CN103205181B - A kind of nanometer heavy-duty coating - Google Patents
A kind of nanometer heavy-duty coating Download PDFInfo
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- CN103205181B CN103205181B CN201310133278.1A CN201310133278A CN103205181B CN 103205181 B CN103205181 B CN 103205181B CN 201310133278 A CN201310133278 A CN 201310133278A CN 103205181 B CN103205181 B CN 103205181B
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Abstract
The present invention relates to a kind of nanometer heavy-duty coating, mark contains following component by weight: bisphenol-A epoxy vinyl ester 20 ~ 70wt%, vinylbenzene 1 ~ 30wt%, the nano combined electro-conductive fiber 1 ~ 20wt% of polypyrrole base, nano silicon 1 ~ 15wt%, dispersion agent 0.1 ~ 10wt%, modified alta-mud 0.1 ~ 6wt%, organic solvent 5 ~ 30wt%.Coating provided by the present invention is not containing any heavy metal material, and salt-fog resistant time is greater than 3000 hours, and acid and alkali-resistance is greater than 1000 hours.
Description
Technical field
The present invention relates to a kind of heavy-duty coating, particularly relate to a kind of nanometer heavy-duty coating.
Background technology
Heavy-duty coating refers to relatively conventional protective system, can apply in relatively harsh corrosive environment, and has a class protective system that can reach the protection period longer than conventional protective system.Heavy-duty coating main application fields has: 1. emerging oceanographic engineering: Offshore Units, seashore and bay structure, offshore oil platform; 2. Modern Traffic transport: freeway guardrail, bridge, ships and light boats, freight container, train and railway facility, automobile, airport installation; 3. energy industry: water conservancy project equipment, water pot, petroleum refinement equipment, oil stockpile equipment (oil pipe, oil tank), power transmission and transforming equipment, nuclear power, colliery; 4. large size industrial enterprise: the pipeline of paper making equipment, medical equipment, food chemistry equipment, metal vessel inside and outside wall, chemical industry, iron and steel, petrochemical plant, storage tank, mine smelting, cement mill equipment, the ground having corrosive medium, wall cement components; 5. urban operating mechanism: gas line and facility (as gas chamber), natural gas line, drinking-water facility, refuse treatment plant etc.
Because the Application Areas that product is special makes product have special feature if use under severe conditions, and there is the long-effective corrosion life-span.Heavy-duty coating, in chemical atmosphere and ocean environment, generally can use more than 10 years or 15 years, even if in acid, alkali, salt and solvent medium, and under certain temperature condition, also can use more than 5 years; And the important symbol of heavy-duty coating is thick-film, the coating dry film thickness of general protective system is 100 μm or about 150 μm, heavy-duty coating build, then more than 200 μm or 300 μm, also has 500 μm ~ 1000 μm, even up to 2000 μm.
Heavy-duty coating conventional at present has zinc-rich paint, iron oxide red coating, MIO coating etc.
Zinc-rich paint is a kind of coating containing a large amount of zinc, and zinc content is between 85-95%, and film only thick 100 microns, comprises organic zinc-rich paint and inorganic zinc coating.Such as CN102417784A discloses a kind of epoxy zinc-enriched paint, and described coating take epoxy resin as base-material, and cashew nut oil polymeric amide is solidifying agent, and super-fine zinc dust is main rust-stabilising pigment, adds a certain amount of auxiliary agent, solvent etc. formulated by a certain percentage.Epoxy zinc-enriched paint provided by the present invention is applicable to dip coating manner application, and the paint film after application has fabulous corrosion-resistant, chemically-resistant and solvent resistance.CN101691457A discloses a kind of inorganic zinc coating, and this kind of its weight percent of coating consists of: 75% ~ 80% zinc powder, 5% ~ 8% water glass/potassium, 2% ~ 3% potassium methyl silicate/sodium, the water of surplus.
