CN114277365B - Zinc-impregnated member re-corrosion prevention technology - Google Patents
Zinc-impregnated member re-corrosion prevention technology Download PDFInfo
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- CN114277365B CN114277365B CN202111609010.1A CN202111609010A CN114277365B CN 114277365 B CN114277365 B CN 114277365B CN 202111609010 A CN202111609010 A CN 202111609010A CN 114277365 B CN114277365 B CN 114277365B
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- 238000005536 corrosion prevention Methods 0.000 title description 3
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- 238000005336 cracking Methods 0.000 claims description 4
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- 238000004321 preservation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
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- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical group [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
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- 238000003618 dip coating Methods 0.000 description 4
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
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- 229910052742 iron Inorganic materials 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a re-anticorrosion process for a zincification part, which comprises the following process flows in sequence after the zincification of the zincification part is finished: the first step: removing ash in the residual temperature; and a second step of: finely removing; and a third step of: chromium-free passivation; fourth step: primary coating; fifth step: heating and ceramization, wherein a carbon-containing SiO xNy ceramic layer is generated on the surface layer of the zinc impregnation piece; sixth step: secondary coating; seventh step: repeating the sixth step for one to three times to obtain a finished product, wherein the finished product comprises a steel matrix, a zinc-iron alloy layer, a zinc passivation film layer, a carbon-containing SiO xNy ceramic layer and an organic polysilazane layer from inside to outside. According to the invention, on the basis of original zinc impregnation, the anticorrosion coating is added, so that the corrosion resistance of the zinc impregnation under the high-temperature high-humidity high-sulfur environment can be effectively improved.
Description
Technical Field
The invention relates to the technical field of rail accessory anti-corrosion treatment, in particular to a zinc impregnation piece re-corrosion technology.
Background
Powder zincification is a method for the surface corrosion protection treatment of iron and steel products, and is widely applied to railway track fittings. Powder zincating is a process in which zinc powder is diffused into an iron matrix by atoms at high temperature, thereby forming a zinc-iron alloy layer on the surface of a workpiece. The specific implementation is that the workpiece with cleaned surface is buried in a sealed container filled with a zinc-impregnation agent, heated to the vicinity of the melting point of zinc, kept for a certain time, and then cooled to room temperature along with a furnace. Compared with electroplating, the method does not need toxic electroplating liquid, and the treatment temperature is 100-250 ℃ lower than hot galvanizing. The powder zinc impregnation layer has the characteristics of good adhesive force, collision resistance, no brittleness and the like, and can achieve high corrosion resistance by passivation after zinc impregnation.
However, under certain conditions, only passivation treatment after zincification is still insufficient, for example, even though a zincified workpiece is subjected to passivation treatment under high-temperature, high-humidity and high-sulfur environments, the zincified workpiece is still corroded in a relatively short time, so that the maintenance amount is greatly increased, and in order to improve the corrosion resistance of the zincified workpiece under such conditions, many attempts have been made, for example, the dacromet coating is used for enhancing the corrosion resistance after zincification, but the dacromet coating contains chromium ions which are strong carcinogens, has serious environmental hazard, and the metal corrosion prevention field has been gradually exited.
Therefore, under the condition of keeping the prior advantages of zincification and passivation, the improvement is needed to improve the corrosion resistance of the zincification piece under the environment of high temperature, high humidity and high sulfur, and the corrosion resistance of the steel product after zincification is needed to be studied.
