CN107502925B - Aqueous chloride galvanizing brightener - Google Patents
Aqueous chloride galvanizing brightener Download PDFInfo
- Publication number
- CN107502925B CN107502925B CN201710568155.9A CN201710568155A CN107502925B CN 107502925 B CN107502925 B CN 107502925B CN 201710568155 A CN201710568155 A CN 201710568155A CN 107502925 B CN107502925 B CN 107502925B
- Authority
- CN
- China
- Prior art keywords
- brightener
- percent
- main
- water
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
Abstract
In order to solve the problems, the water-based chloride zinc-plating brightener improves the performance of the brightener and reduces the pollution of products in the production and use processes by improving the proportion and the processing technology. In order to achieve the effect, the water-based chloride zinc-plating brightener is prepared by combining a modified main brightener intermediate with a carrier organic matter, wherein the modified main brightener intermediate is prepared by a first main brightener and a second main brightener in proportion, and a finished water-based chloride zinc-plating brightener is prepared by the first main brightener in a proportion of 20-30g/L, the second main brightener in a proportion of 60-70g/L, a softener in a proportion of 250-350g/L and sodium benzoate in a proportion of 40-80 g/L.
Description
Technical Field
The invention relates to a brightener, in particular to a water-based chloride zinc plating brightener and a preparation process thereof.
Background
Chloride galvanizing began to be put into production in China at the end of the 60 th century in 20 th century, and developed rapidly after the 80 th century in 20 th century. At present, acid chloride galvanization is the most widely applied in the galvanization industry, the process adopts an oil-soluble chloride galvanization brightener, uses o-chlorobenzaldehyde and benzalacetone as main brightening agents, uses a large amount of surfactant as a carrier, and has the advantages of high light-emitting speed, high brightness and high current efficiency. Secondly, the dispersion ability is poor, and the coating thickness is not uniform for complex workpieces. And thirdly, the COD in the discharged wastewater is caused, the discharge standard established by the state is that the COD does not exceed 30mg/L, and because a large amount of brightener is applied, the main component of the brightener is also called as the surfactant of the carrier, and because no good surfactant treatment and recovery technology exists, the problem that the COD is difficult to reach the standard is caused, and the subsequent investment on environmental protection is overlarge. Fourthly, the passivation is difficult due to the inclusion of organic matters in the coating.
To this end, the patent numbers are: 201010299325.6 patent of invention A synthetic main brightener for preparing zinc plating brightener is also disclosed, the formula components are: 59-61% of salicylaldehyde, 24-26% of formaldehyde and 14-16% of 2.4-dichlorobenzaldehyde, the formula components are prepared according to the proportion, added into a reaction kettle and mixed and stirred uniformly, then alkaline liquor with the content of 50% is added according to the proportion of 350-400 ml/L, the pH value is adjusted to 6.3-6.7, the temperature is heated to 75-85 ℃, and the temperature is kept for 3-4 hours. Cooling to room temperature, filtering with filter cloth, adding the filtered precipitate into a drier for drying, and drying in a dryer to obtain the final product. When in use, the brightener is prepared by the brightener and a high-temperature carrier, is used for potassium salt zinc plating, has the advantages of quick polishing, no oxidation, good electroplating quality, high coating brightness, stability, durability and no discoloration.
However, in such a scheme, the organic matters are still too much, the pollution of the whole electroplating solution is very serious, and the environment-friendly effect cannot be realized.
Disclosure of Invention
In order to solve the problems, the water-based chloride zinc-plating brightener improves the performance of the brightener and reduces the pollution of products in the production and use processes by improving the proportion and the processing technology.