Iron oxide red coating is main film forming binder with resin, by adding ferric oxide red colorant, specialist additive, auxiliary agent, solvent etc., the heavy antisepsis priming paint be prepared from.Such as CN102311670A discloses a kind of iron oxide red paint, it is characterized in that being made up of by following weight percent following component: red iron oxide: 42-47%; Titanium dioxide: 0.7-1.2%; Lithium base Peng Run soil: 1.2%-1.6%; Attapulgite: 1.3%-1.7%; Butyral resin: 0.45%-0.63%; White dextrin: 0.58%-0.82%; White glue with vinyl: 0.45%-0.65%; Methyl alcohol: 32.35%-34.2%; Ethanol: 15.97%-17.2%.
MIO coating take iron mica as the coating of main pigments, includes acid modified alcoholic, chlorinated rubber, ethenyl copolymer, epoxy resin.Such as CN102964967A discloses a kind of protective system, be made up of the raw material of following parts by weight: epoxy resin 61820-35 part, butylated amino resin 10-18 part, flaky graphite 5-10 part, grey iron mica 3-6 part, aluminium sesquioxide 5-8 part, tertiary amine curing catalyst 3-7 part, silane coupling agent 2-6 part, ethanol ether acetic ester 8-15 part, thinner 3-6 part, cellulose acetate 7-11 part.Described thinner be diacetone alcohol, pimelinketone, ethanol, methyl alcohol, ethylene glycol or ether one or more.
Protective system conventional on the market above-mentioned at present can not satisfy the demands in newly built construction, frontier, is mainly manifested in: such as salt spray resistance is not high, is generally no more than 1000 hours; Comprehensive anticorrosive performance is single, acidproof alkaline error; Containing plurality of heavy metal (lead, chromium etc.) in protective system, to human body and to defects such as environments.
Summary of the invention
The object of the present invention is to provide a kind of nanometer heavy-duty coating, coating provided by the present invention is not containing any heavy metal material, and salt-fog resistant time is greater than 3000 hours, and acid and alkali-resistance is greater than 1000 hours.
Nanometer heavy-duty coating provided by the present invention, mark contains following component by weight: bisphenol-A epoxy vinyl ester 20 ~ 70wt%, be such as 22wt%, 25wt%, 28wt%, 33wt%, 36wt%, 40wt%, 43wt%, 48wt%, 54wt%, 59wt%, 63wt%, 66wt%, 69wt% etc., vinylbenzene 1 ~ 30wt%, be such as 3wt%, 6wt%, 9wt%, 14wt%, 18wt%, 20wt%, 25wt%, 27wt% etc., electro-conductive fiber 1 ~ 20wt%, be such as 2wt%, 5wt%, 8wt%, 10wt%, 14wt%, 16wt%, 18wt% etc., nano silicon 1 ~ 15wt%, be such as 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 14wt% etc.
As optimal technical scheme coating provided by the present invention, mark contains following component by weight: bisphenol-A epoxy vinyl ester 30 ~ 65wt%, vinylbenzene 5 ~ 25wt%, electro-conductive fiber 3 ~ 15wt%, nano silicon 3 ~ 10wt%.
As optimal technical scheme coating provided by the present invention, mark contains following component by weight: bisphenol-A epoxy vinyl ester 40 ~ 60wt%, vinylbenzene 5 ~ 20wt%, electro-conductive fiber 3 ~ 10wt%, nano silicon 3 ~ 7wt%.
Bisphenol-A epoxy Vinylite is by methacrylic acid and the bisphenol A epoxide resin Vinylite by Reactive Synthesis.Make it extremely active owing to there is unsaturated double-bond at molecular chain two ends, have high reaction activity, energy rapid solidification, obtains the goods of high strength very soon; Adopt methacrylic acid synthesis, the methyl on ester bond limit can shield simultaneously, improves hydrolytic resistance; And resin is few containing ester bond amount, alkaline resistance properties is high.
Vinylbenzene is the organic compound formed with a hydrogen atom of benzene substituted ethylene, and the electronics of vinyl and phenyl ring conjugation are water insoluble, are dissolved in ethanol, ether, dissolve bisphenol-A epoxy Vinylite in the present invention, play solvency action.
Electro-conductive fiber generally refers to that electric conductivity is greater than 10
-7Ω
-1.cm
-1fiber.This fibrid has good electroconductibility and weather resistance, particularly still has good durable antistatic under the low humidity.
