CN103275448B - Preparation method of modified packing ion enhanced polytetrafluoroethylene composite - Google Patents
Preparation method of modified packing ion enhanced polytetrafluoroethylene composite Download PDFInfo
- Publication number
- CN103275448B CN103275448B CN201310255669.0A CN201310255669A CN103275448B CN 103275448 B CN103275448 B CN 103275448B CN 201310255669 A CN201310255669 A CN 201310255669A CN 103275448 B CN103275448 B CN 103275448B
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- glass fibre
- crystal whisker
- type zinc
- nano titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 54
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 48
- -1 polytetrafluoroethylene Polymers 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000012856 packing Methods 0.000 title abstract 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000011787 zinc oxide Substances 0.000 claims abstract description 54
- 239000003365 glass fiber Substances 0.000 claims abstract description 51
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 41
- 239000011159 matrix material Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 32
- 150000002500 ions Chemical class 0.000 claims abstract description 29
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims description 47
- 238000012986 modification Methods 0.000 claims description 38
- 230000004048 modification Effects 0.000 claims description 38
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 37
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 36
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 33
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 27
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000000945 filler Substances 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 15
- 238000012545 processing Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000002203 pretreatment Methods 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 9
- 229910021431 alpha silicon carbide Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229960004418 trolamine Drugs 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 206010070834 Sensitisation Diseases 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 230000008313 sensitization Effects 0.000 claims description 4
- 238000004448 titration Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000011049 filling Methods 0.000 abstract description 2
- 239000004760 aramid Substances 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 229920002313 fluoropolymer Polymers 0.000 description 9
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
The invention relates to a preparation method of a modified packing ion enhanced polytetrafluoroethylene composite. A matrix of the composite is polytetrafluoroethylene; filling ions comprise tetrapod-like zinc oxide whiskers, aramid fibers, glass fibers and nano titanium dioxide; the masses of the tetrapod-like zinc oxide whiskers, the aramid fibers, the glass fibers and nano titanium dioxide account for 10-12%, 5-7%, 3-4% and 2-3% of the mass of polytetrafluoroethylene powder; the polytetrafluoroethylene powder is in 120-150 meshes; the tetrapod-like zinc oxide whiskers are 12-14 micrometers in length; the diameters of roots of the tetrapod-like zinc oxide whiskers are 3-5 micrometers; the aramid fibers are 2-2.5mm in length; each monofilament is 8-10 micrometers in diameter; the glass fibers are glass fiber powder in 120-140 meshes; and the particle size of nano titanium dioxide is 15-30nm. The modified enhanced polytetrafluoroethylene composite has the advantages of high mechanical strength, good abrasive resistance, good thermal conductivity, lower linear expansion coefficient and excellent antistatic property, the mechanical properties and thermostability of the polytetrafluoroethylene composite are improved greatly, and the application field of the composite is further extended.
Description
Technical field
The present invention relates to field of new, be specifically related to a kind of preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material.
Background technology
In macromolecular structure, fluoroplastics are a kind of superpolymer containing fluorine atom (F) or fluorine atom group.By the method for processing forming of similar plastics, make section bar, unit product or part, these are all commonly referred to as fluoroplastics or fluorine plastic product.And generally fluoroplastic polymer is that monomer is obtained by copolymerization or homopolymerization synthesis, these monomers have: fluorochemical monomer is as tetrafluoroethylene, vinyl fluoride, R 1216, vinylidene etc.The form that they exist can be solution, pellet, powder etc.Section bar or unit product is obtained by various moulding process, section bar is obtained component by secondary processing method, these fluorine plastic products, with performances such as the insulativity of its excellence, heatproof stability, erosion resistance, self-lubricatings, are widely used in space flight and aviation, electric, the field such as chemical industry, building, machinery.Family more than 20 is had to be engaged in the company of fluoroplastics production at present in the world, these companies are mainly distributed in the countries and regions such as the U.S., Japan and West Europe, wherein with the industrial scale of the company such as Du Pont, Daikin Industries, Dyneon, Asahi Glass, ICI, Ausimont for larger.In the