CN102443825A - High-concentration chromium sulfate-ammonium fluoride trivalent chromium electroplating solution and preparation method thereof - Google Patents
High-concentration chromium sulfate-ammonium fluoride trivalent chromium electroplating solution and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high concentration chromium sulfate-ammonium fluoride trivalent chromium electroplating solution and a preparation method thereof. The preparation method comprises steps that: (10 pure water with a volume of 2/3 of that a preset total electroplating solution volume is added into a vessel, and is heated; 30-70g/L of a buffering agent boric acid is added to the water, and is dissolved by stirring; (2) 60-150g/L of sodium chloride, 50-100g/L of ammonium chloride, 30-80g/L of ammonium fluoride, and 8-10g/L of ammonium bromide are added to the solution, and are dissolved by stirring; (3) 30-50g/L of an auxiliary complexing agent is added to the solution, and is dissolved by stirring; the pH value of the solution is regulated to 2.5-3.0; (4) 110-210g/L of a main salt chromium sulfate is added to the solution, and is dissolved by stirring; the pH value of the solution is regulated to 2.8-3.0; (5) 0.1-0.5g/L of polyethylene glycol is added to the mixture; pure water is added until a full dose is reached; the temperature is maintained at 55-60 DEG C; and aging is carried out for more than 12 hours with the maintained temperature, such that a finished product is obtained. According to the invention, advantages of two technological systems which are a total-sulfate system and a chloride system are integrated and optimized. An obtained chrome plating layer is uniform, white, and bright. The displacement is wide, and a full-bright decorative effect is achieved. The current efficiency of the electroplating solution is high, and the deposition speed of the electroplating solution is high. Therefore, with the electroplating solution, an obtained effect is better than that with a common total-sulfate trivalent chromium electroplating technological system in markets.
Description
(1) technical field: the present invention relates to a kind of trivalent chromium plating liquid and preparation method thereof; Specifically be a kind of high-concentration sulfuric acid chromium---Neutral ammonium fluoride trivalent chromium plating liquid and preparation method thereof; The present invention can be widely used in the surface decoration chromium plating of component such as machinery, electronics, electrical equipment, instrument, automobile, with the solidity to corrosion that improves these component and ornamental.
The (2) background technology: chromium coating has higher hardness and good wear resistance, solidity to corrosion, ornamental because of it; Therefore the protecting decorative coating that is widely used in component such as machinery, electronics, electrical equipment, instrument, automobile, household electrical appliances is that electroplating industry is used one of the widest plating.The electroplating process that obtains chromium coating at present mainly contains two kinds, and a kind of is traditional sexavalent chrome electroplating technology, and another kind is the trivalent chromium plating Technology.Because the toxicity of sexavalent chrome Electroplating Production is big, pollution is heavy, the wastewater treatment difficulty, and the water source that is caused, soil and air environmental pollution have caused the great attention of countries in the world; For example the galvanized electric equipment products of European Parliament's promulgation ROHS instruction regulation complete prohibition sexavalent chrome on July 1st, 2006 uses in the European market, completely forbids the sexavalent chrome Electroplating Production before EPA is defined in 2010; China also proposes very strict requirement to chromic production discharging about the environmental regulation of cleaner production.In order to replace the sexavalent chrome electroplating technology, people have carried out big quantity research to the lower trivalent chromium plating of toxicity.The trivalent chromium plating technology of in Electroplating Production, using at present mainly contains two individual system, and a kind of is the whole sulphate process system, and a kind of is the chloride process system.It is high similar with sexavalent chrome coating color and luster that the whole sulphate process system has the coating white luminance; Anode is the less advantage of main environmental pollution degree with oxygen evolution reaction; But whole sulphate process system ubiquity plating bath master salt metal content is low, bath stability is poor, current efficiency is low, sedimentation velocity is slow, short tank liquor of production feed supplement cycle is safeguarded the complicated loaded down with trivial details shortcoming of adjustment; And anode is analysed oxygen chromic oxidation is very easily taken place, and generates the sexavalent chrome contaminating impurity and cause plating bath to stop production to lose efficacy; Therefore the whole sulphate process system generally adopts precious metal to film anode to suppress chromic generation, perhaps adds reducing substances to eliminate chromic accumulation; The anodic input cost is short high work-ing life but precious metal is filmed, and the reducing substance that is added also can final oxidized formation impurities accumulation and influence the ordinary production of plating bath, so the less use in actual Electroplating Production of whole sulphate trivalent chromium process system.And in electroplating actual production, use more muriate trivalent chromium process system at present, have anode to separate out the shortcoming that chlorine influences production environment, and the white luminance of gained coating is also not as the whole sulphate process system; But chloride system master salt metal content is higher; The plating bath production stability is good; The high sedimentation velocity of current efficiency is fast; Generally can not generate sexavalent chrome impurity in the electroplating process, and can use the graphite anode production cost low, so muriate trivalent chromium process system obtains more application in actual Electroplating Production.
