CN109652827A - A kind of trivalent chromium sulfate plating solution and its manufacture craft and electroplating technology - Google Patents
A kind of trivalent chromium sulfate plating solution and its manufacture craft and electroplating technology Download PDFInfo
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- CN109652827A CN109652827A CN201910037607.XA CN201910037607A CN109652827A CN 109652827 A CN109652827 A CN 109652827A CN 201910037607 A CN201910037607 A CN 201910037607A CN 109652827 A CN109652827 A CN 109652827A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
Abstract
The present invention relates to a kind of trivalent chromium sulfate plating solutions, including conductive salt, A preparation, B preparation, C preparation, D preparation, wetting agent and pure water.The present invention can make the workpiece for being electroplated out using it obtain the good trivalent chrome plating of appearance under 25-40 DEG C of room temperature, its thickness of coating can reach 1 micron or more, the workpiece for being electroplated out using it can enhance its corrosion resistance, hardness, electric conductivity, slickness, heat resistance and wearability, the deposition rate of its layers of chrome reaches 0.1-0.2 [mu, it is realized in the case where guaranteeing processing quality can save electric energy and reduction use cost, and the Lab color value of coating can be according to the needs of plating in 65 < L < 80, -1 < a < 1, it is freely adjusted in the range of 2 <b < 6, enable the color of coating from silvery white color adjustment to brownish black, it is good with stability, covering power is strong, the good and environmentally friendly advantage of covering power.
Description
Technical field
The present invention relates to a kind of trivalent chromium sulfate plating solution and its manufacture craft and electroplating technology.
Background technique
Since chrome layer has good hardness, wearability, corrosion resistance and dicoration, most widely used plating is had become
One of kind.Traditional hexavalent chromium solution causes serious pollution to the environment, national governments all reinforce legislation management, make Cr VI will gradually by
It eliminates.And trivalent chromium plating liquor ratio hexavalent chromium plating liquid is more environmentally friendly, for this purpose, develop environmental protection, hexavalent chromium plating can be replaced
Trivalent chromium plating scheme be imperative.
Currently, common trivalent chromium plating liquid system is divided into chloride system and sulfate system, chloride system is in electricity
During plating, a large amount of chlorine is had in the state of high current density, on anode and is precipitated, the precipitation of chlorine equally can be right
Environment causes biggish pollution, and the chloride ion in electroplate liquid easily corrodes equipment, so that the service life of equipment can be reduced.
And the sulfate system in trivalent chromium plating liquid system is compared with chloride system, sulfate system more ring
It protects, but the trivalent chromium plating solution of sulfate system is typically necessary and carries out in the environment of 50 DEG C -60 DEG C (even higher temperature)
Plating is big with power consumption, deposition rate is slow, thickness of coating is thin, current density range is narrow and the plating of workpiece color is uneven
Even deficiency, if notification number is CN108034969A, patent name is that " a kind of sulfate trivalent chromium plates chromium plating bath and its application
Method ", the sulfate trivalent chromium plating chromium plating bath made using the formula just have plating required temperature height, power consumption
Greatly, the deficiencies of deposition rate is slow, thickness of coating is thin and current density range is narrow, deposition rate generally only in 0.02-
0.05 [mu, current density only in 2.7-12A/dm2, the thickness of workpiece coating is most thick only at 0.1-0.2 microns,
Even if its extend electroplating time can not thickening part coating thickness.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of trivalent chromium sulfate plating solution and its manufacture craft and electricity
Depositing process can obtain the good trivalent chrome plating of appearance to the workpiece for being electroplated out using it under 25-40 DEG C of room temperature,
The Lab color value of coating can freely adjust in the range of certain data according to the needs of plating, enable the color of coating from
Silvery white color adjustment is to brownish black, and its electroplate liquid has that stability is good, covering power is strong, covering power is good and environmentally friendly excellent
Point can enhance its corrosion resistance, hardness, electric conductivity, slickness, heat resistance and wear-resisting out using the present invention workpiece that is electroplated
Property, the deposition rate of layers of chrome reach 0.1-0.2 [mu, thickness of coating reaches 1 micron or more, current density range
5-75 A/dm can be extended to2, electric energy can be saved and reduce use cost by realizing in the case where guaranteeing processing quality, no
But it solves and at present workpiece be electroplated using the chloride system in hexavalent chromium solution and trivalent chromium plating liquid system
Can have the problem of pollution to environment, meanwhile, also solve at present using the sulfate system in trivalent chromium plating liquid system come
Plating is carried out with power consumption is big, deposition rate is slow, thickness of coating is thin, current density range is narrow and workpiece color electricity to workpiece
Plate non-uniform problem.The present invention is achieved through the following technical solutions:
A kind of trivalent chromium sulfate plating solution comprising following weight ratio composition: conductive salt 20%-40%, A preparation 10%-30%,
B preparation 5%-10%, C preparation is less than or equal to 2%, D preparation and is less than or equal to 2%, wetting agent 0.2%-0.6%, remaining is pure water.