Nano silicon particle diameter is very little, and superficial attractive forces is strong, and surface energy is large, and the aspects such as chemical purity is high, dispersing property good, thermal resistance, resistance have special performance, and has superior stability, reinforcing, thickening property and thixotropy.Nano silicon has tridimensional network, has huge specific surface area, shows great activity, reticulated structure can be formed when coating is dry, add intensity and the smooth finish of coating simultaneously, and improve the suspension of pigment, the color of coating can be kept not fade for a long time.
In addition, nano silicon also has the special optical performance that Normal silica does not have, and it has extremely strong uv-absorbing, infrared external reflection characteristic.Show through ultraviolet-visible pectrophotometer test, it to the uv absorption rate within wavelength 400nm up to more than 70%, also more than 70% is reached to the infrared reflectivity beyond wavelength 800nm, it adds in coating can form shielding effect to coating, reach the object of anti-ultraviolet ageing and thermal ageing, add the thermal insulation of coating simultaneously.
As optimal technical scheme coating provided by the present invention, also containing dispersion agent 0.1 ~ 10wt%, be such as 0.3wt%, 0.6wt%, 1wt%, 3wt%, 6wt%, 8wt% etc., modified alta-mud 0.1 ~ 6wt%, be such as 0.3wt%, 0.6wt%, 0.9wt%, 1.5wt%, 2wt%, 3wt%, 3.5wt%, 4.4wt%, 5.2wt%, 5.7wt% etc., organic solvent 5 ~ 30wt% is such as 7wt%, 9wt%, 13wt%, 16wt%, 19wt%, 22wt%, 27wt%, 29wt% etc.
As optimal technical scheme coating provided by the present invention, described coating is also containing dispersion agent 0.4 ~ 6wt%, modified alta-mud 0.5 ~ 3wt%, organic solvent 10 ~ 20wt%.
The dispersion of dispersion agent in coating, electro-wetting principle, one be dispersant adsorption in powder particles, by moistening for the powder particles of cohesion; Two is that macromolecule dispersing agent is adsorbed on powder particles surface, increases pigment and the interparticle surface charge of stopping composition, improves interparticle electrostatic repulsion, and effectively increase interparticle sterically hindered, make the stable dispersion of powder particles in liquid become possibility.Divide according to molecular structure, dispersion agent is generally divided into two large classes: inorganic dispersant and organic dispersing agent.In the majority with polyphosphoric acid salt in inorganic dispersant, as Sodium hexametaphosphate 99, Potassium tripolyphosphate, sodium polyphosphate and tetrapotassium pyrophosphate.The mechanism of its effect is by hydrogen bond and chemisorption, plays electrostatic repulsion stabilization.Its advantage be to mineral dye and stopping composition dispersion effect good, but with the rising of pH value and temperature, polyphosphoric acid salt is easily hydrolyzed, not good to extended storage stability.Organic dispersing agent comprises polyacrylate, polystyrene/maleic acid salt, polyisobutene/maleic acid salt etc.Their feature is, produce strong absorption or anchorage effect on powder surface, have longer molecular chain sterically hindered to be formed, the end of the chain has water-soluble, and what have also auxiliaryly has electrostatic repulsion, reaches stable result.
Organic dispersing agent is because of its molecular weight difference, and performance can be different; Lower molecular weight type dispersion agent has one or more polar group be spatially close, they are adsorbed on surface of pigments, stabilizing powder particle is used for spatial masking, thus make viscosity degradation, this kind of dispersion agent is mainly used in mineral dye, because mineral dye is ionic structure, have higher surface polarity, dispersion agent is easy to absorption.And pigment dyestuff is because its surface is containing C, H, O group, without ionic activity, so often use the dispersion agent of high molecular, have the more surface that group is adsorbed on pigment dyestuff of sticking, it can form lasting adsorption layer on pigment dyestuff.But the too great Yi flocculation of the molecular weight of dispersion agent.So select to select according to pigment and stopping composition type during the type of dispersion agent.The present invention's dispersion agent used can be organic dispersing agent, is preferably acrylic copolymer solution, the more preferably dispersion agent of BYK2020.
