CN1052512A - Mechanized zinc-plating technology with electric zinc powder - Google Patents

Mechanized zinc-plating technology with electric zinc powder Download PDF

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Publication number
CN1052512A
CN1052512A CN 89109362 CN89109362A CN1052512A CN 1052512 A CN1052512 A CN 1052512A CN 89109362 CN89109362 CN 89109362 CN 89109362 A CN89109362 A CN 89109362A CN 1052512 A CN1052512 A CN 1052512A
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zinc
add
workpiece
gram
plating
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CN 89109362
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何明奕
周亚平
徐勇
角景明
刘丽
李胜长
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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Priority to CN 89109362 priority Critical patent/CN1052512A/en
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Abstract

Mechanized zinc-plating technology with electric zinc powder is that employing 280 to 300 purpose electric furnace zinc powders are raw material.And being equipped with the dispersion activator, smoothing agent, nucleating agent etc. modulates a kind of sedimentary slurries of zinc powder that are beneficial to, and the ferrous metals workpiece is carried out mechanical zinc-plating.It can be zinc-plated to 6~8 meters long all kinds of Welded Steel Pipe outside surfaces; Also can to scattered smallclothes surface galvanizing such as screw, tube stub, line hardware according to different batchings, zinc-plated bed thickness can in the 10-80 micron, regulate, the coating outward appearance is bright and clean, even, functional.