It is the potassium sulfate of 30-50% that the conductive salt, which is by weight ratio, ammonium sulfate, the 1- of the sodium sulphate of 10-20%, 1-10%
10% magnesium sulfate and 10-30% boric acid composition, the conductive salt made of above-mentioned formula can effectively improve electroplate liquid specific gravity and
Effectively maintain the conductive capability of electroplate liquid.
The A preparation includes following weight ratio composition: the complexing agent of the chromium sulfate of 30-50%, 5-20%, remaining is pure
Water, chromium ion consumed by electroplate liquid can effectively be supplemented by being thus formulated manufactured A preparation.
The B preparation is the mixture of carboxylic acid composition, B preparation include weight ratio composition be the formic acid of 10-50%, acetic acid,
Two kinds or three kinds or more in oxalic acid, hydroxyacetic acid, lactic acid, malic acid, tartaric acid, malonic acid, amion acetic acid and nitrilotriacetic acid
Mixing, remaining is pure water, be thus formulated the B preparation produced can be effectively facilitated chromium ion cathode surface be precipitated.
The C preparation is the compound of the elements such as sulfur-bearing, oxygen, nitrogen, and C preparation includes the sulphur that weight ratio composition is 2-20%
For the mixing of one of urea, sodium thiosulfate, imidazoles, pyridine and imidazopyridine derivatives or two kinds or more, remaining is
Pure water；Thus C preparation made of being formulated can effectively increase the range of current density, maintain the color and thickness of coating.
The D preparation is containing unsaturated aldehyde radical, the compound of alkyl, and D preparation includes that weight ratio composition is 2-20%
The mixing of one of formaldehyde, acetaldehyde, formaldehyde derivatives and acetaldehyde derivatives or two kinds or more, remaining is pure water；Thus it is formulated
Manufactured D preparation can effectively eliminate the striped on coating, keep coating appearance bright.
Further, the wetting agent includes the sodium alkyl sulfonate and sulfosuccinate that weight ratio composition is 1-10%
The mixture of sodium salt, remaining is pure water.Thus wetting agent made of being formulated can be effectively reduced the surface tension of plating solution, remove plating
The point of layer and pin hole etc..
Further, the present invention also provides a kind of manufacture craft of trivalent chromium sulfate plating solution and its electroplating technologies: step
Rapid one: firstly, weighing the weight of conductive salt, A preparation, B preparation, C preparation, D preparation, wetting agent and pure water respectively by each weight ratio
Amount, then, by pure water injection using in reactive tank made of PVC, ABS or polythene material, the power supply of reactive tank uses direct current
Then the pure water injected in reactive tank is heated to 60-70 DEG C by electricity.
Step 2: conductive salt is added in the reactive tank of keeping warm mode, and conductive salt is stirred until being completely dissolved.
Step 3: A preparation and B preparation are put into reactive tank, are stirred until by A preparation and B preparation to being completely dissolved
It or until stirring evenly, and is 60 DEG C by the temperature setting of reactive tank, reactive tank keeps the temperature 8 hours with 60 DEG C of steady temperature.
Step 4: the pH value of the pH value of up-regulation reaction tank liquid or downward reaction tank liquid according to the needs of production,
The every up-regulation 0.1 of the pH value of liquid in reactive tank is that concentration is used to adjust for the NaOH solution of 1.5ml/L, liquid in reactive tank
It is that concentration is used to adjust for the dilute sulfuric acid of 3mol/L that the pH value of body is every, which to lower 0.1,.