(3) summary of the invention: the object of the present invention is to provide a kind of high-concentration sulfuric acid chromium---Neutral ammonium fluoride trivalent chromium plating liquid and preparation method thereof; Complex optimum of the present invention the advantage of whole sulphate and two process systems of muriate, adopt high-concentration sulfuric acid chromium as main salt, kept sulfate trivalent chromium to electroplate the high characteristic of gained coating white luminance, on appearance luster, be superior to muriate trivalent chromium process system; Adopt chlorate as conducting salt, improved the electroconductibility of plating bath, kept the fast advantage of the high sedimentation velocity of chloride process system current efficiency; Through optimize screening with Neutral ammonium fluoride as main complexing agent, improved the concentration of trivalent chromium complex ion in the plating bath, make plating bath have the advantage that the good stability production feed supplement cycle grows; And on electroplate liquid formulation is formed, broken the routine that present trivalent chromium plating technical field generally adopts organic monoacid salt coordination chromium ion, made this prescription on actual electroplating effect, have clear superiority.Gained chromium coating of the present invention is evenly bright in vain, and it is broad to walk, and reaches complete bright decorative effect; The high sedimentation velocity of plating bath current efficiency is fast, is superior to the whole sulphate trivalent chromium plating process system that generally on market, uses.
A kind of high-concentration sulfuric acid chromium of the present invention---Neutral ammonium fluoride trivalent chromium plating liquid, its plating bath consists of: chromium sulphate 110-210 grams per liter is (with Cr
2(SO
4)
36H
2The O meter), sodium-chlor 60-150 grams per liter, ammonium chloride 50-100 grams per liter; Boric acid 30-70 grams per liter, Neutral ammonium fluoride 30-80 grams per liter, brometo de amonio 8-10 grams per liter; Auxiliary complex-former carboxylate salt total amount is the 30-50 grams per liter, wetting agent polyoxyethylene glycol 0.1-0.5 grams per liter, and all the other are aqueous solvent.
The processing parameter of described electroplate liquid is: working temperature 20-40 ℃, and cathode current density 10-20A/dm
2, bath pH value 2.5-3.2, electroplating time 2-15 minute, anode was a graphite anode.
Described auxiliary complex-former carboxylate salt is made up of two kinds low molecular organic salts of weak acid, a kind of in one type of ammonium salt that is selected from formic acid, acetate, oxalic acid, Padil or the sodium salt, a kind of in the another kind of salt that is selected from tartrate, oxysuccinic acid, Hydrocerol A, EDTA; The consumption of wherein back one type of low molecular organic salt of weak acid is last type 1.5-2 a times.