Disclosure of Invention
Therefore, the invention aims to provide a re-anticorrosion process for the galvanized part, so that the anticorrosion coating is added on the basis of the original zinc impregnation, and the anticorrosion capability of the galvanized part in the high-temperature high-humidity high-sulfur environment can be effectively improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A re-anticorrosion technology for a zincification part comprises the following technological processes sequentially carried out after the zincification of the zincification part is finished:
The first step: removing ash at the residual temperature, and separating the zinc-impregnated member from zinc ash;
and a second step of: fine ash removal, namely thoroughly removing residual zinc ash on the zinc-impregnated member and removing part of zinc layer;
and a third step of: chromium-free passivation is carried out on the galvanized part;
fourth step: coating for the first time, namely coating the passivated zinc-impregnated member with organic polysilazane for the first time;
fifth step: heating and ceramifying, putting the zinc-impregnated member dip-coated with the organic polysilazane into an atmosphere furnace, heating, partially cracking the organic polysilazane, generating a carbon-containing SiO xNy ceramic layer on the surface layer of the zinc-impregnated member, further penetrating zinc into the steel member, and enabling the pure zinc layer of the zinc-impregnated member to disappear.
Sixth step: coating the ceramic zinc-impregnated part with organic polysilazane for the second time, and drying and curing;
Seventh step: repeating the sixth step for one to three times to enable the thickness of the organic polysilazane coating to reach the required thickness, and obtaining a finished product;
The finished product comprises a steel matrix, a zinc-iron alloy layer, a zinc passivation film layer, a carbon-containing SiO xNy ceramic layer and an organic polysilazane layer from inside to outside.
Further, in the third step, the chromium-free passivation treatment process adopts a chromium-free passivation agent for passivation, and the formula of the chromium-free passivation agent is as follows: the corrosion inhibitor comprises a film forming agent, a complexing agent, a corrosion inhibitor, a pH value regulator and water, wherein the content (in percentage by mass) of the film forming agent is 10% -25%, the content of the complexing agent is 1% -5%, the content of the corrosion inhibitor is 2% -6%, the content of the pH value regulator is 1% -6%, the rest is water, the film forming agent is a main component of a passivating agent and is a modified aqueous acrylic resin, the brand of the film forming agent is D-225, the complexing agent is oxalic acid, the corrosion inhibitor is a mixture composed of two inorganic salts A and B, A is molybdate, B is phosphate, the proportion is 1.5:1, and the pH value regulator is an acetic acid-sodium acetate buffer solution.
In the fourth step, the organic polysilazane may be diluted with a polar or nonpolar volatile organic solvent (without alcohol solvents), and the concentration after dilution should be not less than 20%.
Further, in the fourth step, one or a mixture of any two of silicon powder, silicon dioxide powder, boron powder, titanium white powder and aluminum powder can be added into the organic polysilazane, and the addition amount is 0-0.3:1 according to the volume ratio.
Further, in the fifth step, the heating temperature is 450-550 ℃, the heating is performed under the protection of nitrogen, and the heating time is 1-24 hours.
Further, in the sixth step, the drying and curing temperature is 80-180 ℃ and the drying and curing time is 0.5-12 hours.
The invention has the following beneficial effects:
1. the outermost layer of the invention is the organic polysilazane which is cured, has smooth surface and strong hydrophobicity, and can effectively prevent water from being adhered to the surface of the zinc impregnation piece.
2. After the organic polysilazane at the outermost layer is solidified, the hardness is high, the erosion of wind sand in the nature can be effectively resisted for a long time, and the protection effect is good.
3. After the organic polysilazane of the outermost layer is solidified, the high-temperature resistance is good, the problem of softening and delamination can not occur at high temperature, the ceramic layer is formed by cracking at the temperature exceeding 450 ℃, and the formed ceramic layer still has high hardness and good corrosion resistance.
4. After the organic polysilazane of the outermost layer is solidified, the invention has good acid and alkali resistance, so that the corrosion resistance of the galvanized part is greatly improved.