In order to achieve the effect, the water-based chloride zinc-plating brightener is prepared by combining a modified main brightener intermediate with a carrier organic matter, wherein the modified main brightener intermediate is prepared by a first main brightener and a second main brightener in proportion, and the preparation method of the first main brightener comprises the following steps: taking the following components in percentage by mass:
15 to 20 percent of o-chlorobenzaldehyde,
10 to 15 percent of benzylidene acetone,
35 to 55 percent of formaldehyde,
the balance of water; adding the mixture into a reaction kettle, dropwise adding a saturated solution of sodium metabisulfite and sodium hydroxide, wherein the mass percentage of the sodium metabisulfite and the sodium hydroxide in the saturated solution is not lower than 41%, stirring at the speed of 45-60round/min, reacting for one hour to obtain a white precipitate, filtering, and drying the white precipitate at the temperature of 80 ℃ for 30-45 minutes to obtain white powder;
the preparation method of the second main brightener comprises the following steps: taking the following components in percentage by mass:
5 to 7 percent of heliotropin,
15 to 30 percent of diformaldehyde,
10 to 15 percent of salicylaldehyde,
the rest is water; adding the mixture into a reaction kettle, adding a 30 mass percent sodium hydroxide saturated solution, stirring and reacting for two hours at a speed of 45-60round/min, obtaining white precipitate through reduced pressure distillation, filtering, and drying the white precipitate for 30-45 minutes at a temperature of 80 ℃ to obtain white powder after preparation;
preparing a finished product of the water-based chloride zinc-plating brightener by using the proportion of 20-30g/L of the first main brightener, 60-70g/L of the second main brightener, 350g/L of the softener and 40-80g/L of sodium benzoate, placing the raw materials into a reaction kettle, heating to 130-140 ℃, reacting for 2 hours, carrying out centrifugal drying, and finally drying to obtain the finished product.
Preferably, the first main brightener comprises the following components in percentage by mass:
15 percent of o-chlorobenzaldehyde,
10 percent of benzylidene acetone,
55 percent of formaldehyde,
and 30% of water. The formaldehyde in such a proportion has more components, low cost and good brightening effect, but the final sewage treatment difficulty is more complex.
Preferably, the first main brightener comprises the following components in percentage by mass:
20 percent of o-chlorobenzaldehyde,
15 percent of benzylidene acetone,
35 percent of formaldehyde,
and 30% of water. In the proportion, the formaldehyde is less, the pollution is less, but the cost of the raw materials is higher.
Preferably, the second main brightener comprises the following components in percentage by mass:
5 percent of heliotropin,
30 percent of diformaldehyde,
10 percent of salicylaldehyde,
55% of water. The concentration of the second main brightener is higher under the proportion, the electroplating effect is better, but the cost is slightly higher.
Preferably, the second main brightener comprises the following components in percentage by mass:
7 percent of heliotropin,
15 percent of diformaldehyde,
15 percent of salicylaldehyde,
and (5) 63% of water. The proportion maximally saves the cost on the premise of basically meeting the electroplating effect.
Preferably, 10-20g/L of auxiliary brightener is also added in the process of preparing the finished product of the aqueous chloride galvanizing brightener.
Due to the adoption of the technical scheme, the invention has the beneficial effects that: compared with the prior art, the method better meets the requirements of environment-friendly and clean production, and especially reduces the COD of the wastewater discharged in the production process of the product by 50-80 percent compared with the prior art. The production process saves energy, changes the prior oily property into water-based property, is suitable for various environments, reduces the pressure of the acidic galvanizing process and the alkaline galvanizing process on environmental protection treatment, and is very helpful for the treatment of three wastes and the washing effect.
Detailed Description
Example 1: the water-based chloride zinc-plating brightener is prepared by combining a modified main brightener intermediate with a carrier organic matter, wherein the modified main brightener intermediate is prepared by a first main brightener and a second main brightener in proportion, and the preparation method of the first main brightener comprises the following steps: taking the following components in percentage by mass:
20 percent of o-chlorobenzaldehyde,
15 percent of benzylidene acetone,
35 percent of formaldehyde,
and 30% of water.
Adding the mixture into a reaction kettle, dropwise adding a saturated solution of sodium metabisulfite and sodium hydroxide, wherein the mass percentage of the sodium metabisulfite and the sodium hydroxide in the saturated solution is 45%, stirring at the speed of 60 rounds/min, reacting for one hour to obtain a white precipitate, filtering, and drying the white precipitate at the temperature of 80 ℃ for 45 minutes to obtain white powder;
the preparation method of the second main brightener comprises the following steps: taking the following components in percentage by mass:
5 percent of heliotropin,
30 percent of diformaldehyde,
10 percent of salicylaldehyde,
55% of water. Adding the mixture into a reaction kettle, adding a sodium hydroxide saturated solution with the mass percent of 30%, stirring and reacting for two hours at the speed of 60round/min, obtaining white precipitate through reduced pressure distillation, filtering, drying the white precipitate for 30 minutes at the temperature of 80 ℃, and obtaining white powder after the preparation is finished;
preparing a finished product of the water-based chloride zinc-plating brightener by using the proportion of 20g/L of a first main brightener, 70g/L of a second main brightener, 350g/L of a softener and 80g/L of sodium benzoate, placing the raw materials into a reaction kettle, heating to 130-140 ℃, reacting for 2 hours, carrying out centrifugal drying, and finally drying to obtain the finished product.