Prepare that above-mentioned a kind of high-concentration sulfuric acid chromium---the method for Neutral ammonium fluoride trivalent chromium plating liquid comprises the steps:
⑴ add the pure water of predetermined total plating bath volume 2/3 earlier in plating tank, be heated to 55-60 ℃, adds buffer reagent boric acid again, stirs dissolving fully;
⑵ add conducting salt sodium-chlor respectively, ammonium chloride, and main complexing agent Neutral ammonium fluoride, the anodic inhibitor brometo de amonio stirs dissolving fully;
⑶ add auxiliary complex-former, after stirring is dissolved fully, uses the pH value of concentrated hydrochloric acid adjustment solution to be 2.5-3.0;
⑷ add and become owner of the salt chromium sulphate, stir dissolving fully after, the pH value of using massfraction 20%NaOH solution to adjust solution is 2.8-3.0;
⑸ add the wetting agent polyoxyethylene glycol, replenishes pure water to predetermined total plating bath volume; Keeping the temperature of plating bath is 55-60 ℃, and the insulation ageing got final product more than 12 hours.
The present invention has following characteristics:
1. the chromium sulphate that adopts high density is as electroplating main salt; Improve the current efficiency and the sedimentation velocity of electroplate liquid with higher metal chromium ions content; The production feed supplement cycle that prolongs plating bath is improved production stability, has kept the gained chromium coating to have the high advantage of the careful white luminance of sulfate process system crystallization simultaneously.The gained chromium coating is superior to muriate trivalent chromium process system on decorative appearance.
2. adopt sodium-chlor ammonium chloride as conducting salt, have, in actual production, raise the efficiency energy-saving and cost-reducing than the fast electrochemistry advantage of the high sedimentation velocity of general whole sulphate trivalent chromium bath good conductivity current efficiency.Because halide-ions has precedence over the discharge oxidation of trivalent chromic ion on anode, be oxidized to chromic electrode process thereby effectively suppressed trivalent chromium, has eliminated the hidden danger of sexavalent chrome impurity to the plating bath pollution failure.
3. preferably composite through to multiple complexing agent; Developed a kind of with Neutral ammonium fluoride as main complexing agent; Low molecular carboxylic acid salt is as the solution system of auxiliary complex-former, and it is moderate to make in the plating bath of the present invention the formed multicomponent complex of trivalent chromic ion have an electrochemical stability, and high low area current potential equalization discharge walks broad; The advantage that the good color and luster of gained coating uniformity is consistent, and can main salt content of chromium ion higher with concentration change when big (23 ~ 45 grams per liter) obtain the chromium coating of good appearance.
4. adopt the boric acid that generally uses as buffer reagent; And in plating bath the shock-absorbing capacity of the anti-pH value variation of comprehensive performance under the synergy of other organic monoacid salt; Effectively guaranteed the production stability that the anti-pH value of plating bath changes, making electroplating time can prolong coating can thicken.
5. adopt low-molecular-weight polyethylene glycol (polymerization degree 200 ~ 400) as wetting agent, coating of the present invention is had promoter action, show as the compact crystallization degree and the luminance brightness of obvious raising chromium coating, strengthened the decorative appearance effect of chromium coating.
6. adopt graphite anode to reduce the Electroplating Production cost; Therefore the present invention does not generate deleterious sexavalent chrome impurity in plating production process, solved the technical barrier that the whole sulphate trivalent chromium plating generally can not use graphite anode.
The present invention compared with prior art has the following advantages and effect:
1. the trivalent chromium plating liquid employing high-concentration sulfuric acid chromium of the present invention's development is main salt; Chromium metal concentration can reach 45 grams per liters; Be 3 ~ 10 times of general whole sulphate trivalent chromium plating liquid, thereby prolonged the plating bath production feed supplement cycle and improved the stability and the working efficiency of Electroplating Production.
2. to adopt halogenide be conducting salt in the present invention, and than the good conductivity of whole sulphate trivalent chromium process system, the high sedimentation velocity of current efficiency is fast; Bath voltage reduces the power consumption minimizing in the electroplating process, and is energy-saving and cost-reducing in actual production.And the halide-ions that adds has changed the electrode behavior of on anode, analysing oxygen; Effectively suppress trivalent chromic ion and be oxidized to chromic phenomenon; Therefore can not use the expensive precious metal anode of filming, also need not add reducing substances to suppress chromic accumulation.