Step 5: C preparation, D preparation and wetting agent are put into the reactive tank for keeping 60 DEG C of steady temperatures, until by C
Preparation, D preparation and wetting agent stir until being completely dissolved or stirring evenly, and then, reactive tank is 10-15A/ with current density
dm2To trivalent chromium sulfate plating solution is just made after the liquid electrolytic being contained in it 2-4 hours, which is electroplated
The current density range realization of liquid can be extended to 5-75A/dm2。
Step 6: under 25-40 DEG C of room temperature by the workpiece to be electroplated put into the trivalent chromium sulfate plating solution into
Row plating 2-8 minutes, the deposition rate for the workpiece coating being electroplated using the trivalent chromium sulfate plating solution is micro- in 0.1-0.2
M/min, the thickness of workpiece coating reaches 1 micron or more, is swept after trivalent chromium sulfate plating solution long-time use using XRF
Instrument is retouched to scan the impurity in liquid, and puts into suitable cleaner in trivalent chromium sulfate plating solution, cleaner
Investment can precipitate the metal impurities that trivalent chromium sulfate plating solution generates in the plating process, then, using cotton core pair
Trivalent chromium sulfate plating solution is filtered, and to filter out the metal impurities of precipitating, and completes filtered sulfate trivalent chromium
Electroplate liquid can continue cycling through use.
Further, in the step 6, the cleaner includes that the metal sulphide that weight ratio composition is 5-25% is caught
Catch one of agent xanthate, xanthate derivative, black powder, baiyao, benzothiazole mercaptan, benzimidazole mercaptan and benzo uh azoles mercaptan
Or two kinds or more of mixing, remaining is pure water.
Further, in the step 6, the input amount of the cleaner is resulting according to the scanning of XRF scanner
For impurity level come what is put into, the input amount of the cleaner is that XRF scanner scans 1/10th of resulting impurity level.
A kind of trivalent chromium sulfate plating solution of the invention, including it is conductive salt, A preparation, B preparation, C preparation, D preparation, wet
Moisten agent and pure water.Conductive salt of the invention be 30-50% by weight ratio potassium sulfate, weight ratio be 10-20% sodium sulphate, again
Amount than be 1-10% ammonium sulfate, weight ratio be 1-10% magnesium sulfate and weight ratio be 10-30% boric acid be formulated, will be by
Conductive salt made of above-mentioned formula can improve the ratio of electroplate liquid of the invention as one of formula of the invention, this conductive salt is formed
Weight, to ensure that the conductive capability of electrodeposit liquid of the invention reaches optimal state；And it the production of A preparation and comes into operation and can supplement
The chromium ion that the present invention consumes in the plating process, the addition of B preparation can promote chromium ion to be precipitated and supplement A system in cathode surface
The part of agent underconsumption, A preparation and being applied in combination for B preparation can greatly improve electroplating efficiency of the invention, make coating
Deposition rate reaches 0.1-0.2 [mu, slow with the electrodeposit liquid deposition rate that can solve current, deposition rate only exist
The deficiency of 0.02-0.05 [mu；The investment of C preparation, which realizes the present invention, can increase the range of current density, maintain coating
Color and thickness, so that current density range of the invention is increased to 5-75A/dm2；The investment of D preparation can improve this hair
The depth capability of bright electroplate liquid enables the invention to be effectively removed the striped on coating, to ensure the brightness of coating；It is wet
Moisten production and the investment of agent for reducing the surface tension of electroplate liquid of the invention, can effectively eliminate using present invention plating
The flaws such as point and pin hole on the coating of workpiece out, C preparation, D preparation and being applied in combination for wetting agent can ensure that this hair
Bright electroplating effect is good and high using the yields of the workpiece of the invention for being electroplated out；Using formula and manufacture craft of the invention
The electroplate liquid produced, carrying out the coating that electrodeposit is deposited to workpiece is crome metal, no pollution to the environment, using very
Environmental protection, and the color of workpiece coating surface is visibly homogeneous, which obviate there is the non-uniform phenomenon of local color, is electroplated out through it
The workpiece come has good covering power and covering power, will not generate workpiece encounters power-off during plating
Undesirable consequence, meanwhile, also realizing can be electroplated under 25-40 DEG C of room temperature, save electric energy and reduction to realize
The low purpose of use cost.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
A kind of trivalent chromium sulfate plating solution comprising following weight ratio composition: conductive salt 20%-40%, A preparation 10%-
30%, B preparation 5%-10%, C preparation is less than or equal to 2%, D preparation and is less than or equal to 2%, wetting agent 0.2%-0.6%, remaining is system
It is used as the pure water of electroplate liquid.