Description

Mechanized zinc-plating technology with electric zinc powder
Mechanized zinc-plating technology with electric zinc powder belongs to the overlay coating technical field.
Traditional ferrous metal surface galvanizing technology is hot dip process and plating.Thicker, the good corrosion resistance of or immersion coating, but need high temperature, energy consumption, zinc consumption more than 460 ℃ bigger, one ton of workpiece consumption of general every plating zinc, 80~120 kg.The zinc that wherein forms coating on workpiece only accounts for 30~50% of total zinc consumption, and remaining zinc forms zinc gray and cadmia because of oxidation or with the heating container reaction.Or immersion is unsuitable for plating threaded workpiece in addition.And workpiece also is heated to more than 460 ℃ by zinc liquid when being plated, and the temper brittleness that is in iron and steel produces the district, steel has been produced detrimentally affect.
The galvanized workpiece outward appearance that electroplating technology is produced is better, but thickness of coating is generally 10~20 microns, only is applicable to the decorative surface coating.
Mechanical zinc-plating process is for being applied to the novel process in the industry in recent years, and it is to adopt activator, metal zinc, impact media and water to be mixed into slurry, workpiece and the above-mentioned slurry formation coating that rolls in machinery drum.Because the effect of turning force, zinc granule is attached under impact effect and forms zinc coating on the working-surface, zinc coating is to be inlayed by the countless zinc that are flats to form, similar a kind of uniform crystal structure, fine with the tack of iron-based, the homogeneity of coating surpasses hot-dip galvanizing technique, and the zinc layer zinc consumption of same thickness only is 30~40% of hot dip process.
The initial stage of mechanical plating is operated in United States Patent (USP) U, S, A Pat2640001; All on the books in 2640002, the chemical activating agent that mechanical plating is adopted has been discussed in U, S, A Pat NO 3460977 later, the block or bar-shaped chemical activating agent with the certain speed dissolved has been proposed among the NO3328197, it mainly is to adopt citric acid.Among the USA Pat NO 3268356 chemical activating agent has been proposed and metal powder adds continuously in the mode that increases progressively, with density and the homogeneity of improving coating.
English Patent GBNO104160 has proposed employing high purity zinc powder, and wherein plumbous and arsenic content is no more than 0.2%, and the employing diameter is that 0.4~0.8 millimeter shot is an impact media.
Propose among the Japanese Patent Laid-Optn Patent 12405/72 to adopt the high purity zinc powder, bond to organic binder bond and form coating on the workpiece.
Existing mechanical zinc-plating process is that workpiece, impact media and water are added cylinder, add a small amount of acid solution cleaning workpiece surface in rolling according to the corrosion degree of workpiece; Add copper sulfate and on workpiece, deposit a copper layer as substrate; Add activator, add zinc powder simultaneously one by one; Add the coating that rolls and can obtain to require in 20~40 minutes in the material back.The workpiece plating is finished by pouring out in the cylinder, separates workpiece and impact media, and workpiece uses after vanning after flushing, the drying, impact media clean repeatedly.The main raw material that this current technology adopts is the pure metal zinc powder, because its granularity extremely inhomogeneous (being generally 80~100 orders), zinc granule is activatory degree difference in rolling process, the track difference of motion, cause inhomogeneous, the compactness and the erosion resistance that influence the zinc layer of coating, its utilization in actual production is restricted.
Existing mechanical zinc-plating process, countries in the world all are applied to the surface galvanizing of scattered smallclothes, as screw, fastening piece, iron nail malleable iron pipe fitting and the full tool of circuit etc., the length of workpiece is no more than 10~12 English inch, single-piece weight should not be above 1 to 2 pound, more common mechanical plating equipment main frame is many prismatics cylinder of liner rubber or plastics at present, and the working position of cylinder is generally horizontal by 20~30 ° of angles.
The objective of the invention is to adopt electric furnace zinc powder, control uniform grain sizes, be equipped with a certain amount of chemical activating agent, smoothing agent, in a purpose-made device, finish galvanizing process to promote the zinc powder slurries that sedimentary nucleating agent is formed on workpiece.
The mechanical zinc-plating process that the present invention proposes has following characteristics:
1. adopt the raw material zinc powder of electric furnace zinc powder, designed special-purpose activation and zincincation for this reason as mechanical zinc-plating.
2. adopt custom-designed steel pipe mechanical galvanized machine (for the applicant proposes, number of patent application is the steel pipe mechanical galvanized machine of 89202514x).The outer surface of steel tube that can realize 6-8 rice is zinc-plated.
3. adopt existing multi-edge column-shaped mechanical zinc-plating machine, can carry out zinc-plated scattered smallclothes such as screw, hot-water heating pipe fittings.
The mechanical zinc-plating process that the present invention relates to is called for short V-1 type technology, the technical indicator of the electric furnace zinc powder that adopts is as follows: granularity 250~300 orders, full zinc amount 88~95%, metallic zinc amount 85~90%, cadmium 0.1~1.5%, aluminium 0.5~2%, copper 0.1~1%, lead 1~3%, iron 0.02~0.1%, arsenic 0.01~0.02%.The production process of this zinc powder is: the zinc ore after selected is directly used furnace melting, zinc liquid is blow molded into powder with high pressure positive blower in reducing atmosphere.The alloying element cadmium that contains in this zinc powder, copper, aluminium, lead all are the snappiness metals, can with the combination of zinc fine embedded, can improve the outward appearance of coating to a certain extent, the content of iron seldom can not work the mischief to coating, can increase the hardness of coating on the contrary.This zinc powder is through screening, and adds the retention agent prevent natural oxidation, passivation, just can be used as the special-purpose zinc powder of this mechanical zinc-plating process.