3. be that main complexing agent can be so that chromium sulphate keeps good plating flexibility under higher concentration with the inorganic salt Neutral ammonium fluoride, its actual effect as previously mentioned.And the whole sulphate trivalent chromium technology that research is at present used; Generally adopt organic carboxylate as main complexing agent; And when the chromium sulphate main salt concentration is low (common metal chromium 4-10 grams per liter), could realize the practical application performance of plating bath, thereby the present invention has tangible practical advantages.
4. the wide ranges good stability life cycle of the anti-pH variation of plating bath is long, and the plating bath use temperature is low can work at normal temperatures, and technological operation is easy.
5. the present invention adopts graphite anode Electroplating Production cost low, does not produce deleterious sexavalent chrome impurity in the electroplating process, therefore has the obvious practicability advantage than whole sulphate trivalent chromium process system.
6. the electroplating bath components of the present invention's development is simple, and the raw material market is in liberal supply, aboundresources, and cost is lower, has excellent cost performance, and market application foreground is wide.
The (4) embodiment:
Specific embodiment of the present invention is following:
The raw material of 6 six kinds of trivalent chromium plating liquid of embodiment 1-embodiment forms and consumption (is the example explanation to prepare 1 liter of electroplate liquid) is as shown in table 1, with 6 six kinds of electroplate liquids of embodiment 1-embodiment, tests with Hull Cell and to check its serviceability; Cofabrication sexavalent chrome standard chromium plating solution carries out Hull Cell experiment with as a comparison, and its result is as shown in table 2.
The content of sexavalent chrome standard chromium plating solution is: chromic anhydride 250 grams per liters, sulfuric acid 2.5 grams per liters, trivalent chromium 3 grams per liters.
The raw material of table 1 embodiment 1-6 trivalent chromium plating liquid is formed and consumption
Embodiment 1-6 trivalent chromium plating liquid making method is following:
⑴ add the pure water of predetermined total plating bath volume 2/3 earlier in plating tank, be heated to 55-60 ℃, adds buffer reagent boric acid again, stirs dissolving fully;
⑵ add conducting salt sodium-chlor respectively according to quantity, ammonium chloride, and main complexing agent Neutral ammonium fluoride, the anodic inhibitor brometo de amonio stirs dissolving fully;
⑶ add a kind of in formic acid, acetate, oxalic acid, the Padil according to quantity, adds a kind of among oxysuccinic acid, tartrate, Hydrocerol A, the EDTA more according to quantity, stir dissolving fully after, using the pH value of concentrated hydrochloric acid adjustment solution is 2.5 ~ 3.0;
⑷ add according to quantity and become owner of the salt chromium sulphate, stir dissolving fully after, the pH value of using massfraction 20%NaOH solution to adjust solution is 2.8-3.0;
⑸ add the wetting agent polyoxyethylene glycol according to quantity, replenishes pure water to predetermined total plating bath volume; Keeping the temperature of plating bath is 55-60 ℃, and the insulation ageing got final product more than 12 hours.
Table 2 embodiment 1-6 electroplate liquid and sexavalent chrome standard plating bath Hull Cell experimental result
Hull Cell current density range calculation formula is pressed:
D
k=I(5.1-5.24lgL) L=0.1~8.8cm
The Hull Cell anode of the embodiment 1 ~ 6 of trivalent chromium bath adopts the graphite cake anode, and the Hull Cell anode of sexavalent chrome plating bath adopts stereotype.The latten(-tin) (100 * 65 millimeters) of 0.5 millimeter thickness is all adopted in the negative electrode test piece, and test piece is handled with the 360# liquid honing before electroplating.
Can find out from the experimental result shown in the table 2; The trivalent chromium plating liquid of the different concns of embodiment 1 ~ 6 all has broad light district current density range; Demonstrate electroplate liquid of the present invention and have good walking property; And can change under the condition greatly at main salt concentration and other concentration of component, obtain the bright coating of coating outward appearance uniformity.With the contrast of sexavalent chrome standard plating bath, the luminance brightness of its dispersive ability of electroplate liquid of the present invention and walking property and coating outward appearance all will surmount traditional sexavalent chrome and electroplate.Prove that thus trivalent chromium plating liquid provided by the present invention has good use properties.