It is the potassium sulfate of 30-50% that the conductive salt, which is by weight ratio, ammonium sulfate, the 1- of the sodium sulphate of 10-20%, 1-10%
10% magnesium sulfate and 10-30% boric acid composition, the conductive salt made of above-mentioned formula can effectively improve electroplate liquid specific gravity and
Effectively maintain the conductive capability of electroplate liquid.
The A preparation includes following weight ratio composition: the complexing agent of the chromium sulfate of 30-50%, 5-20%, remaining is production
The pure water of A preparation；Complexing agent is that stable complex compound is formed by chromic salt or trivalent chromium；Complexing agent can be supplemented further
The part of chromium sulfate underconsumption, chromium ion consumed by electroplate liquid can effectively be supplemented by being thus formulated manufactured A preparation.
The B preparation is the mixture of carboxylic acid composition, B preparation include weight ratio composition be the formic acid of 10-50%, acetic acid,
Two kinds or three kinds or more in oxalic acid, hydroxyacetic acid, lactic acid, malic acid, tartaric acid, malonic acid, amion acetic acid and nitrilotriacetic acid
Mixing, remaining be make B preparation pure water, the B preparation for promote chromium ion cathode surface be precipitated.
The C preparation is the compound of the elements such as sulfur-bearing, oxygen, nitrogen, and C preparation includes the sulphur that weight ratio composition is 2-20%
For the mixing of one of urea, sodium thiosulfate, imidazoles, pyridine and imidazopyridine derivatives or two kinds or more, remaining is
Make the pure water of C preparation；Thus C preparation made of being formulated can effectively increase the range of current density, maintain the face of coating
Color and thickness.
The D preparation is containing unsaturated aldehyde radical, the compound of alkyl, and D preparation includes that weight ratio composition is 2-20%
The mixing of one of formaldehyde, acetaldehyde, formaldehyde derivatives and acetaldehyde derivatives or two kinds or more, remaining production D preparation are used
Pure water；Thus D preparation made of being formulated can effectively eliminate the striped on coating, keep coating appearance bright.
In one embodiment, the wetting agent includes the sodium alkyl sulfonate and sulfo group that weight ratio composition is 1-10%
The mixture of succinate sodium salt, remaining is the pure water for making wetting agent.Thus wetting agent made of being formulated can effectively drop
The surface tension of low plating solution removes point and pin hole of coating etc..
The present invention also provides a kind of manufacture craft of trivalent chromium sulfate plating solution and its electroplating technologies: step 1: firstly,
Weigh the weight of conductive salt, A preparation, B preparation, C preparation, D preparation, wetting agent and pure water respectively by each weight ratio, it then, will
Using in reactive tank made of PVC, ABS or polythene material, the power supply of reactive tank uses direct current for pure water injection, then, will
Pure water in injection reactive tank is heated to 60-70 DEG C.
Step 2: conductive salt is added in the reactive tank of keeping warm mode, and conductive salt is stirred until being completely dissolved.
Step 3: A preparation and B preparation are put into reactive tank, are stirred until by A preparation and B preparation to being completely dissolved
It or until stirring evenly, and is 60 DEG C by the temperature setting of reactive tank, reactive tank keeps the temperature 8 hours with 60 DEG C of steady temperature.
Step 4: the pH value of the pH value of up-regulation reaction tank liquid or downward reaction tank liquid according to the needs of production,
The every up-regulation 0.1 of the pH value of liquid in reactive tank is that concentration is used to adjust for the NaOH solution of 1.5ml/L, liquid in reactive tank
It is that concentration use to adjust for the dilute sulfuric acid of 3mol/L that the pH value of body is every, which to lower 0.1, finally makes the pH value of reaction tank liquid
Range is adjusted to 3.0-3.8, preferred as pH value, reacts the pH value most preferably 3.5 of tank liquid.