The product is aqueous liquid, and has no foam and alcohol solvent. And simultaneously, the odor of o-chlorobenzaldehyde is not generated. Results of the hall cell experiment:
the experimental conditions are as follows:
potassium chloride: 220g/L zinc chloride: 65g/L boric acid: 30g/L of brightener: 1mL/L of softener: 20mL/L temperature: current density at 25 degrees celsius: 1A/dm 2250 ML Hell cell.
Wherein, the brightener is respectively compared with the traditional oil-soluble brightener and the brightener prepared by the invention, and the result is as follows;
(1) the brightness of the water-based brightener is higher than that of the oil-soluble brightener, so that the mirror surface brightness can be really achieved.
(2) Dispersibility test
After 10 minutes of electroplating, the oil-soluble brightener plates out the test piece, the high-area plating layer is thick, the low-area plating layer is thin, and the condition of obvious uneven thickness is presented.
The water-soluble brightener can plate out test pieces, high areas and low areas, the thickness of the plating layer is uniform, and the dispersibility is very good. The difference of the zinc layer thickness in the high and middle and low regions is small in the 6u low region and 5u although the difference of the work potential is small.
(3) Flexibility testing
Electroplating for 5 hours, the test piece plated by the traditional brightener can generate a snap sound when being folded and bent, the plating layer can burst and fall off immediately, and the test piece plated by the aqueous brightener can not fall off and shows super-strong flexibility,
(4) color passivation film detection
When the same color passivation process is used for detection, the oil-soluble brightener plates out the test piece, after color passivation, the passive film can be wiped off by alcohol, and the water-soluble brightener plates out the test piece, after color passivation, the passive film can not be wiped off by alcohol, thus showing good binding force. The adoption of the water-based light agent is beneficial to passivation because the organic matter in the coating is less in impurity.
Example 2: the water-based chloride zinc-plating brightener is prepared by combining a modified main brightener intermediate with a carrier organic matter, wherein the modified main brightener intermediate is prepared by a first main brightener and a second main brightener in proportion, and the preparation method of the first main brightener comprises the following steps: taking the following components in percentage by mass:
17 percent of o-chlorobenzaldehyde,
13 percent of benzylidene acetone,
50 percent of formaldehyde,
20% of water; adding the mixture into a reaction kettle, dropwise adding a saturated solution of sodium metabisulfite and sodium hydroxide, wherein the mass percent of the sodium metabisulfite and the sodium hydroxide in the saturated solution is 43%, slowly stirring at a speed of 45 rounds/min because the product concentration is high and the water content is low, reacting for one hour to obtain a white precipitate, filtering, and drying the white precipitate at a temperature of 80 ℃ for 30 minutes to obtain white powder;
the preparation method of the second main brightener comprises the following steps: taking the following components in percentage by mass:
5 percent of heliotropin,
20 percent of diformaldehyde,
10 percent of salicylaldehyde,
water: 65 percent; adding the mixture into a reaction kettle, adding a sodium hydroxide saturated solution with the mass percent of 30%, stirring and reacting for two hours at the speed of 60round/min, obtaining white precipitate through reduced pressure distillation, filtering, and drying the white precipitate for 45 minutes at the temperature of 80 ℃ to obtain white powder after preparation;
preparing finished product water-based chloride zinc-plating brightener by the proportion of 30g/L of first main brightener, 60g/L of second main brightener, 300g/L of softener and 40g/L of sodium benzoate, placing the raw materials into a reaction kettle, heating to 130 ℃, reacting for 2 hours, carrying out centrifugal drying, and finally drying to obtain the finished product.
The product is aqueous liquid, and has no foam and alcohol solvent. And simultaneously, the odor of o-chlorobenzaldehyde is not generated. Results of the hall cell experiment:
the experimental conditions are as follows:
potassium chloride: 220g/L zinc chloride: 65g/L boric acid: 30g/L of brightener: 1mL/L of softener: 20mL/L temperature: current density at 25 degrees celsius: 1A/dm 2250 ML Hell cell.