Need to prove that the foregoing description 1-6 is just to brief description of the present invention, rather than limitation of the present invention, anyly do not exceed the intraparenchymatous innovation and creation of the present invention, all fall in protection scope of the present invention.
Claims (4)
1. a high-concentration sulfuric acid chromium---Neutral ammonium fluoride trivalent chromium plating liquid, it is characterized in that plating bath consists of: chromium sulphate 110-210 grams per liter is (with Cr
2(SO
4)
36H
2The O meter), sodium-chlor 60-150 grams per liter, ammonium chloride 50-100 grams per liter; Boric acid 30-70 grams per liter, Neutral ammonium fluoride 30-80 grams per liter, brometo de amonio 8-10 grams per liter; Auxiliary complex-former carboxylate salt total amount is the 30-50 grams per liter, wetting agent polyoxyethylene glycol 0.1-0.5 grams per liter, and all the other are aqueous solvent.
2. a kind of high-concentration sulfuric acid chromium according to claim 1---Neutral ammonium fluoride trivalent chromium plating liquid is characterized in that: the processing parameter of described electroplate liquid is: working temperature 20-40 ℃, and cathode current density 10-20A/dm
2, bath pH value 2.5-3.2, electroplating time 2-15 minute, anode was a graphite anode.
3. a kind of high-concentration sulfuric acid chromium according to claim 1 and 2---Neutral ammonium fluoride trivalent chromium plating liquid; It is characterized in that: described auxiliary complex-former carboxylate salt is made up of two kinds low molecular organic salts of weak acid; A kind of in a kind of ammonium salt that is selected from formic acid, acetate, oxalic acid, Padil or the sodium salt, another kind is selected from a kind of in the salt of tartrate, oxysuccinic acid, Hydrocerol A, EDTA; The consumption of wherein back one type of low molecular organic salt of weak acid is last type 1.5-2 a times.
4. a kind of high-concentration sulfuric acid chromium as claimed in claim 1---the preparation method of Neutral ammonium fluoride trivalent chromium plating liquid is characterized in that comprising the steps:
⑴ add the pure water of predetermined total plating bath volume 2/3 earlier in plating tank, be heated to 55-60 ℃, adds buffer reagent boric acid again, stirs dissolving fully;
⑵ add conducting salt sodium-chlor respectively, ammonium chloride, and main complexing agent Neutral ammonium fluoride, the anodic inhibitor brometo de amonio stirs dissolving fully;
⑶ add auxiliary complex-former, after stirring is dissolved fully, uses the pH value of concentrated hydrochloric acid adjustment solution to be 2.5-3.0;
⑷ add and become owner of the salt chromium sulphate, stir dissolving fully after, the pH value of using massfraction 20%NaOH solution to adjust solution is 2.8-3.0;
⑸ add the wetting agent polyoxyethylene glycol, replenishes pure water to predetermined total plating bath volume; Keeping the temperature of plating bath is 55-60 ℃, and the insulation ageing got final product more than 12 hours.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103510130A (en) * | 2012-06-26 | 2014-01-15 | 武汉材料保护研究所 | Trivalent hard chromium electroplating method |
| CN104388989A (en) * | 2014-11-14 | 2015-03-04 | 无锡信大气象传感网科技有限公司 | Trivalent chromium electroplating liquid and preparation method thereof |
| CN105018974A (en) * | 2015-08-21 | 2015-11-04 | 无锡桥阳机械制造有限公司 | Trivalent chromium electroplate liquid and preparing method thereof |
| WO2015121790A3 (en) * | 2014-02-11 | 2016-01-21 | Muñoz Garcia Carlos Enrique | Continuous trivalent chromium plating method |
| CN105696028A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Trivalent chromium electroplating solution and electroplating method |
| CN106521610A (en) * | 2016-12-22 | 2017-03-22 | 西安博岳环保科技有限公司 | Combined titanium anode for hexavalent chromium electroplating and preparation method thereof |