This technological process must satisfy following technological principle: at first the surface of workpiece to be plated must expose the iron-based body, the iron-based that exposes should have certain activity, be beneficial to attract copper, zine ion to move and deposit to iron-based, this process can be called cleaning, cleaning process is different from traditional plating and or immersion need be set up special pickling workshop, but carries out in the zinc-plated main frame cylinder of this technology.Workpiece is in the state of stirring, and the surface is subjected to the impact and the barreling of impact media, and the dirt settling on the workpiece is clashed into cracking, helps the immersion of clean-out system, and the dirt that breaks away from workpiece easily mixes emulsification in the slurries.Adopt this method, washing speed is fast, effective, the clean-out system consumption is few.Workpiece after the cleaning, surface exposure goes out iron-based, for zinc powder depositions a large amount of after making and by the bump stratification, can in slurries, add copper-bath, at the copper layer that forms about 1 micron on the workpiece surface, be convenient to the zinc deposition, the add-on of copper-bath is decided on the surface-area of workpiece to be plated, is generally 30~150 milliliters/square metre.Set up on the part and just can carry out the deposition of zinc behind the copper base and collide the effect that stratified process, this process exist chemistry and two aspects of physics.
Chemical process is a process of adjusting slurry environments, and slurries should play following effect:
1. the surface of workpiece was no longer oxidized after protection had been cleared up, and good wetting property is arranged.
2. the oxidation and the passive film of zinc and other alloying element particle surfaces are removed.
3. the zinc particle after activated should keep the dispersion suspension state, and diffusibility is preferably arranged.
Adopt in the V-1 type technology behind hydrochloric acid and the Dilution of sulphuric acid to set up above-mentioned chemical environment, in the process after continuous, strong acid adds in right amount as a kind of retention agent, in slurries, add several salts to form the solution that a kind of continous-stable has above-mentioned effect simultaneously, and make PH remain on 1~4, facts have proved that this pH value is the service efficiency with zinc powder, the efficient of add-on and formation coating has great relation, and the salt of employing is compositions such as zinc chloride, ammonium chloride, sodium-chlor, zinc sulfate, sodium sulfate, ammonium sulfate and phosphoric acid salt.
The dispersion of zinc powder in slurries be by disperseing activator A to finish, the preparation that disperses activator A as follows:
1. in 1000 milliliters of there-necked flasks, add 350 ml waters earlier, stir and add 3.5 gram polyvinyl alcohol down successively, 8 gram sodium lauryl sulfates and 0.8 gram sodium bicarbonate also are heated to 65 ℃ under water-bath, after adding the whole dissolvings of material, add compound (90 gram dibutyl maleates, dibutyl phthalate 10 gram) 50% add 1.5 gram ammonium persulfate aqueous solutions again after waiting to stir several minutes, be warming up to 70~72 ℃, evenly add the residue compound in 6 hours under the constant temperature and add 0.5 ammonium persulfate aqueous solution at last again, continue to stir after 2 hours, taking off inclines, and cools off stand-by.
2. getting a certain amount of carbon number is equal to or greater than 18 hard ester acid and is dissolved in the suitable quantity of water, in water-bath, be heated to 70 ℃, constantly stir simultaneously, behind whole molten finishing, the sodium hydroxide of equivalent is divided into several batches of addings, and then constant temperature 30 minutes, an amount of glycerine and polyvinyl alcohol added at last, after stirring evenly, take off the cooling stand-by.
In second kind of liquid, add 15% first kind of liquid, mixing, promptly get required dispersion activator.
For guaranteeing all even flat appearance of zinc coating, can in slurries, add a spot of smoothing agent, can adopt glue protein and Vinyl Acetate Copolymer, polyoxyethylene glycol etc. in the V-1 technology.
What V-1 technology was different with existing technology is obviously to shorten the time that forms the zinc layer, and the thickness of zinc coating is not only relevant with the zinc powder amount that adds, also relevant with the time, can form coating within the predetermined time by zinc coating thickness as requested, the controlling factor that obtains this effect is to have adopted to promote zinc powder deposit and form the nucleating agent that loose crystallization is rolled into a ball on workpiece, and nucleating agent can be zinc oxide, titanium oxide, weisspiessglanz or tin protochloride, stannous sulfate, lead chloride, the plumbic acetate of super indium etc.The effect of nucleating agent is to impel zinc powder fast deposition on workpiece, constitutes similar crystalline structure, inlays to strengthen under the mechanical collision power effect of medium to form firm successive zinc layer.
Above-mentioned slurries are after galvanizing process is finished, and PH5~6 of fluctuating naturally can be considered as the base-material of producing micro-chemical fertilizer or composite chemical fertilizer through adjusting.