5. According to the invention, even if the organic polysilazane of the outermost layer is worn out and leaks out of the ceramic layer, the hardness and acid and alkali resistance of the ceramic layer are higher than those of the organic polysilazane, and the ceramic layer can be continuously protected.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions in the embodiments of the present invention are clearly and completely described, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Examples:
A re-anticorrosion technology for a zincification part comprises the following technological processes at the end of zincification:
The first step: removing ash at the residual temperature, and separating the zinc-impregnated member from zinc ash;
the method comprises two ash removal processes:
Firstly, mechanical screening, namely after the work piece zincification and heat preservation are finished, cooling the zincification piece in air along with a heated sealed container, and when the temperature is cooled to 270-330 ℃, separating the work piece from zinc powder and other auxiliary materials by using a special vibration separating screen, wherein a negative pressure dust removing device is covered on the special vibration separating screen so as to maintain the environment in a workshop.
Then, washing with water to remove floating ash, cooling the workpiece with tap water to remove ash at 200-250deg.C, namely filling tap water into a large water tank, immersing the workpiece in water, taking out the workpiece with a mesh belt lifter, arranging a spray pipe at the top of the lifter, and spray cleaning with clean tap water.
For green production, an overflow pipe is arranged at the upper part of a large water tank, dirty water in the water tank flows into a collecting tank through the overflow pipe, a filter press is arranged at the top of the collecting tank, the dirty water is filtered by the filter press, clear water flowing out of the filter press is stored in a clear water tank, a water pump is arranged in the clear water tank, and the clear water is used for spray cleaning at the top of a lifting machine.
And a second step of: fine ash removal, namely thoroughly removing residual zinc ash on the zinc-impregnated member and removing partial pure zinc on the surface;
This step also includes two processes:
Firstly, polishing a roller, namely putting a zinc-impregnated member obtained by cooling and dedusting a workpiece by tap water into a special roller machine, wherein the roller machine is provided with a roller, a pulling sheet is arranged on the inner wall of the roller, gears are arranged outside the roller and are meshed and driven to rotate, fine sand and quartz sand with the diameter of 3-5mm are simultaneously put into the roller machine, the weight ratio of the fine sand to the quartz sand is 1:1, the weight ratio of the sand to the workpiece is 2-3:1, tap water is finally added, so that the liquid level is enabled to be over the workpiece, when the roller rotates, the pulling sheet on the inner wall of the roller is used for stirring, quartz sand, fine sand and the workpiece are rubbed in the process, zinc ash with strong surface viscosity of the workpiece is removed, part of pure zinc on the surface is rubbed and removed, and after the set time is reached, pouring and screening are carried out.
Secondly, cleaning and ash removing, wherein the sieved zinc-impregnated member is subjected to cleaning and ash removing by an ash removing device (the device disclosed in my patent application number 202121857082.3 and an ash removing device in a zinc-impregnated member passivation area) before passivation of the zinc-impregnated member, and the device has the following structure:
The device comprises a workpiece hanging basket, a first cleaning tank, a second cleaning tank and a draining device, wherein the first cleaning tank, the second cleaning tank and the draining device are sequentially arranged;
The first cleaning tank is an industrial ultrasonic cleaning tank and comprises a stainless steel tank body and an ultrasonic generator, wherein the ultrasonic generator is arranged at the bottom of the tank body;
The second cleaning tank is a spray type cleaning tank and comprises a water accumulation tank body, spray pipes, water pipes and a water pump, wherein one spray pipe is arranged above each of the front side and the rear side of the water accumulation tank body, a water outlet is formed in the bottom of the water accumulation tank body, the water outlet is connected with the water pipes, the water pipes are connected with the water pump, the water pump is connected with the spray pipes, and spray holes are formed in the spray pipes;
The draining device comprises a draining rack and a drainage ditch, wherein the draining rack is in the shape of a parallel bar and comprises 4 brackets and two transverse bars, the two transverse bars are arranged on the 4 brackets in parallel, the brackets are fixedly arranged on the ground, and the drainage ditch is arranged on the ground below the draining rack;
the work piece hanging basket includes the basket body and hangs the pull rod, it is the door type to hang the pull rod, and upper portion central point puts and is being provided with rings, and both sides outwards bulge, be convenient for place on the waterlogging caused by excessive rainfall frame, hang the pull rod setting on the basket body, the equipartition has the hole on the basket body.