Step 5: C preparation, D preparation and wetting agent are put into the reactive tank for keeping 60 DEG C of steady temperatures, until by C
Preparation, D preparation and wetting agent stir until being completely dissolved or stirring evenly, and then, reactive tank is 10-15A/ with current density
dm2To after the liquid electrolytic being contained in it 2-4 hours just be made trivalent chromium sulfate plating solution；A preparation, B preparation, C preparation,
The design for the current density that the design of liquid pH value, reactive tank are electrolysed in the Combination Design of D preparation and wetting agent, reactive tank
Design with electrolysis time, which finally realizes the current density range of the trivalent chromium sulfate plating solution, can be extended to 5-75A/
dm2。
Step 6: under 25-40 DEG C of room temperature by the workpiece to be electroplated put into the trivalent chromium sulfate plating solution into
Row plating 2-8 minutes, the deposition rate for the workpiece coating being electroplated using the trivalent chromium sulfate plating solution is micro- in 0.1-0.2
M/min, the thickness of workpiece coating reaches 1 micron or more, is swept after trivalent chromium sulfate plating solution long-time use using XRF
Instrument is retouched to scan the impurity in liquid, and puts into suitable cleaner in trivalent chromium sulfate plating solution, cleaner
Investment can precipitate the metal impurities that trivalent chromium sulfate plating solution generates in the plating process, then, using cotton core pair
Trivalent chromium sulfate plating solution is filtered, and to filter out the metal impurities of precipitating, and completes filtered sulfate trivalent chromium
Electroplate liquid can continue cycling through use.
Further, in the step 6, the cleaner includes that the metal sulphide that weight ratio composition is 5-25% is caught
Catch one of agent xanthate, xanthate derivative, black powder, baiyao, benzothiazole mercaptan, benzimidazole mercaptan and benzo uh azoles mercaptan
Or two kinds or more of mixing, remaining is the pure water for making cleaner.
Further, in the step 6, the input amount of the cleaner is resulting according to the scanning of XRF scanner
For impurity level come what is put into, the input amount of the cleaner is that XRF scanner scans 1/10th of resulting impurity level；When making
Electroplating time is preferred, and plating Best Times are 3-5 minutes.
Embodiment 1:
A kind of trivalent chromium sulfate plating solution comprising following weight ratio composition: conductive salt 30%, A preparation 20%, B preparation 6%,
C preparation 0.5%, D preparation 1%, wetting agent 0.3%, remaining is pure water.
The conductive salt be by weight ratio be 46% potassium sulfate, 15% sodium sulphate, 8% ammonium sulfate, 9% magnesium sulfate and
22% boric acid composition.
The A preparation includes following weight ratio composition: 45% chromium sulfate, 16% complexing agent, remaining for production A preparation
Pure water；
The B preparation be include formic acid, hydroxyacetic acid, three second of malic acid, tartaric acid and ammonia that weight ratio composition is 10-50%
The mixing of acid, remaining is the pure water for making B preparation.
The C preparation includes the thio urea that weight ratio composition is 2-20%, remaining is the pure water for making C preparation.Institute
Stating thio urea can be used the thio urea that Guangzhou De Sheng Chemical Co., Ltd. production article No. is LN.
It is the formaldehyde derivatives of 2-20% and mixing for acetaldehyde derivatives that the D preparation agent, which includes weight ratio composition, remaining
For the pure water for making D preparation.
In one embodiment, the wetting agent includes the sodium alkyl sulfonate and sulfo group that weight ratio composition is 1-10%
The mixture of succinate sodium salt, remaining is the pure water for making wetting agent.It is abundant emerging that Guangzhou can be used in the sodium alkyl sulfonate
The sodium alkyl sulfonate that safe trade Co., Ltd's sale article No. is K12, the sulfosuccinic acid ester sodium salt can be used federal in Guangdong
The sulfosuccinic acid ester sodium salt of fine Co., Ltd's sale.
Embodiment 2:
A kind of trivalent chromium sulfate plating solution comprising following weight ratio composition: conductive salt 35%, A preparation 16%, B preparation 8%,
C preparation 1.5%, D preparation 1.5%, wetting agent 0.5%, remaining is pure water.
The conductive salt be by weight ratio be 42% potassium sulfate, 19% sodium sulphate, 6% ammonium sulfate, 5% magnesium sulfate and
28% boric acid composition.
The A preparation includes following weight ratio composition: 38% chromium sulfate, 19% complexing agent, remaining for production A preparation
Pure water.
The B preparation includes the mixing of lactic acid, malic acid and nitrilotriacetic acid that weight ratio composition is 10-50%, remaining is
Make the pure water of B preparation.
