CN102676048B - Modified polyphenylene sulfide coating and application thereof - Google Patents
Modified polyphenylene sulfide coating and application thereof Download PDFInfo
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Abstract
The invention discloses a modified polyphenylene sulfide coating and the application thereof. The modified polyphenylene sulfide coating consists of the following components by weight percentage: 60-90 percent of polyphenylene sulfide resin, 3-25 percent of poly-perfluorinated ethylene propylene resin, 3-20 percent of ethylene-tetrafluoroethylene copolymer resin, 1-5 percent of molybdenum disulfide, 1-5 percent of graphite and the balance of filler, wherein the filler is any one of or a mixture of zinc oxide, aluminum oxide, silicon carbide and chromium sesquioxide. The modified polyphenylene sulfide coating disclosed by the invention has the advantages that the compatibility among the components is good; a prepared coating layer has higher corrosion resistance, higher self-lubricity and strong wear-resistant ability, is resistant to high temperature, is highly insulated, has good toughness, can bear impact force capable of being borne by a metal surface, has excellent bond performance with a metal material and is particularly suitable for the using and working condition of cold/hot sudden changes which cannot be borne by glass lining equipment; and through spraying the coating disclosed by the invention on the surface of the metal matrix material, a manufactured work piece has excellent physical-chemical performance, a long service life and a wide application range.
Description
Technical field
The present invention relates to polyphenyl thioether modified paint and application thereof, particularly resistance to wear, corrosion-resistant polyphenyl thioether modified paint and application thereof.
Background technology
In industrial installation, the kinetic friction mechanism of equipment, carry gritty crude oil pipeline, carry the friction means that is subject to using in corrosive environment containing the flue of dust etc. containing the chemical pipeline of granule materials, discharge, the particularly long-term gritty crude oil pipeline of conveying under severe cold and hot environment and the flue of discharge containing dust, the dual harm that in use can be denuded and corrode, cause described parts short work-ing life, replacement frequency is high, increase running cost, brought larger difficulty also to continuity and the security of suitability for industrialized production.
The harm that is worn and corrodes in order to reduce above-mentioned parts, people use have resistance to wear, the material of corrosion resistance nature casts above-mentioned parts.Described have resistance to wear, the material of corrosion resistance nature comprises metallic substance, inorganic materials, macromolecular material, and existing these three kinds of materials exist respectively following problem: (1), resistance to wear, corrosion resistant metallic substance, it is all expensive alloy material, as titanium-nickel-Chromium Stainless Steel, its price is not only several times even tens times of common iron, and its work-ing life is very limited, maintain and replace cost is also very high; (2), resistance to wear, corrosion resistant inorganic materials, as glass (iron-based lass lining), cast stone, corundum etc., because enbrittling, be difficult to processing, and raw materials cost is also higher; (3), resistance to wear, corrosion resistant macromolecular material, because of the shortcoming such as poor heat resistance, intensity be low, its use range has been subject to larger restriction.
The problems referred to above that exist in order to overcome prior art, at present, also have comprising the resistance to wearing of a kind of base resin, corrosion resistant coating is sprayed on metal matrix material surface and forms coating, obtain having resistance to wear, the matrix material of corrosion resistance nature.The shortcoming such as alloy material cost is high although this matrix material has overcome to a certain extent, the difficult processing of inorganic materials, macromolecular material intensity are low, but contriver finds this material and still has these problems in actual mechanical process: between (1), metal matrix material and its surperficial coating, bonding force is poor, coating is easily peeled off from body material, allowed metal-coating composite material lose corrosion-resistant, wear-resistant performance; (2), coating frictional coefficient is high, wear resistance is low; (3), erosion resistance is low, work-ing life is short.
Summary of the invention
The object of the invention is to overcome metal-coating composite material that in prior art, metal matrix material surface spraying coating forms, the coating existing easily from basic material peel off, wear resistance and the low shortcoming of erosion resistance, provide good with metal matrix material bonding force, resistance to wear and the polyphenyl thioether modified paint of corrosion resistance and good.
Second object of the present invention is to provide the application of polyphenyl thioether modified paint.
The 3rd object of the present invention be to provide with polyphenyl thioether modified paint preparation resistance to wear, the method for corrosion resistance nature matrix material.