The specific cleaning process is as follows:
Firstly, placing a galvanized part subjected to roller ash removal into a workpiece hanging basket, then hanging the workpiece hanging basket by a crane, placing the workpiece hanging basket into a first cleaning tank, and placing a cleaning solution of a cleaning ash removing agent before passivation of the galvanized part in the first cleaning tank, wherein the cleaning ash removing agent before passivation of the galvanized part is a special cleaning agent developed by me, the cleaning ash removing agent before passivation of the galvanized part can be effectively performed, the effect is good, ultrasonic cleaning is performed for a period of time, most zinc ash on the surface of the galvanized workpiece is cleaned and removed, and because the solution in the first cleaning tank does not flow, a small amount of zinc ash and cleaning solution can remain on the workpiece hanging basket and the basket body, hanging the workpiece hanging basket into a second cleaning tank by the crane, spraying and cleaning for a period of time, thoroughly cleaning the residual zinc ash and the cleaning solution, and hanging the workpiece hanging basket onto a draining rack for draining.
And a third step of: chromium-free passivation is carried out on the galvanized part;
This step also involves two processes:
firstly, soaking and passivating, namely placing a work basket with a galvanized part into a container with a chromium-free passivating solution, and soaking and passivating, wherein the specific formula of a chromium-free passivating agent (the chromium-free passivating agent, I have applied for patent, application number 202010354383.8 and a chromium-free passivating agent for powder zinc impregnation) in the chromium-free passivating solution is as follows:
The corrosion inhibitor comprises a film forming agent, a complexing agent, a corrosion inhibitor, a pH value regulator and water, wherein the film forming agent is modified aqueous acrylic resin (D-225), the content (in terms of mass fraction) is 18%, the complexing agent is oxalic acid, the content is 2.8%, and the corrosion inhibitor is a mixture composed of two inorganic salts A and B, wherein A is molybdate, and B is phosphate, wherein A: b=1.5:1, the content of corrosion inhibitor is 4.0%, the content of the pH regulator is 4.5% of acetic acid-sodium acetate buffer solution, and the rest is deionized water.
And secondly, drying, namely placing the passivated zinc-impregnated part into a mesh belt conveying dryer, and drying at the temperature of 150 ℃.
Fourth step: coating, namely, coating organic polysilazane on the passivated zinc-impregnated member for the first time;
This step also includes two processes:
Firstly dip-coating, diluting dimethyl polysilazane and monomethyl polysilazane to 60% by using n-butyl ether, loading the diluted polysilazane and the diluted polysilazane into a container of dip-coating equipment, and dip-coating a passivated zinc-impregnated piece in a suspension mode, so that the surface of the zinc-impregnated piece is uniformly coated with the upper layer of organic polysilazane.
In the process, one or a mixture of any two of silicon powder, silicon dioxide powder, boron powder, titanium dioxide powder and aluminum powder can be added into the organic polysilazane, the addition amount is 0-0.3:1 according to the volume ratio,
In the process, a negative pressure air draft environment-friendly device is arranged above the dip-coating device, and is connected with the waste gas absorption tower outside the workshop, so that the workshop environment is maintained.
Secondly, negative pressure convulsions are dried, with the zinc impregnation spare that has dip-coated organic polysilazane in negative pressure convulsions airing device, get rid of n-butyl ether solvent, dry, negative pressure convulsions airing device, including drying stores pylon, exhaust hood, negative pressure air exhauster and organic waste gas absorption tower, set up the exhaust hood above the drying stores pylon, the exhaust hood is connected with the negative pressure exhaust exhauster, and the negative pressure exhaust is connected with organic waste gas absorption tower. The negative pressure air draft airing device has the advantages of high airing speed, high efficiency and environmental protection pollution.