The physical action of mechanical plating craft process mainly shows two aspects of fluidised form motion of mechanical collision power and mixed liquor, and mainly the function by equipment realizes.This technology equipment used be exactly the applicant be that the galvanized machine that proposes in the application documents of 89202514x is finished at application number.It can be similar to the super long workpiece surface galvanizing of steel pipe to all kinds of Welded Steel Pipes or shape.Because the thickness of zinc coating can be regulated in 10~80 micrometer ranges, need only get final product according to the thickness requirement control feeding quantity of product in the production.If this technology cooperates with existing multi-edge column-shaped mechanical zinc-plating machine, can be to screw, scattered smallclothes such as hot-water heating pipe fitting carry out zinc-plated.
The working method of this technology is as follows: workpiece is packed in the galvanized machine, add impact media and water, the amount of impact media is decided on the shape of workpiece, be generally 0.8~1.5 times of workpiece weight, the granularity of impact media can be used the 4-5 millimeter, the 3-4 millimeter, the 2-3 millimeter, 1-2 millimeter, 0.5-1 millimeter, 0.2-0.5 millimeter wait the mixing of several specifications to form.The add-on of water gets final product with submergence workpiece and medium.The step of machining after material is packed into is 1. cleanings.2. set up copper base (needing 3~5 minutes).3. according to the area of workpiece to be plated and the zinc coating thickness of desire plating, by calculated amount activator A, salt and smoothing agent are once added in the slurries, rolling evenly gets final product.4. zinc-plated.Evenly add zinc powder and nucleating agent continuously or one by one, add a small amount of sulfuric acid in case of necessity and rotated 10~20 minutes at 1-4, required time apparent thickness and deciding to keep pH value.5. coating is strengthened.Evenly rotated 5~10 minutes.6. discharging.
Embodiment one,
Diameter is the steel pipe of 1 English inch, and every fixed length is 6 meters, and corrosion degree is general, no greasy dirt, once feed 1 ton, and desire is plated 60 microns of thickness.
The steel amount is added in the steel pipe mechanical galvanized machine of indication of the present invention, adding 1 ton of glass pill degree is 4~5 millimeters, 2~3 millimeters, 1~2 millimeter respectively accounts for 1/3rd, adding entry makes its submergence workpiece and impact media (pill) add 8000 milliliters of hydrochloric acid, rotate and change water after 10 minutes, add 3000 milliliters of copper sulfate and 1000 milliliters of sulfuric acid again, rotated 3~5 minutes, on pipe, obtain a uniform base copper, add the activator A that 315ml prepares subsequently, 1890 gram zinc chloride, 1575 gram ammonium chlorides, 756 gram sodium-chlor, 950 milliliters Vinyl Acetate Copolymer, begin to add zinc powder after mixing, in 20 minutes, add 20160 grams, 300 order electric furnace zinc powders, add nucleating agent tin protochloride 1134 gram and 2500 milliliters of sulfuric acid simultaneously, be rotated further 5~10 minutes behind reinforced the finishing steel pipe glass ball and slurries are poured out from machine drum, main frame enters next cycle, and sieve apparatus separates steel pipe and glass ball, it is pending that slurries are put into settling tank, steel pipe flushing after drying send stockyard, and the hopper of packing into after the flushing of glass ball reuses, 35~50 minutes work periods, the outer surface of steel tube thickness of coating is 56~62 microns.
Embodiment two.
Specification is the bolt of φ 10~50,100 kilograms of gross weights.Clean mach greasy dirt on the bolt with metal cleaner or traditional caustic soda, soda ash solution, with putting into cylinder after the clear water rinsing, add 100 kilograms of glass balls, adopting granularity is 3~4 millimeters, 2~3 millimeters, 1~2 millimeter, 0.5~1 millimeter, 0.2~0.5 millimeter, blending ratio 1: 1: 1: 1: 1: 1.Add entry and make its submergence workpiece and glass ball, add 750 milliliters of technical pure hydrochloric acid, rotated 5~10 minutes by calculating.Add 400 milliliters of copper-baths and 200 milliliters of sulfuric acid after changing water, rotated 3~5 minutes, and on workpiece, obtained a uniform copper layer, add 450 milliliters of activator A that prepare subsequently, 270 gram zinc chloride, 225 gram ammonium chlorides, 106 gram sodium-chlor, 16 milliliters of glue protein solution, begin to add zinc powder after mixing, in 15 minutes, add 1920 grams, 300 purpose electric furnace zinc powders, add nucleating agent lead chloride 162 gram and 250~300 milliliters of sulfuric acid simultaneously, be rotated further 5~10 minutes behind reinforced the finishing.The cylinder that verts is then poured bolt, glass ball, slurries into sieve apparatus, the main frame return enters next cycle, sieve apparatus is finished bolt simultaneously, the cleaning of glass ball, separation, the separate discharge of slurries, bolt enters the far-infrared dryer drying, the reuse of glass ball material bin after cleaning, 30~40 minutes work periods, 28~34 microns of thickness of coating.
Embodiment three,
20 millimeters malleable iron Y-junctions of specification, 100 kilograms of gross weights, the thread of joint is through processing, clean loading method with example two, require 60 microns of galvanized layer thicknesses, cleaning adds 50 millimeters/square metre of copper-baths after changing water, rotates 10 minutes, enter the zinc-plated stage, add 790 milliliters of activator A, 479 gram zinc sulfate, 390 gram ammonium sulfate, 189 gram sodium sulfate, 20 milliliters of Vinyl Acetate Copolymer solution begin to add zinc powder after mixing, added 3360 grams, 300 order zinc powders in 20 minutes, 280 gram nucleating agent stannous sulfate and 250~300 milliliters of sulfuric acid, reinforced finishing is rotated further 10 minutes, and by example two mode dischargings, the zinc coating thickness that obtains is 55~65 microns.