As optimal technical scheme coating provided by the present invention, described coating by weight mark contains following component: bisphenol-A epoxy vinyl ester 20 ~ 70wt%, vinylbenzene 1 ~ 30wt%, electro-conductive fiber 1 ~ 20wt%, nano silicon 1 ~ 15wt%, dispersion agent 0.1 ~ 10wt%, modified alta-mud 0.1 ~ 6wt%, organic solvent 5 ~ 30wt%.
As optimal technical scheme coating provided by the present invention, described coating by weight mark contains following component: bisphenol-A epoxy vinyl ester 30 ~ 65wt%, vinylbenzene 5 ~ 25wt%, electro-conductive fiber 3 ~ 15wt%, nano silicon 3 ~ 10wt%, dispersion agent 0.4 ~ 6wt%, modified alta-mud 0.5 ~ 3wt%, organic solvent 10 ~ 20wt%.
As optimal technical scheme coating provided by the present invention, described coating by weight mark contains following component: bisphenol-A epoxy vinyl ester 40 ~ 60wt%, vinylbenzene 5 ~ 20wt%, electro-conductive fiber 3 ~ 10wt%, nano silicon 3 ~ 7wt%, dispersion agent 0.4 ~ 6wt%, modified alta-mud 0.5 ~ 3wt%, organic solvent 10 ~ 20wt%.
As optimal technical scheme coating provided by the present invention, described electro-conductive fiber is composite conducting fiber, is preferably organic composite electro-conductive fiber, more preferably polypyrrole base organic montmorillonite nano composite conducting fiber.
Composite conducting fiber is using the polymkeric substance containing conducting particles as a kind of composition, by being not the second composition containing the similar polymers of conducting particles or another kind of polymkeric substance, adopts conjugate spinning to form.Composite conducting fiber has good rub resistance, resistance to surrender, resistance to oxidation and corrosion resistance, therefore for coating can be made in coating to have excellent rub resistance, resistance to surrender, resistance to oxidation and corrosion resistance nature.
Organic composite electro-conductive fiber uses carbon black compound or metallic compound compound electrically conductive organic fibre to form, and not by the impact of ambient temperature and humidity, has excellent physical and mechanical properties.
Polypyrrole base organic montmorillonite nano composite conducting fiber can strengthen the plasticity-of coating, intensity and heat resist ability, reduces the perviousness etc. of gas, liquid.Polypyrrole base organic montmorillonite nano composite conducting fiber can adopt prior art to be prepared, if the people such as Su Haixia are with iron trichloride (FeCl
3) be oxygenant, paratoluenesulfonic acid sodium salt (TSANa) is doping agent, make the pyrroles (Py) entered through organo montmorillonite (OMMT) interlayer of organic intercalation agent modification that oxidative polymerization occur, prepare the polypyrrole with satisfactory electrical conductivity/organo montmorillonite (Su Haixia, Zeng Xingrong.The preparation of polypyrrole/organic montmorillonite nano composite material and electroconductibility thereof.Shanghai Metallurgy Inst., Chinese Academy of Sciences; Materials Physics and Chemistry (specialty) Ph D dissertation 2000 year); Or preparation method disclosed in CN1597769A.
As optimal technical scheme coating provided by the present invention, described modified alta-mud is organic bentonite, is preferably organic amine modified alta-mud.The wilkinite adding modification can give the certain thixotropy of coating and structural viscosity, plays the anti-settling effect of thickening.Modified alta-mud of the present invention organic amine used can be n-octyl amine, amino dodecane, cetylamine, stearylamine, cetyl trimethylammonium bromide or acrylamide etc.
Preferably, described organic solvent is benzene kind solvent, is preferably benzene, toluene or dimethylbenzene, or its mixture, more preferably dimethylbenzene.In the present invention, organic solvent used mainly plays diluting effect, with adjusting coating viscosity.
Nanometer heavy-duty coating provided by the invention, can also comprise the conven-tional adjuvants in coating, as pigment, and thickening material, sanitas, one or more the mixture in defoamer etc.