In order to realize first object of the present invention, the invention provides following technical scheme:
Polyphenyl thioether modified paint, percentage composition meter by weight, composed of the following components:
Polyphenylene sulfide 60～90%,
Exhaustive fluorinated ethylene propylene 3～25%,
Ethylene-tetrafluoroethylene copolymer resins 3～20%,
Molybdenumdisulphide 1～5%,
Graphite 1～5%,
Filler surplus,
Described filler is any one or a few the mixture in zinc oxide, aluminum oxide, silicon carbide and chromium sesquioxide.
In above-mentioned coating, described polyphenylene sulfide can be linear polyphenylthioether, can be also branched chain type polyphenylene sulfide.Preferably branched chain type polyphenylene sulfide, particularly when the limiting viscosity of branched chain type polyphenylene sulfide is that 5～20mL/g is (take α-chloronaphthalene as solvent, at the soltion viscosity of 208 ℃) time, above-mentioned polyphenyl thioether modified paint has the better superior physicals such as corrosion-resistant, wear-resistant, high temperature resistant, high insulation and cementability.
The weight percentage of above-mentioned polyphenylene sulfide preferably 60～80%.
The weight percentage of above-mentioned exhaustive fluorinated ethylene propylene preferably 5～20%.
The weight percentage of above-mentioned ethylene-tetrafluoroethylene copolymer resins preferably 5～20%.
In above-mentioned coating, any several mixtures in described filler preferential oxidation zinc, aluminum oxide, silicon carbide and chromium sesquioxide.Zinc oxide in described filler can be common zinc oxide, can be also ZnOw.Because ZnOw has the molecular structure of pawl type, not only can play filling effect, and can embed in base resin molecule, make intermolecular easier combination, make between the each component of coating consistency better, thereby make above-mentioned polyphenyl thioether modified paint there is better rigidity and wear resistance, therefore, above-mentioned zinc oxide preferential oxidation zinc whisker.
Preferably, the length-to-diameter ratio of above-mentioned ZnOw is preferably 5: 1～and 30: 1, be preferably 10: 1～30: 1.
In order further to make above-mentioned coating there is higher rigidity and wear resistance, the preferred Alpha-alumina of above-mentioned aluminum oxide; Described Alpha-alumina, because it has good hardness, is filled in coating, has improved rigidity and the wear resistance of coating.
In order further to make above-mentioned polyphenyl thioether modified paint have better rigidity and wear resistance, the particle diameter of above-mentioned silicon carbide and chromium sesquioxide is preferably and is less than or equal to 0.01mm again.
In order to realize second object of the present invention, the invention provides following technical scheme: the application of polyphenyl thioether modified paint, by above-mentioned polyphenyl thioether modified paint be used in metal matrix material make resistance to wear, corrosion resistance nature matrix material.
In order to realize the 3rd object of the present invention, the invention provides following technical scheme: with the preparation of above-mentioned polyphenyl thioether modified paint resistance to wear, the method for corrosion resistance nature matrix material, comprise above-mentioned polyphenyl thioether modified paint is sprayed in metal matrix material, heating, melting and solidification film forming.