development, processing and application etc. of fluoroplastics, through the development of 40 years, Chinese fluoroplastics processing industry was made significant headway, and meanwhile, had a considerable amount of technical specialist troop and good sales network.Along with expanding economy, in the last few years, constantly introduced external advanced production equipment technology and required novel material at home, its demand was also constantly expanding, thus the processing of fluoroplastics and production obtain develop rapidly.Between 2001-2003 3 years, the annual production of Chinese polytetrafluoroethylene (PTFE) resin rises to 17914 t from 11032 t, and rate of growth every year on average has all exceeded 20%, and China has become PTFE goods big country.The method for processing forming of fluoroplastics has a lot, mainly contains blowing, injection moulding, mold pressing, extruding (plunger is extruded, paste extrusion), transfer mould, dipping, spraying, electroless plating etc.And tetrafluoroethylene (PTFE) is although its difficult forming, over-all properties is very good, and the proportion accounting for whole fluoroplastics output is quite large, greatly about about 70%, is applied to the numerous areas such as chemical industry, machinery, electric and electronic, automobile.Polytetrafluoroethylene (PTFE) molecular structure, determine PTFE and show excellent performance, performance mainly contains: PTFE has highly nonpolar material, have excellent electrical insulation capability, splendid chemical stability, frictional coefficient is little, water-intake rate is very low, excellent heat stability.Wide in range use temperature, ageing-resistant performance and radiation resistance outstanding.But any material is not perfect, and PTFE material is no exception, and the constructional feature of PTFE determines and it creates the following shortcoming: poor is subject to loading force, and mechanical property is lower.The physical strength of PTFE is very little, and hardness is also lower, and elasticity is low, and elongation at break is larger.Poor thermal conductivity.The thermal conductivity of PTFE is bad, and its thermal conductivity is lower, material being made like this not go in heat conduction surrounding medium in time, cause thermal fatigue than being easier to, thus greatly can reduce the work-ing life of material.Linear expansivity is larger.PTFE linear expansivity is larger comparatively speaking, is 13 times of iron and steel, so PTFE material ratio is easier to that cracking occurs wait calorifics phenomenon, this also can reduce the work-ing life of PTFE material.Shaping and secondary processing is difficult.When molding sintering is shaping, the shrinking percentage of PTFE goods can be larger, and be 1%-5%, PTFE is much bigger compared with the 0.1%-0.6% of rigid polyvinyl chloride, is so just not easy the accurate dimension controlling its goods.Its melt viscosity is very high, and the secondary processing technique such as injection molding, calendering formation that common plastics is conventional is not suitable for PTFE material, and can only use the method for like powder metallurgy.Wear no resistance.PTFE abrasion are also larger, thus limit the application of PTFE.Creep resistant is poor.Affect by its Working environment, under long-duration load, can there is larger creep in PTFE, then accumulate over a long period and cold flow will occur.The cold flow of PTFE also makes its application be restricted.Its intrinsic insulation characterisitic of PTFE (order of magnitude of insulation resistivity reaches 18) static charge in friction, stripping or induction process is easy to accumulate on the surface of PTFE pressing, just impulsive discharge may be caused after the static charge of accumulation acquires a certain degree, thus electronic circuit system may be disturbed to run, the insulation dielectric around it may be punctured time more serious, thus destroy the operation of whole system.
Summary of the invention
The invention provides a kind of preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material, with solve existing polytetrafluoroethylmaterial material mechanical property low, wear no resistance, poor thermal conductivity, linear expansivity are comparatively large and antistatic property is poor defect.
The present invention is achieved by the following technical solutions: matrices of composite material is tetrafluoroethylene, fill ion and comprise four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide, wherein four acicular type zinc oxide crystal whisker, aramid fiber, the quality of glass fibre and nano titanium oxide accounts for the 10-12% of polytetrafluorethylepowder powder quality respectively, 5-7%, 3-4% and 2-3%, described tetrafluoroethylene is 120-150 object polytetrafluorethylepowder powder, described four acicular type zinc oxide crystal whisker length 12-14 μm, base diameter 3-5 μm, described aramid fiber length is 2-2.5mm, filament diameter 8-10 μm, described glass fibre is 120-140 object glass fibre powder, described nano titanium oxide particle diameter is 15-30nm, described four acicular type zinc oxide crystal whisker needs to carry out modification in accordance with the following methods: weigh 0.5-0.8 g silane coupling agent and be dissolved in 60-70ml acetone, then drips oxalic acid adjustment PH to 5 ~ 6, leaves standstill 20-25 minute, then weigh 12-14g four