The C preparation includes the mixing of thio urea and sodium thiosulfate that weight ratio composition is 2-20%, remaining is system
It is used as the pure water of C preparation.
The D preparation includes the mixing of formaldehyde, acetaldehyde and formaldehyde derivatives that weight ratio composition is 2-20%, remaining is
Make the pure water of D preparation.
In one embodiment, the wetting agent includes the sodium alkyl sulfonate and sulfo group that weight ratio composition is 1-10%
The mixture of succinate sodium salt, remaining is the pure water for making wetting agent.
Embodiment 3:
A kind of trivalent chromium sulfate plating solution comprising following weight ratio composition: conductive salt 23%, A preparation 25%, B preparation
10%, C preparation 2%, D preparation 0.5%, wetting agent 0.6%, remaining is pure water.
It is 38% potassium sulfate, 20% sodium sulphate, 9% ammonium sulfate, 10% magnesium sulfate that the conductive salt, which is by weight ratio,
It is formed with 23% boric acid.
The A preparation includes following weight ratio composition: 32% chromium sulfate, 12% complexing agent, remaining for production A preparation
Pure water；
The B preparation includes the mixing of lactic acid, malic acid, tartaric acid and nitrilotriacetic acid that weight ratio composition is 10-50%,
The remaining pure water for production B preparation.
The C preparation includes the sodium thiosulfate that weight ratio composition is 2-20%, remaining is the pure water for making C preparation.
The D preparation includes the acetaldehyde that weight ratio composition is 2-20%, remaining is the pure water for making D preparation.
In one embodiment, the wetting agent includes the sodium alkyl sulfonate and sulfo group that weight ratio composition is 1-10%
The mixture of succinate sodium salt, remaining is the pure water for making wetting agent.
Manufacture craft and galvanizer of the invention when will be used using the weight of embodiment 1, embodiment 2 and embodiment 3
The trivalent chromium sulfate plating solution of skill and the sulfate system of current trivalent chromium plating liquid system are respectively electroplated workpiece,
Its properties correlation data is as follows:
As can be known from the above table, at 25 DEG C -40 DEG C, realize to be electroplated electroplating temperature of the invention at normal temperature, electricity
It plates temperature to need compared in 50 DEG C -60 DEG C or higher temperature with the electroplating temperature of current sulfate system, save significantly
About electric resources, use cost is remarkably reduced, the electroplate liquid made using formula and manufacture craft of the invention
Deposition velocity in 0.1-0.2 [mu, with current sulfate system generally only in 0.02-0.05 [mu compared with
Compared with, deposition velocity significantly improved；Meanwhile the electroplate liquid made using formula and manufacture craft of the invention
Thickness of coating can reach 1 micron or more and its current density range can be expanded to 5-75A/dm2, and itself and current sulfate
System to the thickness of coating of workpiece most it is thick only at 0.1-0.2 microns and its current density range only in 2.7-12A/dm2It compares
Compared with the thicker sulfate wider with the expanded scope of current density, and being made using the present invention of thickness of coating of the invention
Trivalent chromium plating solution can be completed to be electroplated in 3-5 minutes to workpiece, electroplating efficiency can be as current chloride system
Efficiently, but chlorine will not can be precipitated in electroplating process of the invention as the chloride system in trivalent chromium plating liquid system,
The substance or gas for having pollution to environment will not be generated, use it is very environmentally friendly, and it corrosion reaction slot, container or will not set
Service life standby and that equipment will not be reduced.
The present invention is not limited to above-mentioned preferred forms, anyone obtain under the inspiration of the present invention other it is any with
The identical or similar product of the present invention, is within the scope of the present invention.