The present invention adopts polyphenylene sulfide, exhaustive fluorinated ethylene propylene and the composite use of ethylene-tetrafluoroethylene copolymer resins, the common base resin as coating of the present invention, wherein, polyphenylene sulfide, claim again polyphenylene sulfoether resin, be the polymkeric substance that molecular chain contains phenylene sulfide repeated structural unit, be divided into linear polyphenylthioether and branched chain type polyphenylene sulfide, have preferably resistance to wear, the advantage such as erosion resistance, thermotolerance, weathering resistance, high-insulativity; Ethylene-tetrafluoroethylene copolymer resins, claim again fluororesin 40, by ethene and tetrafluoroethylene, (mo l) formed with 1: 1, by ethene and tetrafluoroethylene, replaced the multipolymer of chain link, there is the over-all propertieies such as good shock-resistant, creep resistance, high compression-strength, life-time service temperature-60～+ 180 ℃; Exhaustive fluorinated ethylene propylene, is the multipolymer of tetrafluoroethylene and perfluoro propylene, has physical strength, chemical stability, electrical insulating property, ageing resistance and the non-stickiness similar with the tetrafluoroethylene that is known as " kings of plastics ", can be at-85～205 ℃ of life-time service.Between coating composition of the present invention, there is fabulous consistency, make to have had both by coating prepared by coating of the present invention physical chemistry, the mechanics of machinery characteristic of described three kinds of base resin excellences, in the proportional range of three kinds of base resins of the present invention, paint spay-coating of the present invention forms coating in metal matrix material, under molten state, molecular chain is wound around mutually, the chain rupture of part superpolymer, grafting or block again, thereby form molecule interface contact uniform polyphenylene sulfide perfluoroethylene-propylene ethylene-tetrafluoroethylene copolymer high polymer alloy mutually, make the more described three kinds of base resin performances of coating prepared with coating of the present invention more excellent, particularly resistance to wear better with corrosion resistance nature, the bonding force of coating and metal matrix material is better, coating is difficult for peeling off from body material, adopt molybdenumdisulphide and graphite to make auxiliary lubricant, filled up the textural defect of described three kinds of base resins, strengthened the self lubricity of coating of the present invention, make wear-resistant ability strong, adopt above-mentioned filler to make propping agent, strengthened rigidity and the wear resistance of coating of the present invention.
Compared with prior art, beneficial effect of the present invention: polyphenyl thioether modified paint of the present invention, between component, consistency is good, and the coating of preparation has the following corrosion-resistant and physical and chemical performance advantage such as resistance to wear:
(1), there is higher erosion resistance, the coating salt tolerant acid (36%w of preparation, " %w " of the present invention represents quality percentage composition, nitric acid (40%w), sulfuric acid (70%w), phosphoric acid (60%w) down together),, caustic soda (40%w), ammoniacal liquor, calcium chloride, the corrosion of the acid such as acetic acid, acetone, chloroform, ethanol petrol (volume ratio 20: 80), alkali, salt, organic solvent;
(2), there is self lubricity, frictional coefficient is low, antiwear property is strong;
(3), good toughness, can bear the surging force that metallic surface can be born;
(4), have good cohesive force with the metal matrix material such as iron and steel, aluminium, stainless steel, sticking power is high, is specially adapted to the applying working condition of the cold and hot cataclysm that glass-lined equipment can not bear;
(5), surface highly polished, scale inhibition performance is good, in use procedure, particularly under hard water environment, uses less scaling;
(6), high insulation, high temperature resistant, there is higher thermostability and weathering resistance preferably, can be in liquid (20～160 ℃) and the medium-term and long-term use of air (40～260 ℃).
Because coating of the present invention has as above advantage, by by paint spay-coating of the present invention on metal matrix material surface, the workpiece physical and chemical performance excellence producing, long service life, applied range.
Embodiment
Below in conjunction with test example and embodiment, the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing based on content of the present invention all belong to scope of the present invention.
Embodiment 1～7
The polyphenyl thioether modified paint of embodiment 1～7, percentage composition meter by weight, is mixed by component as shown in embodiment in table 1 1～7 respectively.
Comparative example 1～3
The polyphenyl thioether modified paint of comparative example 1～3, percentage composition meter by weight, is mixed and is formed by component as shown in comparative example in table 1 1～3 respectively.
Table 1
In table 1:
Branched chain type polyphenylene sulfide is coating level, particle diameter≤45um, and limiting viscosity is 5～20mL/g;
Linear polyphenylthioether resin is coating level, particle diameter≤45um.
Exhaustive fluorinated ethylene propylene, particle diameter≤15um, is the F46 exhaustive fluorinated ethylene propylene of being produced by Quzhou sky over the river fluorine chemistry company limited;
Ethylene-tetrafluoroethylene copolymer resins, particle diameter≤15um, is the F40 exhaustive fluorinated ethylene propylene of being produced by Yancheng Yong Hui fluoroplastics company limited.
Embodiment 8～12 use polyphenyl thioether modified paint preparations are resistance to worn, corrosion resistance nature matrix material
With coating described in embodiment 1～5, prepare respectively resistance to wear, the test piece of corrosion resistance nature matrix material, the body material adopting and coating are as shown in following table table 2, body material is of a size of 30 × 20 × 1mm, remove substrate material surface foreign matter, greasy dirt, by paint spay-coating to surface, send in process furnace, in stove, 300～380 ℃ of temperature, toast 10～30 minutes; Plasticizing, levelling after melting, coating that to form thickness be 0.01～0.08mm, is cooled to room temperature, then is placed in 23 ℃ of Homothermal Proof Box and does after status adjustment, to detect test in 72 hours.