Conven-tional adjuvants to add the coating property that can make to obtain more outstanding.Pigment can make coating have predetermined color and luster, and pigment optimization of the present invention does not contain the anti-corrosion paint of heavy metal, as red lead, zinc yellow, zinc phosphate, strontium chromate and zinc molybdate.Thickening material can make coating have good thixotropy, and the present invention selects nonionic polyurethane compounds.Sanitas can suppress the mould-growth in coating, makes coating keep steady quality.Sanitas of the present invention is preferably isothiazolinone.Defoamer can suppress foam, makes not easily to produce shrinkage cavity and flake during coating application, and defoamer of the present invention can adopt the mixture of water drain silica and mineral oil.The addition of conven-tional adjuvants can add according to the general knowledge of those skilled in the art.
Coating provided by the present invention obtains by the preparation method of routine.
Nanometer heavy-duty coating provided by the invention coating provided by the present invention not only has excellent physical and mechanical properties, and not containing any heavy metal material, and salt-fog resistant time is greater than 3000 hours, acid and alkali-resistance is greater than 1000 hours.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
As no specific instructions, various raw material of the present invention all can be obtained by commercially available; Or prepare according to the ordinary method of this area.Unless otherwise defined or described herein, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.In addition any method similar or impartial to described content and material all can be applicable in the inventive method.
The experimental technique of unreceipted actual conditions in the following example, measures according to national standard usually.If there is no corresponding national standard, then according to general international standard, normal condition or carry out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all numbers are weight part, and all per-cent is weight percentage.
Embodiment 1
Mark contains following component by weight: bisphenol-A epoxy vinyl ester 20wt%, vinylbenzene 15wt%, carbon black composite conducting trevira 10wt%, nano silicon 10wt%.
Embodiment 2
Mark contains following component by weight: bisphenol-A epoxy vinyl ester 70wt%, vinylbenzene 1wt%, polyaniline composite conductive fiber 1wt%, nano silicon 15wt%, dispersion agent 0.1wt%, amino dodecane modified alta-mud 6wt%, dimethylbenzene 5wt%.
Embodiment 3
Mark contains following component by weight: bisphenol-A epoxy vinyl ester 30wt%, vinylbenzene 30wt%, polypyrrole base organic montmorillonite nano composite conducting fiber 20wt%, nano silicon 1wt%, acrylic copolymer solution 5wt%, organic amine modified alta-mud 3wt%, dimethylbenzene 15wt%.
Embodiment 4
Mark contains following component by weight: bisphenol-A epoxy vinyl ester 65wt%, vinylbenzene 5wt%, polypyrrole base organic montmorillonite nano composite conducting fiber 5wt%, nano silicon 5wt%, BYK202010wt%, cetyl trimethylammonium bromide modified alta-mud 0.1wt%, dimethylbenzene 30wt%.
Embodiment 5
Mark contains following component by weight: bisphenol-A epoxy vinyl ester 40wt%, vinylbenzene 10wt%, polypyrrole base organic montmorillonite nano composite conducting fiber 8wt%, nano silicon 7wt%, BYK20203wt%, cetylamine modified alta-mud 2wt%, toluene 10wt%.
Performance Detection: the coating obtained according to a conventional method by embodiment 1-5 carries out Performance Detection.
The content of heavy metal element: detect according to GB18582-2007 " interior decoration finishing material limits of harmful substances ", result does not all detect heavy metal element.
Salt spray resistance: according to GB/T1763-1979 " paint film chemical reagent resistance assay method ", carry out 3000h test with 3%NaCl, result display is all without exception.
Alkali resistance: GB/T1763-1979 " paint film chemical reagent resistance assay method ", carries out 1000h test with 10%NaOH, and result display is all without exception.