Claims (5)
1. a kind of trivalent chromium sulfate plating solution, it is characterised in that: it includes following weight ratio composition: conductive salt 20%-40%,
A preparation 10%-30%, B preparation 5%-10%, C preparation is less than or equal to 2%, D preparation and is less than or equal to 2%, wetting agent 0.2%-0.6%,
Remaining is pure water；
It is the potassium sulfate of 30-50% that the conductive salt, which is by weight ratio, ammonium sulfate, the 1-10% of the sodium sulphate of 10-20%, 1-10%
Magnesium sulfate and 10-30% boric acid composition；
The A preparation includes following weight ratio composition: the complexing agent of the chromium sulfate of 30-50%, 5-20%, remaining is pure water；
The B preparation includes formic acid, acetic acid, oxalic acid, hydroxyacetic acid, lactic acid, malic acid, the winestone that weight ratio composition is 10-50%
Two kinds or three kinds or more of mixing in acid, malonic acid, amion acetic acid and nitrilotriacetic acid, remaining is pure water；
The C preparation includes thio urea, sodium thiosulfate, imidazoles, pyridine and the imidazo pyrrole that weight ratio composition is 2-20%
The mixing of one of piperidine derivatives or two kinds or more, remaining is pure water；
The D preparation includes one in the formaldehyde that weight ratio composition is 2-20%, acetaldehyde, formaldehyde derivatives and acetaldehyde derivatives
Kind or two kinds or more of mixing, remaining is pure water.
2. a kind of trivalent chromium sulfate plating solution according to claim 1, it is characterised in that: the wetting agent includes weight
Ratio composition is the sodium alkyl sulfonate of 1-10% and the mixture of sulfosuccinic acid ester sodium salt, remaining is pure water.
3. the manufacture craft and its electroplating technology of a kind of trivalent chromium sulfate plating solution, it is characterised in that: the sulfate trivalent chromium
The manufacture craft and its electroplating technology of electroplate liquid are as follows: step 1: firstly, weighing conductive salt, A preparation, B respectively by each weight ratio
Pure water injection is then used PVC, ABS or polythene material system by the weight of preparation, C preparation, D preparation, wetting agent and pure water
At reactive tank in, the power supply of reactive tank uses direct current, then, the pure water injected in reactive tank is heated to 60-70 DEG C；
Step 2: conductive salt is added in the reactive tank of keeping warm mode, and conductive salt is stirred until being completely dissolved；
Step 3: A preparation and B preparation are put into reactive tank respectively, are stirred until by A preparation and B preparation to being completely dissolved
It or until stirring evenly, and is 60 DEG C by the temperature setting of reactive tank, reactive tank keeps the temperature 8 hours with 60 DEG C of steady temperature；
Step 4: the pH value of the pH value of up-regulation reaction tank liquid or downward reaction tank liquid according to the needs of production, reaction
The every up-regulation 0.1 of the pH value of liquid in slot is that concentration is used to adjust for the NaOH solution of 1.5ml/L, the liquid in reactive tank
It is that concentration is used to adjust for the dilute sulfuric acid of 3mol/L that pH value is every, which to lower 0.1,；
Step 5: by C preparation, D preparation and wetting agent put into keep 60 DEG C of steady temperatures reactive tank in, until by C preparation,
D preparation and wetting agent stir until being completely dissolved or stirring evenly, and then, reactive tank is 10-15A/dm with current density2It is right
It is contained in after liquid electrolytic 2-4 hours in it and trivalent chromium sulfate plating solution is just made, the trivalent chromium sulfate plating solution
Current density range realization can be extended to 5-75A/dm2；
Step 6: the workpiece to be electroplated is put into the trivalent chromium sulfate plating solution under 25-40 DEG C of room temperature and carries out electricity
Plating 2-8 minutes, the deposition rate of the workpiece coating being electroplated using the trivalent chromium sulfate plating solution 0.1-0.2 microns/
Minute, the thickness of workpiece coating reaches 1 micron or more, can be scanned with XRF after trivalent chromium sulfate plating solution long-time use
Instrument scans the impurity in liquid, and in the trivalent chromium sulfate plating solution suitable cleaner of investment, the investment of cleaner
The metal impurities that trivalent chromium sulfate plating solution generates in the plating process can be precipitated, then, using cotton core to sulfuric acid
Salt trivalent chromium plating solution is filtered, and to filter out the metal impurities of precipitating, and completes filtered sulfate trivalent chromium plating
Liquid can continue cycling through use.
4. the manufacture craft and its electroplating technology of a kind of trivalent chromium sulfate plating solution according to claim 3, feature
Be: in the step 6, the cleaner includes metal sulphide agent for capturing xanthate, the Huang that weight ratio composition is 5-25%
One of medicine derivative, black powder, baiyao, benzothiazole mercaptan, benzimidazole mercaptan and benzo uh azoles mercaptan or two kinds or more
Mixing, remaining is pure water.