Wherein, the brightener is respectively compared with the traditional oil-soluble brightener and the brightener prepared by the invention, and the result is as follows;
(1) brightness the aqueous brightener was higher than the oil soluble brightener, but slightly darker than the brightness in example 1.
(2) Dispersibility test
After 10 minutes of electroplating, the oil-soluble brightener plates out the test piece, the high-area plating layer is thick, the low-area plating layer is thin, and the condition of obvious uneven thickness is presented.
The water-soluble brightener can plate out test pieces, high areas and low areas, the thickness of the plating layer is uniform, and the dispersibility is very good. The station difference of the zinc layer thickness in the high, middle and low areas is inferior to that of the embodiment 1 in the 6u low area and 4u station difference, but the zinc layer thickness is still superior to that of the coating in the prior art.
(3) Flexibility testing
Electroplating for 5 hours, the test piece plated by the traditional brightener can generate a snap sound when being folded and bent, the plating layer can burst and fall off immediately, and the test piece plated by the aqueous brightener can not fall off and shows super-strong flexibility,
(4) color passivation film detection
When the same color passivation process is used for detection, the oil-soluble brightener plates out the test piece, after color passivation, the passive film can be wiped off by alcohol, and the water-soluble brightener plates out the test piece, after color passivation, the passive film can not be wiped off by alcohol, thus showing good binding force. The adoption of the water-based light agent is beneficial to passivation because the organic matter in the coating is less in impurity.
Example 3:
the water-based chloride zinc-plating brightener is prepared by combining a modified main brightener intermediate with a carrier organic matter, wherein the modified main brightener intermediate is prepared by a first main brightener and a second main brightener in proportion, and the preparation method of the first main brightener comprises the following steps: taking the following components in percentage by mass:
15 percent of o-chlorobenzaldehyde,
10 percent of benzylidene acetone,
55 percent of formaldehyde,
and 30% of water. Adding the mixture into a reaction kettle, dropwise adding a saturated solution of sodium metabisulfite and sodium hydroxide, wherein the mass percentage of the sodium metabisulfite and the sodium hydroxide in the saturated solution is not lower than 41%, stirring at the speed of 45-60round/min, reacting for one hour to obtain a white precipitate, filtering, and drying the white precipitate at the temperature of 80 ℃ for 30-45 minutes to obtain white powder;
the preparation method of the second main brightener comprises the following steps: taking the following components in percentage by mass:
7 percent of heliotropin,
15 percent of diformaldehyde,
15 percent of salicylaldehyde,
and (5) 63% of water.
Adding the mixture into a reaction kettle, adding a 30 mass percent sodium hydroxide saturated solution, stirring and reacting for two hours at a speed of 45-60round/min, obtaining white precipitate through reduced pressure distillation, filtering, and drying the white precipitate for 30-45 minutes at a temperature of 80 ℃ to obtain white powder after preparation;
preparing a finished product of the water-based chloride zinc-plating brightener by using 20g/L of a first main brightener, 70g/L of a second main brightener, 250g/L of a softening agent, 60g/L of sodium benzoate and 10-20g/L of an auxiliary brightener, placing the raw materials into a reaction kettle, heating to 140 ℃, reacting for 2 hours, carrying out centrifugal drying, and finally drying to obtain the finished product.
The product is aqueous liquid, and has no foam and alcohol solvent. And simultaneously, the odor of o-chlorobenzaldehyde is not generated. Results of the hall cell experiment:
the experimental conditions are as follows:
potassium chloride: 220g/L zinc chloride: 65g/L boric acid: 30g/L of brightener: 1mL/L of softener: 20mL/L temperature: current density at 25 degrees celsius: 1A/dm 2250 ML Hell cell.
Wherein, the brightener is respectively compared with the traditional oil-soluble brightener and the brightener prepared by the invention, and the result is as follows;
(1) the brightness aqueous brightener is higher than the oil-soluble brightener.
(2) Dispersibility test
After 10 minutes of electroplating, the oil-soluble brightener plates out the test piece, the high-area plating layer is thick, the low-area plating layer is thin, and the condition of obvious uneven thickness is presented.