Acid resistance: GB/T1763-1979 " paint film chemical reagent resistance assay method ", carries out 1000h test with 10%HCl, and result display is all without exception.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (9)
1. a nanometer heavy-duty coating, is characterized in that, mark is made up of following material component by weight: bisphenol-A epoxy vinyl ester 20 ~ 70wt%, vinylbenzene 1 ~ 30wt%, organic composite electro-conductive fiber 1 ~ 20wt%, nano silicon 1 ~ 15wt%; Dispersion agent 0.1 ~ 10wt%, organic amine modified alta-mud 0.1 ~ 6wt%, organic solvent 5 ~ 30wt%.
2. coating according to claim 1, it is characterized in that, mark is made up of following material component by weight: bisphenol-A epoxy vinyl ester 30 ~ 65wt%, vinylbenzene 5 ~ 25wt%, organic composite electro-conductive fiber 3 ~ 15wt%, nano silicon 3 ~ 10wt%; Dispersion agent 0.1 ~ 10wt%, organic amine modified alta-mud 0.1 ~ 6wt%, organic solvent 5 ~ 30wt%.
3. coating according to claim 1, is characterized in that, mark is made up of following material component by weight: bisphenol-A epoxy vinyl ester 40 ~ 60wt%, vinylbenzene 5 ~ 20wt%, organic composite electro-conductive fiber 3 ~ 10wt%, nano silicon 3 ~ 7wt%; Dispersion agent 0.1 ~ 10wt%, organic amine modified alta-mud 0.1 ~ 6wt%, organic solvent 5 ~ 30wt%.
4. coating according to claim 1, it is characterized in that, mark is made up of following material component by weight: bisphenol-A epoxy vinyl ester 30 ~ 65wt%, vinylbenzene 5 ~ 25wt%, organic composite electro-conductive fiber 3 ~ 15wt%, nano silicon 3 ~ 10wt%, dispersion agent 0.4 ~ 6wt%, organic amine modified alta-mud 0.5 ~ 3wt%, organic solvent 10 ~ 20wt%.
5. coating according to claim 1, it is characterized in that, mark is made up of following material component by weight: bisphenol-A epoxy vinyl ester 40 ~ 60wt%, vinylbenzene 5 ~ 20wt%, organic composite electro-conductive fiber 3 ~ 10wt%, nano silicon 3 ~ 7wt%, dispersion agent 0.4 ~ 6wt%, organic amine modified alta-mud 0.5 ~ 3wt%, organic solvent 10 ~ 20wt%.
6. coating according to claim 1, is characterized in that, described organic composite electro-conductive fiber is polypyrrole base organic montmorillonite nano composite conducting fiber.
7. coating according to claim 1, is characterized in that, described organic solvent is benzene kind solvent.
8. coating according to claim 7, is characterized in that, described organic solvent is benzene, toluene or dimethylbenzene, or its mixture.
9. coating according to claim 8, is characterized in that, described organic solvent is dimethylbenzene.
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| CN103205181B true CN103205181B (en) | 2016-03-30 |
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| CN105219230A (en) * | 2015-11-14 | 2016-01-06 | 华文蔚 | A kind of oceanographic engineering heavy-duty coating |
| CN105651105A (en) * | 2016-01-25 | 2016-06-08 | 中山昊天节能科技有限公司 | Multifunctional air energy power generation device |
| CN106010148B (en) * | 2016-07-18 | 2018-03-27 | 四川理工学院 | Highly conductive coating of silvering graphite olefinic carbon pipe compound resin and preparation method thereof |
| CN106398478A (en) * | 2016-10-21 | 2017-02-15 | 过冬 | Anti-bacteria coating and preparation method thereof |
| CN106634455A (en) * | 2016-10-21 | 2017-05-10 | 过冬 | Heavy-duty anticorrosion paint for ocean engineering and preparation method of heavy-duty anticorrosion paint |
| CN107151514A (en) * | 2017-06-23 | 2017-09-12 | 华娜 | A kind of ocean engineering anticorrosive paint and preparation method thereof |
| CN107083147A (en) * | 2017-06-26 | 2017-08-22 | 俞秀英 | A kind of anticorrosive paint and preparation method thereof |
| CN112160014A (en) * | 2020-09-17 | 2021-01-01 | 扬州市金杨电镀设备有限公司 | Three-cylinder barrel plating machine |
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