Described in comparative example 4～6 use comparative examples 1～3 polyphenyl thioether modified paint preparation resistance to wear, the test piece of corrosion resistance nature matrix material, preparation method is with embodiment 8～12, the body material of employing and coating are as shown in following table table 2.
Test piece to embodiment 8～12, comparative example 4～6 detects test, and test item is as follows:
Appearance of coat: visual method;
Rub(bing)test: test piece is put on reciprocating frictional testing machines, and Material Matting is identical with test piece base material; Applying load 0.5MPa, speed 1m/s (per minute comes and goes 120 times), stroke 250mm, combined stroke 1000m, medium is tap water, observes surface of friction, surveys friction pair wear loss;
Salt-fog test: specimen size 30 × 20 × 1mm, coat-thickness 0.08mm, tests by GB/T10125-1997;
HCl test: technical hydrochloric acid (36%w), soaking at room temperature 7 days, observes corrosion phenomenon;
Caustic soda test: liquid caustic soda (Na OH content is 40%w), room temperature bubble 7 days, observes corrosion phenomenon;
Acetic acid test: industrial acetic (98%w), room temperature 7 days, observes corrosion phenomenon;
Ethanol petrol weathering test: ethanol (20 parts by volume), gasoline (80 parts by volume), fully mix, put into test piece, airtight, under room temperature, soak 90 days, observe corrosion phenomenon;
Xenon light aging test: specimen size 30 × 20 × 1mm, coat-thickness 0.08mm, is placed in xenon light aging test case by test piece, and 3kW xenon lamp irradiates 1000h, observes and changes;
Freezing test: specimen size 30 × 20 × 1mm, coat-thickness 0.08mm, is placed in cold box by test piece, and-45 ℃, 1000h, observes and changes;
Coating toughness and adhesion test: to through the test piece of above-mentioned freezing test, folder diameter 1mm steel wire doubling 4 times (positive and negative each 2 times), observes coating damage, form comes off;
Weight loss on heating test: body material is that carbon steel or stainless test piece Heating temperature are 500 ℃, body material is that the test piece Heating temperature of aluminium is 360 ℃, constant temperature 1h, calculating is because of the weight loss on heating of weight loss on heating, and weight loss on heating is the weight that after test, test piece loses and the per-cent of testing front test piece weight.
The result that above-mentioned test piece is tested is as shown in following table table 2:
Table 2
From the test piece test-results of table 2 illustrated embodiment 8～12, comparative example 4～6, can find out: coating described in embodiment 1～5, component and the component ratio selected are suitable, and the coating of preparing shows excellent physico-chemical property; The coating that described in embodiment 1～3 and embodiment 5 prepared by coating, in weight loss on heating test, weight loss on heating is all 0.6% and following, the coating that particularly described in embodiment 4 prepared by coating, weight loss on heating is 0%, coating is not damaged, proved that coated material of the present invention can at high temperature be used, and has resistance to elevated temperatures.
From the test piece test-results of table 2 illustrated embodiment 8～12, can find out: described in embodiment 5, coating has adopted linear polyphenylene sulfide as base resin, the coating of preparing has adopted the coating physico-chemical property that prepared by coating described in the embodiment 1～4 of branched chain type polyphenylene sulfide poor, so the preferred branched chain type polyphenylene sulfide of coating of the present invention is as base resin.
From the test piece test-results of table 2 illustrated embodiment 8～12, comparative example 4, can find out: coating described in comparative example 1, its polyphenylene sulfide consumption is few, and has only used polyphenylene sulfide and exhaustive fluorinated ethylene propylene as base resin, makes the coating physico-chemical property prepared by this coating very poor; From the test piece test-results described in table 2 illustrated embodiment 8～12, comparative example 5, can find out: coating described in comparative example 2, use in high proportion polyphenylene sulfide, make the coating physico-chemical property prepared by this coating also bad, so the consumption of coating polyphenylene sulfide of the present invention selects 60～90%.