Claims (6)

1, a kind of mechanized zinc-plating technology with electric zinc powder, workpiece is removed dirt through cleaning, after setting up the copper base on the workpiece, put into the mechanical zinc-plating cylinder, adding is by zinc powder, activator, smoothing agent, nucleating agent are formed, and slurries add impact media, rotary drum again, finish the casting zinc technology at normal temperatures, it is characterized in that:
(1) adopt the electric furnace zinc powder as its granularity of raw material zinc powder 250-300 order, composition is full zinc amount 88-95%, metallic zinc amount 85-90%, and cadmium 0.1-1.5%, aluminium 0.2-2%, copper 0.1-1%, plumbous 1-3%, iron 0.02-0.1%, arsenic 0.01-0.02%,
(2) slurries are by disperseing activator, and smoothing agent, nucleating agent and a certain amount of strong acid, salt are formed.The control pH value equals 1-4,
(3) can finish the zinc-plated of 6-8 rice overlength pipe fitting.
2, mechanical zinc-plating process as claimed in claim 1 is characterized in that adopting the glass ball as impact media, and its add-on is 0.5 to 1.5 times of workpiece weight.
3,, it is characterized in that disperseing the preparation of activator A to carry out as follows as claim 1,2 described mechanical zinc-plating process:
(1) in 1000 milliliters of there-necked flasks, adds 350 ml waters earlier, stir and add 3.5 gram polyvinyl alcohol down successively, 8 gram sodium lauryl sulfates and 0.8 gram sodium bicarbonate, and under water-bath, be heated to 65 ℃, after adding the whole dissolvings of material, add compound (90 gram dibutyl maleates, 50% waiting to stir and add 1.5 gram ammonium persulfate aqueous solutions after n minute again dibutyl phthalate 10 gram), be warming up to 70-72 ℃, remained compound even the adding in 6 hours under the constant temperature, add 0.5 ammonium persulfate aqueous solution at last again, continue to stir 2 hours, taking off inclines, and cooling stand-by
(2) getting a certain amount of carbon number is equal to or greater than 18 hard ester acid and is dissolved in the suitable quantity of water, on water-soluble, be heated to 70 ℃, constantly stir simultaneously, behind whole molten finishing, the sodium hydroxide of equivalent is divided into several batches of addings, and then constant temperature 30 minutes, an amount of glycerine and polyvinyl alcohol added at last, after stirring evenly, take off the cooling stand-by.
(3) first kind of liquid mixing of interpolation 15% in second kind of liquid promptly gets required dispersion activator.
4, it is characterized in that as claim 1,2,3 described mechanical zinc-plating process smoothing agent is the glue protein, Vinyl Acetate Copolymer, sodium laurylsulfonate, polyoxyethylene glycol, polyoxyethylene glycol.
5,, it is characterized in that nucleating agent is a superfine zinc oxide, titanium oxide, weisspiessglanz as claim 1,2,3,4 described mechanical zinc-plating process.
6, mechanical zinc-plating process as claimed in claim 1 is characterized in that, cleaning process is carried out in the main frame cylinder.
CN 89109362 1989-12-13 1989-12-13 Mechanized zinc-plating technology with electric zinc powder Pending CN1052512A (en)