Fifth step: heating and ceramifying, putting the zinc-impregnated member dip-coated with the organic polysilazane into an atmosphere furnace, heating, partially cracking the organic polysilazane, generating a carbon-containing SiO xNy ceramic layer on the surface layer of the zinc-impregnated member, continuously penetrating the pure zinc layer on the zinc-impregnated member into the zinc-impregnated member under the action of high temperature in the process, forming a zinc-iron alloy layer, and completely disappearing the pure zinc layer.
In the step, nitrogen is introduced into the atmosphere furnace for protection, the heating temperature is 500 ℃, and the heat preservation time is 3 hours, so that the coated organic polysilazane is cracked.
Sixth step: coating the ceramic zinc-impregnated part with organic polysilazane for the second time, and then drying and curing;
In this step, the same concentration of the organic polysilazane as in the fourth step may be used, or an organic polysilazane having a different concentration may be used, or a different kind of organic polysilazane may be used, and in this embodiment, the same concentration of the organic polysilazane as in the fourth step is used.
After the secondary coating, the mixture was dried in a drying oven at 120℃for 3 hours.
Seventh step: repeating the sixth step twice to make the thickness of the organic polysilazane coating reach more than 0.5mm, thus obtaining the finished product.
The finished product comprises a steel matrix, a zinc-iron alloy layer, a zinc passivation film layer, a carbon-containing SiO xNy ceramic layer and an organic polysilazane layer from inside to outside.
The elastic strip produced according to the process steps of this example had a surface with an organo polysilazane hardness of greater than 8H and was sandblasted at a pressure of 0.8MPa for 2 minutes without the organo polysilazane being sandblasted, exhibiting good friction resistance.
The track pressing plate produced according to the process steps of the embodiment has water placed on the surface thereof, the contact angle of the water drops with the track pressing plate is more than 110 degrees, the rolling angle of the water drops is less than 20 degrees, and good hydrophobicity is shown.
After 2400 hours of neutral salt spray test, the galvanized part has a protection level of more than or equal to 5 levels; through 200 sulfur dioxide experiments, red rust does not appear; in the process of 20 times of high-temperature sulfur dioxide experiments, the ambient temperature is maintained at 80 ℃ and the process is carried out under the condition of condensation, and red rust does not appear.
Finally, it is noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and that other modifications and equivalents thereof by those skilled in the art should be included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (3)
1. A process for re-preserving a zinc-impregnated member is characterized by comprising the following steps: after the zincification of the zincification part is finished, the following process flows are sequentially carried out:
the first step: removing ash at the residual temperature, wherein the two processes of mechanical separation and water cleaning to remove floating ash are included;
And a second step of: fine ash removal comprises two processes of roller polishing and cleaning ash removal;
The device used for polishing the roller is a roller machine, the roller machine is provided with a roller, a poking plate is arranged on the inner wall of the roller, a gear is arranged outside the roller, and the roller is driven to rotate through gear engagement;
The device for cleaning and removing the ash is an ash removing device before passivation of the zinc-impregnated member;
And a third step of: performing chromium-free passivation, performing passivation treatment by using passivation solution prepared from a chromium-free passivating agent, and drying;
drying, namely placing the passivated zinc-impregnated member into a mesh belt conveying dryer, and drying at the temperature of 150 ℃;
fourth step: coating, namely, coating organic polysilazane on the passivated zinc-impregnated member for the first time, and performing negative pressure air suction and drying after coating;
The device used in the negative pressure air draft airing process is a negative pressure air draft airing device and comprises an airing hanger, an air draft cover, a negative pressure air draft fan and an organic waste gas absorption tower, wherein the air draft cover is arranged on the airing hanger and connected with the negative pressure air draft fan, and the negative pressure air draft is connected with the organic waste gas absorption tower;
The organic polysilazane can be diluted by polar or nonpolar volatile organic solvents, and the concentration after dilution is more than or equal to 60 percent, wherein the organic solvents do not contain alcohol solvents;
fifth step: heating and ceramifying, namely putting the zinc-impregnated member coated with the organic polysilazane into an atmosphere furnace, heating at the temperature of 450-550 ℃ under the protection of nitrogen for 1-24 hours, and cracking the organic polysilazane to generate a carbon-containing SiOxNy ceramic layer on the surface layer of the zinc-impregnated member;
Sixth step: coating the ceramic zinc-impregnated part with organic polysilazane for the second time, and drying and curing at 80-180deg.C for 0.5-12 hr
Seventh step: repeating the sixth step for one to three times to enable the thickness of the organic polysilazane coating to reach the required thickness, and obtaining a finished product;
the finished product comprises a steel matrix, a zinc-iron alloy layer, a zinc passivation film layer, a carbon-containing SiOxNy ceramic layer and an organic polysilazane layer from inside to outside.