The water-soluble brightener can plate out test pieces, high areas and low areas, the thickness of the plating layer is uniform, and the dispersibility is very good. The difference of the positions of the zinc layer in the high, middle and low regions of the thickness is quite small in the low region of 6u and 5u, which is superior to the plating layer in the prior art.
(3) Flexibility testing
After 5 hours of electroplating, the test piece is plated by the traditional brightener, and folded and bent, a papa sound is generated, the coating cracks and falls off immediately, and when the test piece is plated by the aqueous brightener, the coating does not fall off, and the test piece shows super-strong flexibility, and the coating does not fall off after being folded and bent for at least 4 hours of electroplating.
(4) Color passivation film detection
When the same color passivation process is used for detection, the oil-soluble brightener plates out the test piece, after color passivation, the passive film can be wiped off by alcohol, and the water-soluble brightener plates out the test piece, after color passivation, the passive film can not be wiped off by alcohol, thus showing good binding force. The adoption of the water-based light agent is beneficial to passivation because the organic matter in the coating is less in impurity.
The solution of example 3 is practically most suitable for large-scale plant use with low pollution, but has the disadvantages of more complicated process steps and higher precision requirements for the formulation.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any changes or modifications within the technical field of the present invention by those skilled in the art are covered by the claims of the present invention.
Claims (5)
1. The water-based chloride zinc-plating brightener is prepared by combining a modified main brightener intermediate with a carrier organic matter, and is characterized in that: the modified main brightener intermediate is prepared from a first main brightener and a second main brightener in proportion, wherein the preparation method of the first main brightener comprises the following steps: taking the following components in percentage by mass:
15 to 20 percent of o-chlorobenzaldehyde,
10 to 15 percent of benzylidene acetone,
35 to 55 percent of formaldehyde,
the balance of water; adding the mixture into a reaction kettle, dropwise adding a saturated solution of sodium metabisulfite and sodium hydroxide, wherein the mass percentage of the sodium metabisulfite and the sodium hydroxide in the saturated solution is not lower than 41%, stirring at the speed of 45-60round/min, reacting for one hour to obtain a white precipitate, filtering, and drying the white precipitate at the temperature of 80 ℃ for 30-45 minutes to obtain white powder;
the preparation method of the second main brightener comprises the following steps: taking the following components in percentage by mass:
5 to 7 percent of heliotropin,
15 to 30 percent of diformaldehyde,
10 to 15 percent of salicylaldehyde,
the rest is water; adding the mixture into a reaction kettle, adding a 30 mass percent sodium hydroxide saturated solution, stirring and reacting for two hours at a speed of 45-60round/min, obtaining white precipitate through reduced pressure distillation, filtering, and drying the white precipitate for 30-45 minutes at a temperature of 80 ℃ to obtain white powder after preparation;
preparing a finished product of the water-based chloride zinc-plating brightener by using the proportion of 20-30g/L of the first main brightener, 60-70g/L of the second main brightener, 350g/L of the softener and 40-80g/L of sodium benzoate, placing the raw materials into a reaction kettle, heating to 130-140 ℃, reacting for 2 hours, carrying out centrifugal drying, and finally drying to obtain the finished product.
2. The aqueous chloride zinc plating brightener as set forth in claim 1, wherein: the first main brightener comprises the following components in percentage by mass:
20 percent of o-chlorobenzaldehyde,
15 percent of benzylidene acetone,
35 percent of formaldehyde,
and 30% of water.
3. The aqueous chloride zinc plating brightener as set forth in claim 1, wherein: the second main brightener comprises the following components in percentage by mass:
5 percent of heliotropin,
30 percent of diformaldehyde,
10 percent of salicylaldehyde,
55% of water.
4. The aqueous chloride zinc plating brightener as set forth in claim 1, wherein: the second main brightener comprises the following components in percentage by mass:
7 percent of heliotropin,
15 percent of diformaldehyde,
15 percent of salicylaldehyde,
and (5) 63% of water.