acicular type zinc oxide crystal whisker and be placed in above-mentioned solution, to stirring 5-6 hour at 55-58 DEG C of temperature, then suction filtration, that dry out solvent obtains modification four acicular type zinc oxide crystal whisker is for subsequent use, described aramid fiber needs to carry out following pre-treatment: aramid fiber is soaked 8-10 hour in acetone, then in water and ethanol, boils 2-3 hour respectively, dry for standby, described glass fibre needs to carry out modification in accordance with the following methods: weigh 1-1.2g silane coupling agent and be dissolved in 40-50 ml acetone, then weighs 8-10g glass fibre and is placed in above-mentioned solution, to stirring 0.5-1 hour at 25-30 DEG C of temperature, and then 70-75 DEG C of dry 2-3 hour, for subsequent use after 1-1.5 hour 110-112 DEG C of activation, described nano titanium oxide needs to carry out modification in accordance with the following methods: take 1-1.5g silane coupling agent and be blended in 80-120g water, nano titanium oxide and trolamine are according to mass ratio 1:0.5-1 mixed grinding, take abrasive 15-20g to be distributed in the above-mentioned water body containing silane coupling agent, regulate PH to 8.5-8.8, stir 3-4 hour, then suction filtration, dry that to obtain modified nano-titanium dioxide for subsequent use, the concrete preparation process of matrix material is as follows:
(1), by modification or pretreated four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide mix under high velocity agitation, then add polytetrafluorethylepowder powder ball milling and obtain batch mixing in 25-30 minute;
(2), by mixture coldmoulding in constant voltage 30-40 minute under 40-50MPa condition that batch mixing will obtain again, carry out sintering curing more shaping, time below 180 DEG C, temperature rise rate controls as 65-72 DEG C/h, more than 200 DEG C is 55-58 DEG C/h, finally at 385 DEG C of insulation 4-5 hour, is then cooled to 200 DEG C with the rate of temperature fall of 50-55 DEG C/h, less than 200 DEG C rate of temperature fall are 65-70 DEG C/h, finally be cooled to room temperature, by sample polishing processing, namely obtain ptfe composite goods.
Such scheme can be improved to further:
Described filling ion also comprises silicon carbide, and it accounts for the 2-3% of polytetrafluorethylepowder powder quality; Described silicon carbide selects mean particle size to be the α-SiC particle of 16-17 μm, and it is several filler Ar ion mixing with other in step (1).
Need to carry out following pre-treatment before described α-SiC particle mixing: (1), chlorohydric acid pickling: SiC particle is joined in the hydrochloric acid of massfraction 15-18%, and 4-5 hour is soaked at 28-30 DEG C, filter and wash SiC particle to PH is 6-7, for subsequent use after drying; (2), high temperature oxidation: be oxidized 5 hours at step (2) being dried SiC particle 950-980 DEG C obtained, cooling is rear for subsequent use; (3), nitrate sensitization: step (3) is cooled the SiC particle obtained and soak 3 hours in the magnesium nitrate solution of massfraction 20-22%, then in 3 hours with till the ammonia water titration solution PH of massfraction 10-20% most 9.2, filter and at 420 DEG C dry for standby.
The silane coupling agent of described four acicular type zinc oxide crystal whisker modification is KH-570, and the silane coupling agent of described glass fibre modification is KH-550; Described nano-titanium dioxide modified silane coupling agent is KH-560.
Principle of the present invention is:
(1) by adding grit SiC in tetrafluoroethylene, not only can improve the dimensional stability of PTFE, mechanical property and wear resistance, but also thermotolerance and the creep-resistant property of PTFE material can be improved, and can thermal expansivity be reduced.
(2) due to fiber high-strength degree and rigidity and good thermal conductivity, utilize these advantages, aramid fiber and glass fibre are compound in PTFE matrix, improve frictional behaviour and the mechanical property of polymer P TFE.Research shows, produce when wearing and tearing because matrix and other material occur to rub, fiber can play good carrying effect, can form the transfer film of uniformly continous, thus the wear resistance of matrix material is significantly improved on mating plate surface.
(3) four acicular type zinc oxide crystal whisker (T-ZnO
w) there is the performance that generally common one dimension whisker do not possess, T-ZnO with the isotropy feature of transitivity because of its special three-dimensional space physical structure
wbe uniformly distributed in the base than being easier to, the performance of the matrix material prepared has isotropy, and this is that one dimension crystal whisker materials and granular filler are unapproachable, T-ZnO
wexcept being used to as wild phase to except the mechanical mechanics property effect strengthening body material, much apply such as vibration and noise reducing, antistatic, antibacterial etc. in addition.The present invention is by mixing T-ZnO
wafter can to PTFE matrix, in electrical applications field, especially antistatic application aspect promotes to some extent on the one hand, also can make moderate progress on the other hand in thermal property, improves its thermal conductivity and reduces thermal expansivity.Make this matrix material can have certain using value in electric works field.