2. A process for the re-preservation of a zinc coated article according to claim 1, characterized in that: in the third step, the chromium-free passivating treatment process adopts a chromium-free passivating agent for passivation, and the formula of the chromium-free passivating agent is as follows: the corrosion inhibitor comprises a film forming agent, a complexing agent, a corrosion inhibitor, a pH value regulator and water, wherein the content of the film forming agent is 10-25% by mass percent, the content of the complexing agent is 1-5%, the content of the corrosion inhibitor is 2-6%, the content of the pH value regulator is 1-6%, the rest is water, the film forming agent is a main component of a passivating agent and is a modified aqueous acrylic resin, the brand of the film forming agent is D-225, the complexing agent is oxalic acid, the corrosion inhibitor is a mixture composed of two inorganic salts A and B, A is molybdate, B is phosphate, the proportion is 1.5:1, and the pH value regulator is an acetic acid-sodium acetate buffer solution.
3. A process for the re-preservation of a zinc coated article according to claim 1, characterized in that: in the fourth step, one or a mixture of any two of silicon powder, silicon dioxide powder, boron powder, titanium dioxide and aluminum powder is added into the organic polysilazane, and the addition amount is 0-0.3:1 according to the volume ratio.
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| CN109811300A (en) * | 2019-04-10 | 2019-05-28 | 青岛大牧人机械股份有限公司 | A kind of standard component zincizing technique |
| CN111270231A (en) * | 2020-04-29 | 2020-06-12 | 郑州中原利达新材料有限公司 | Chromium-free passivator for powder zinc impregnation |
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| US6294261B1 (en) * | 1999-10-01 | 2001-09-25 | General Electric Company | Method for smoothing the surface of a protective coating |
| JP2002332561A (en) * | 2001-05-09 | 2002-11-22 | Riken Corp | Partially nitrided piston ring and partially nitrided piston ring |
| EP1870485A1 (en) * | 2006-06-22 | 2007-12-26 | Siemens Aktiengesellschaft | Composition and method for metalizing a component |
| CN103316828B (en) * | 2013-05-28 | 2014-09-10 | 中国船舶重工集团公司第七二五研究所 | Production method for ship fastener complex coating |
| CN108707420A (en) * | 2018-04-03 | 2018-10-26 | 广东工业大学 | A kind of cured polysilazane coating of room-temperature plasma and its preparation method and application |
| CN212383930U (en) * | 2020-09-07 | 2021-01-22 | 烟台首钢磁性材料股份有限公司 | A preparation device for NdFeB permanent magnet ceramic coating |
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| CN101389721A (en) * | 2006-02-23 | 2009-03-18 | 克拉里安特国际有限公司 | Coatings comprising polysilazanes for preventing scaling and corrosion |
| CN109811300A (en) * | 2019-04-10 | 2019-05-28 | 青岛大牧人机械股份有限公司 | A kind of standard component zincizing technique |
| CN111270231A (en) * | 2020-04-29 | 2020-06-12 | 郑州中原利达新材料有限公司 | Chromium-free passivator for powder zinc impregnation |
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