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CN 89109362 CN1052512A (en) 1989-12-13 1989-12-13 Mechanized zinc-plating technology with electric zinc powder

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CN 89109362 CN1052512A (en) 1989-12-13 1989-12-13 Mechanized zinc-plating technology with electric zinc powder

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102400142A (en) * 2010-09-10 2012-04-04 北京中科三环高技术股份有限公司 Surface treatment method of mechanically galvanized composite coating of Nd-Fe-B permanent-magnetic material
CN103668043A (en) * 2013-12-26 2014-03-26 昆明理工大学 Diffusion zincizing coating method
CN104797738A (en) * 2012-12-12 2015-07-22 奎克涂层(澳大利亚)私人有限公司 Alloy coated workpieces
CN106637317A (en) * 2016-12-16 2017-05-10 昆明理工大学 Copper gold powder slurry for mechanical plating and preparation method thereof
CN108048825A (en) * 2017-12-22 2018-05-18 刘珍 A kind of method of steel and iron parts surface mechanical zinc-plating
CN108677182A (en) * 2018-05-14 2018-10-19 昆明理工大学 A kind of mechanical deposit cadmium and cadmium alloy coating activator
CN111020544A (en) * 2019-11-18 2020-04-17 昆明理工大学 Method for plating titanium layer on surface of steel product
CN111058042A (en) * 2019-12-12 2020-04-24 绍兴山耐高压紧固件有限公司 Bolt surface galvanizing process

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102400142B (en) * 2010-09-10 2015-08-19 北京中科三环高技术股份有限公司 A kind of surface treatment method of mechanical zinc-plating composite deposite of Nd-Fe-Bo permanent magnet material
CN102400142A (en) * 2010-09-10 2012-04-04 北京中科三环高技术股份有限公司 Surface treatment method of mechanically galvanized composite coating of Nd-Fe-B permanent-magnetic material
US9885103B2 (en) 2012-12-12 2018-02-06 Kwik-Coat (Aust) Pty Ltd Alloy coated workpieces
CN104797738A (en) * 2012-12-12 2015-07-22 奎克涂层(澳大利亚)私人有限公司 Alloy coated workpieces
EP2931938A4 (en) * 2012-12-12 2016-06-01 Kwik Coat Aust Pty Ltd Alloy coated workpieces
CN104797738B (en) * 2012-12-12 2019-02-05 奎克涂层(澳大利亚)私人有限公司 The workpiece of alloy coat
CN103668043A (en) * 2013-12-26 2014-03-26 昆明理工大学 Diffusion zincizing coating method
CN106637317A (en) * 2016-12-16 2017-05-10 昆明理工大学 Copper gold powder slurry for mechanical plating and preparation method thereof
CN106637317B (en) * 2016-12-16 2018-05-25 昆明理工大学 A kind of mechanical plating Cu-Zn alloy powder slurry and its preparation method
CN108048825A (en) * 2017-12-22 2018-05-18 刘珍 A kind of method of steel and iron parts surface mechanical zinc-plating
CN108677182A (en) * 2018-05-14 2018-10-19 昆明理工大学 A kind of mechanical deposit cadmium and cadmium alloy coating activator
CN108677182B (en) * 2018-05-14 2019-07-16 昆明理工大学 A kind of mechanical deposit cadmium and cadmium alloy coating activator
CN111020544A (en) * 2019-11-18 2020-04-17 昆明理工大学 Method for plating titanium layer on surface of steel product
CN111058042A (en) * 2019-12-12 2020-04-24 绍兴山耐高压紧固件有限公司 Bolt surface galvanizing process

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