| CN111349952A (en) * | 2020-03-06 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
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| CN111850621A (en) * | 2020-07-16 | 2020-10-30 | 上海交通大学 | Trivalent chromium electroplating solution and preparation method thereof |
| WO2021234075A1 (en) * | 2020-05-20 | 2021-11-25 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Method for hard chrome plating using trivalent chromium |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101078131A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院兰州化学物理研究所 | Method for electrodepositing ornamental chromium coating in trivalency chromium coating solution |
| EP2054539A2 (en) * | 2006-08-01 | 2009-05-06 | Fraunhofer-Gesellschaft zur Förderung der Angewandten Forschung e.V. | Method for deposition of chromium layers as hard- chrome plating, electroplating bath and hard- chrome surfaces |
| 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 |
-
2011
- 2011-12-07 CN CN201110401221.6A patent/CN102443825B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101078131A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院兰州化学物理研究所 | Method for electrodepositing ornamental chromium coating in trivalency chromium coating solution |
| EP2054539A2 (en) * | 2006-08-01 | 2009-05-06 | Fraunhofer-Gesellschaft zur Förderung der Angewandten Forschung e.V. | Method for deposition of chromium layers as hard- chrome plating, electroplating bath and hard- chrome surfaces |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 杜荣斌: "氟化物体系三价铬镀铬工艺的研究", 《化学研究》 * |
Cited By (13)
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|---|---|---|---|---|
| CN103510130A (en) * | 2012-06-26 | 2014-01-15 | 武汉材料保护研究所 | Trivalent hard chromium electroplating method |
| WO2015121790A3 (en) * | 2014-02-11 | 2016-01-21 | Muñoz Garcia Carlos Enrique | Continuous trivalent chromium plating method |
| CN104388989A (en) * | 2014-11-14 | 2015-03-04 | 无锡信大气象传感网科技有限公司 | Trivalent chromium electroplating liquid and preparation method thereof |
| CN105696028A (en) * | 2014-11-28 | 2016-06-22 | 中国科学院金属研究所 | Trivalent chromium electroplating solution and electroplating method |
| CN105018974A (en) * | 2015-08-21 | 2015-11-04 | 无锡桥阳机械制造有限公司 | Trivalent chromium electroplate liquid and preparing method thereof |
| CN106521610A (en) * | 2016-12-22 | 2017-03-22 | 西安博岳环保科技有限公司 | Combined titanium anode for hexavalent chromium electroplating and preparation method thereof |
| CN111349952A (en) * | 2020-03-06 | 2020-06-30 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
| CN111349952B (en) * | 2020-03-06 | 2021-06-08 | 广州三孚新材料科技股份有限公司 | Trivalent black chromium electroplating solution for solar heat collector |
| WO2021234075A1 (en) * | 2020-05-20 | 2021-11-25 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Method for hard chrome plating using trivalent chromium |
| FR3110606A1 (en) * | 2020-05-20 | 2021-11-26 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Hard chromium plating process from trivalent chromium |
| FR3110607A1 (en) * | 2020-05-20 | 2021-11-26 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Hard chromium plating process from trivalent chromium |
| CN111676494A (en) * | 2020-07-16 | 2020-09-18 | 上海交通大学 | Trivalent chromium electroplating solution, preparation method and application |
| CN111850621A (en) * | 2020-07-16 | 2020-10-30 | 上海交通大学 | Trivalent chromium electroplating solution and preparation method thereof |
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Address after: 668 No. 435001 Huangshi city of Hubei province xisaishanqu Huangshi Avenue Applicant after: Hubei ZhenHua Chemical Co., Ltd. Address before: 668 No. 435001 Huangshi city of Hubei province xisaishanqu Huangshi Avenue Applicant before: Huangshi Zhenhua Chemical Industry Co., Ltd. |
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