From table 2 illustrated embodiment 8～12, the test piece test-results that described in comparative example 6 prepared by coating, can find out: coating described in comparative example 3, although its polyphenylene sulfide consumption is more suitable, but owing to only having used polyphenylene sulfide and ethylene-tetrafluoroethylene copolymer resins as base resin, make the coating physico-chemical property prepared by this coating also very poor, so the present invention uses polyphenylene sulfide, exhaustive fluorinated ethylene propylene and the composite use of ethylene-tetrafluoroethylene copolymer resins, the common base resin as coating of the present invention, not only between component, there is fabulous consistency, but also make coating of the present invention have both the physical chemistry of described three kinds of base resin excellences, mechanics of machinery characteristic.
Claims (9)
1. polyphenyl thioether modified paint, is characterized in that, percentage composition meter is by weight composed of the following components:
Polyphenylene sulfide 60～90%,
Exhaustive fluorinated ethylene propylene 3～25%,
Ethylene-tetrafluoroethylene copolymer resins 3～20%,
Molybdenumdisulphide 1～5%,
Graphite 1～5%,
Filler surplus,
Described filler is any one or a few the mixture in zinc oxide, aluminum oxide, silicon carbide and chromium sesquioxide;
Described polyphenylene sulfide is branched chain type polyphenylene sulfide.
2. polyphenyl thioether modified paint according to claim 1, is characterized in that, described polyphenylene sulfide take limiting viscosity as 5～20mL/g.
3. according to the arbitrary described polyphenyl thioether modified paint of claim 1～2, it is characterized in that, the weight percentage of described polyphenylene sulfide is 60～80%, the weight percentage of described exhaustive fluorinated ethylene propylene is 5～20%, and the weight percentage of described ethylene-tetrafluoroethylene copolymer resins is 5～20%.
4. according to the arbitrary described polyphenyl thioether modified paint of claim 1～2, it is characterized in that, described zinc oxide is ZnOw.
5. polyphenyl thioether modified paint according to claim 4, is characterized in that, the length-to-diameter ratio of described ZnOw is 5:1～30:1.
6. according to the arbitrary described polyphenyl thioether modified paint of claim 1～2, it is characterized in that, described aluminum oxide is Alpha-alumina.
7. according to the arbitrary described polyphenyl thioether modified paint of claim 1～2, it is characterized in that, the particle diameter of described silicon carbide and chromium sesquioxide is less than or equal to 0.01mm.
8. the application of the arbitrary described polyphenyl thioether modified paint of claim 1～7, is characterized in that, by polyphenyl thioether modified paint be used in metal matrix material, make resistance to wear, corrosion resistance nature matrix material.
9. the preparation method of resistance to wearing described in claim 8, corrosion resistance nature matrix material, is characterized in that, comprises described polyphenyl thioether modified paint is sprayed in metal matrix material, heating, melting and solidification film forming.
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| US10889727B1 (en) | 2018-06-14 | 2021-01-12 | Southwire Company, Llc | Electrical cable with improved installation and durability performance |
| CN113308115A (en) * | 2021-06-11 | 2021-08-27 | 西北师范大学 | Preparation and application of modified zinc oxide-attapulgite/carboxylated polyphenylene sulfide composite material |
| CN114231165B (en) * | 2021-12-27 | 2022-06-28 | 扬州市维纳复合材料科技有限公司 | Polyphenylene sulfide powder coating and preparation method and application thereof |
| CN114702898B (en) * | 2022-04-20 | 2023-02-24 | 浙江新和成特种材料有限公司 | Wear-resistant and corrosion-resistant polyphenylene sulfide coating on metal surface and preparation method thereof |
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| CN1077589C (en) * | 1997-01-19 | 2002-01-09 | 田育甫 | Spraying method for fluoroplastic and fluoroplastic alloy corrosionproof coating |
| CN1095481C (en) * | 2000-12-27 | 2002-12-04 | 古旗高 | Process for preparing high-density high-molecular linear polyphenyl thioether |
| CN100413937C (en) * | 2004-08-11 | 2008-08-27 | 西南石油大学 | Petroleum pipe protective coating and its preparation method and uses |
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