5. The aqueous chloride zinc plating brightener as set forth in claim 1, wherein: 10-20g/L of auxiliary brightener is also added in the process of preparing the finished product of the aqueous chloride zinc plating brightener.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710568155.9A CN107502925B (en) | 2017-07-12 | 2017-07-12 | Aqueous chloride galvanizing brightener |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710568155.9A CN107502925B (en) | 2017-07-12 | 2017-07-12 | Aqueous chloride galvanizing brightener |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107502925A CN107502925A (en) | 2017-12-22 |
| CN107502925B true CN107502925B (en) | 2020-03-31 |
Family
ID=60678638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710568155.9A Active CN107502925B (en) | 2017-07-12 | 2017-07-12 | Aqueous chloride galvanizing brightener |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107502925B (en) |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046648A (en) * | 1975-09-29 | 1977-09-06 | E. I. Du Pont De Nemours And Company | Polyamine additives in alkaline zinc electroplating |
| US4397718A (en) * | 1982-05-24 | 1983-08-09 | Occidental Chemical Corporation | Zinc plating baths with condensating polymer brighteners |
| JPH05112889A (en) * | 1991-08-19 | 1993-05-07 | Yuken Kogyo Kk | Zincate-type zinc-iron alloy plating bath |
| US6238542B1 (en) * | 1998-09-15 | 2001-05-29 | Thomas Helden | Water soluble brighteners for zinc and zinc alloy electrolytes |
| US6830674B2 (en) * | 2002-11-05 | 2004-12-14 | Columbia Chemical Corporation | Brightener additive and bath for alkaline cyanide-free zinc electroplating |
| CN102002739B (en) * | 2010-10-08 | 2012-07-04 | 杜石峰 | Compounded main brightener for preparing zinc-plating brightener |
| CN104789998B (en) * | 2015-05-05 | 2017-02-22 | 广东达志环保科技股份有限公司 | Bright-type alkaline cyanide-free galvanization electroplating solution and preparation method |
| CN104878418B (en) * | 2015-06-29 | 2018-03-13 | 广州超邦化工有限公司 | A kind of non-cyanide alkali galvanizing solution of high stability |
-
2017
- 2017-07-12 CN CN201710568155.9A patent/CN107502925B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107502925A (en) | 2017-12-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3671476A (en) | Electrodeposition color coating composition and method for electrodeposition color coating of metal therewith | |
| CN101864589B (en) | Metal salt-free sealing agent for aluminum alloy anodic oxide film | |
| FR2726008A1 (en) | ALKALINE BATHS AND METHODS FOR THE GALVANOPLASTY OF ZINC AND ZINC ALLOYS | |
| CN110105861B (en) | Full-aqueous release coating for electrochemical aluminum hot stamping foil and preparation method thereof | |
| CN103937367A (en) | White cathodic electrophoretic coating, and preparation method and using method thereof | |
| CN101259990A (en) | Mirror back lacquer resin and mirror back lacquer | |
| CN107502925B (en) | Aqueous chloride galvanizing brightener | |
| CN101407927B (en) | Alkaline zinc-plating additive and process used for cyaniding liquid plating conversion thereof | |
| CN103088327A (en) | Metal surface silane treatment agent containing water-soluble phenolic resin and preparation method thereof | |
| CN105177694A (en) | Electrogilding solution organic impurity removing method | |
| CN105218726A (en) | A kind of metalchelated waterborne styrene-acrylic emulsion and preparation method thereof | |
| CN103102724A (en) | Metal surface silane treating agent containing acrylic acid and preparation method of metal surface silane treating agent | |
| CN104277567A (en) | Highly dispersed luminous aluminum pigment and preparation method thereof | |
| CN110129839A (en) | A kind of preparation method of copper brightener | |
| CN103388164A (en) | Non-cyanide alkaline copper electroplating process and formula | |
| CN103773284B (en) | Weather-resistant water-based adhesive and preparation method thereof | |
| CN103275522A (en) | Method for preparing silane coupling agent cladding modified talcum powder and silver mirror back coating | |
| CN102241935A (en) | Waterborne amino acrylate-based finish for burglar-proof door and preparation method for waterborne amino acrylate-based finish | |
| CN103923551A (en) | Low-film-thickness and high-covering-power black cathode electrophoretic paint and using method thereof | |
| CN102086326A (en) | Novel acrylic resin coating | |
| CN103014690A (en) | Novel pollution-free black passivation solution used for providing galvanized surface | |
| CN110684997B (en) | Zinc-plating electroplating liquid and preparation method thereof | |
| CN100500939C (en) | Technique for coloring copper red on tool steel component by chemical method | |
| CN102337540A (en) | Coating method for replacing electroplating | |
| CN102127760A (en) | Nano mirror spray coating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |