * 2017-06-17 2017-10-13 无锡市恒利弘实业有限公司 A kind of ionic liquid high pressure CO2The method for electroplating super abrasive chromium in metallic substrate surface under anhydrous electroplate liquid system
CN107245737B (en) * 2017-06-17 2019-06-21 无锡市恒利弘实业有限公司 A kind of ionic liquid-high pressure CO2In the method for metallic substrate surface plating super abrasive chromium under anhydrous electroplate liquid system
CN107419304A (en) * 2017-09-04 2017-12-01 重庆立道表面技术有限公司 A kind of trivalent chromium chrome plating impurity tolerance agent and electroplate liquid
WO2019117178A1 (en) * 2017-12-13 2019-06-20 株式会社Jcu Trivalent chromium plating solution and method for chromium-plating using same
EP3725920A4 (en) * 2017-12-13 2021-04-21 JCU Corporation Trivalent chromium plating solution and method for chromium-plating using same
CN108034969A (en) * 2017-12-15 2018-05-15 闽南师范大学 A kind of sulfate trivalent chromium plating chromium plating bath and its application process
CN108950610A (en) * 2018-08-27 2018-12-07 重庆立道新材料科技有限公司 A kind of trivalent chromium chrome plating layer brightening agent and its plating chromium plating bath
CN111206270A (en) * 2020-03-06 2020-05-29 广州三孚新材料科技股份有限公司 Trivalent chromium electroplating solution and preparation method thereof
CN111206270B (en) * 2020-03-06 2021-02-23 广州三孚新材料科技股份有限公司 Trivalent chromium electroplating solution and preparation method thereof

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