5. the manufacture craft and its electroplating technology of a kind of trivalent chromium sulfate plating solution according to claim 3, feature
Be: in the step 6, the input amount of the cleaner is to scan resulting impurity level according to XRF scanner to put into
, the input amount of the cleaner is that XRF scanner scans 1/10th of resulting impurity level.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910037607.XA CN109652827A (en) | 2019-01-16 | 2019-01-16 | A kind of trivalent chromium sulfate plating solution and its manufacture craft and electroplating technology |
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| CN201910037607.XA CN109652827A (en) | 2019-01-16 | 2019-01-16 | A kind of trivalent chromium sulfate plating solution and its manufacture craft and electroplating technology |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110512240A (en) * | 2019-09-04 | 2019-11-29 | 广东涂乐师新材料科技有限公司 | A kind of white chromium electrodeposit liquid of salt acid type highly corrosion resistant trivalent |
| CN112111776A (en) * | 2019-06-19 | 2020-12-22 | 广东禾木科技有限公司 | Cathode passivation protection solution for silver bonding wire |
| WO2022224901A1 (en) * | 2021-04-21 | 2022-10-27 | 株式会社Jcu | Trivalent chromium plating solution and chromium plating method using same |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1368748A (en) * | 1972-02-08 | 1974-10-02 | British Non Ferrous Metals Res | Electrodeposition of chromium |
| EP0079768A1 (en) * | 1981-11-18 | 1983-05-25 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| US4448648A (en) * | 1981-11-18 | 1984-05-15 | International Business Machines Corporation | Trivalent chromium electroplating baths |
| US5196109A (en) * | 1991-08-01 | 1993-03-23 | Geoffrey Scott | Trivalent chromium electrolytes and plating processes employing same |
| CN101280440A (en) * | 2007-04-02 | 2008-10-08 | 比亚迪股份有限公司 | Whole sulphate type trivalent chromium plating solution and electroplating method using the same |
| CN101302633A (en) * | 2008-01-31 | 2008-11-12 | 顿力集团有限公司 | Trivalent chromium electroplating bath solution formula and bath forming method |
| CN101665960A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Trivalent chromium sulfate plating solution and preparation method thereof |
| CN101792917A (en) * | 2010-03-31 | 2010-08-04 | 哈尔滨工业大学 | Preparation method and electroplating method of normal-temperature environment-friendly sulfate trivalent chromium electroplating liquid |
| 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 |
-
2019
- 2019-01-16 CN CN201910037607.XA patent/CN109652827A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1368748A (en) * | 1972-02-08 | 1974-10-02 | British Non Ferrous Metals Res | Electrodeposition of chromium |
| EP0079768A1 (en) * | 1981-11-18 | 1983-05-25 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
| US4448648A (en) * | 1981-11-18 | 1984-05-15 | International Business Machines Corporation | Trivalent chromium electroplating baths |
| US5196109A (en) * | 1991-08-01 | 1993-03-23 | Geoffrey Scott | Trivalent chromium electrolytes and plating processes employing same |
| CN101280440A (en) * | 2007-04-02 | 2008-10-08 | 比亚迪股份有限公司 | Whole sulphate type trivalent chromium plating solution and electroplating method using the same |
| CN101302633A (en) * | 2008-01-31 | 2008-11-12 | 顿力集团有限公司 | Trivalent chromium electroplating bath solution formula and bath forming method |
| CN101665960A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Trivalent chromium sulfate plating solution and preparation method thereof |
| CN101792917A (en) * | 2010-03-31 | 2010-08-04 | 哈尔滨工业大学 | Preparation method and electroplating method of normal-temperature environment-friendly sulfate trivalent chromium electroplating liquid |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 方景礼 等: "《电镀添加剂 理论与应用》", 30 April 2006, 国防工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111776A (en) * | 2019-06-19 | 2020-12-22 | 广东禾木科技有限公司 | Cathode passivation protection solution for silver bonding wire |
| CN110512240A (en) * | 2019-09-04 | 2019-11-29 | 广东涂乐师新材料科技有限公司 | A kind of white chromium electrodeposit liquid of salt acid type highly corrosion resistant trivalent |
| WO2022224901A1 (en) * | 2021-04-21 | 2022-10-27 | 株式会社Jcu | Trivalent chromium plating solution and chromium plating method using same |
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