(4), nano titanium oxide (TiO
2) there is distinctive nanometer size effect, large specific surface area, have stronger interfacial interaction with polymkeric substance, its Filled PTEF that can combine with aramid fiber, glass fibre, plays synergy, TiO
2the supporting capacity of matrix material can be improved, make up fibre fractionation fill less than barren pars fibrosa, thus improve the wear resisting property of matrix material.
The present invention is by modification enhanced polytetrafluoroethylene matrix material, there is the advantage that physical strength is high, wear resistance good, thermal conductivity is good, linear expansivity is less and antistatic property is excellent, improve mechanical property and the thermostability of polytetrafluoroethylmaterial material to a great extent, widen its Application Areas further.
Embodiment
Below by way of specific embodiment, the present invention is described in detail.
Embodiment 1
A kind of preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material, matrices of composite material is tetrafluoroethylene, fill ion and comprise four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide, wherein four acicular type zinc oxide crystal whisker, aramid fiber, the quality of glass fibre and nano titanium oxide accounts for 10% of polytetrafluorethylepowder powder quality respectively, 5%, 3% and 2%, tetrafluoroethylene is 120 object polytetrafluorethylepowder powders, four acicular type zinc oxide crystal whisker length 12 μm, base diameter 3 μm, aramid fiber length is 2mm, filament diameter 8 μm, glass fibre is 120 object glass fibre powder, nano titanium oxide particle diameter is 15nm, four acicular type zinc oxide crystal whisker needs to carry out modification in accordance with the following methods: weigh 0.5g silane coupling agent and be dissolved in 60ml acetone, then drips oxalic acid adjustment PH to 5, leaves standstill 20 minutes, then weigh 12g four acicular type zinc oxide crystal whisker and be placed in above-mentioned solution, to stirring 5 hours at 55 DEG C of temperature, then suction filtration, that dry out solvent obtains modification four acicular type zinc oxide crystal whisker is for subsequent use, aramid fiber needs to carry out following pre-treatment: aramid fiber is soaked 8 hours in acetone, then in water and ethanol, boils 2 hours respectively, dry for standby, glass fibre needs to carry out modification in accordance with the following methods: weigh 1g silane coupling agent and be dissolved in 40 ml acetone, then weighs 8g glass fibre and is placed in above-mentioned solution, to stirring 0.5 hour at 25 DEG C of temperature, and then 70 DEG C of dryings 2 hours, for subsequent use after 1 hour 110 DEG C of activation, nano titanium oxide needs to carry out modification in accordance with the following methods: take 1g silane coupling agent and be blended in 80g water, nano titanium oxide and trolamine are according to mass ratio 1:0.5 mixed grinding, take abrasive 15g to be distributed in the above-mentioned water body containing silane coupling agent, regulate PH to 8.5, stirs 3 hours, then suction filtration, that oven dry obtains modified nano-titanium dioxide is for subsequent use, the concrete preparation process of matrix material is as follows:
(1), by modification or pretreated four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide mix under high velocity agitation, then add polytetrafluorethylepowder powder ball milling and obtain batch mixing in 25 minutes;
(2), by mixture constant voltage coldmoulding in 30 minutes under 40MPa condition that batch mixing will obtain again, carry out sintering curing more shaping, time below 180 DEG C, temperature rise rate controls is 65 DEG C/h, more than 200 DEG C is 55 DEG C/h, finally 385 DEG C of insulations 4 hours, is then cooled to 200 DEG C with the rate of temperature fall of 50 DEG C/h, less than 200 DEG C rate of temperature fall are 65 DEG C/h, finally be cooled to room temperature, by sample polishing processing, namely obtain ptfe composite goods.
Embodiment 2
A kind of preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material, matrices of composite material is tetrafluoroethylene, fill ion and comprise four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide, wherein four acicular type zinc oxide crystal whisker, aramid fiber, the quality of glass fibre and nano titanium oxide accounts for 12% of polytetrafluorethylepowder powder quality respectively, 7%, 4% and 3%, tetrafluoroethylene is 150 object polytetrafluorethylepowder powders, four acicular type zinc oxide crystal whisker length 14 μm, base diameter 5 μm, aramid fiber length is 2.5mm, filament diameter 10 μm, glass fibre is 140 object glass fibre powder, nano titanium oxide particle diameter is 30nm, four acicular type zinc oxide crystal whisker needs to carry out modification in accordance with the following methods: weigh 0.8 g silane coupling agent and be dissolved in 70ml acetone, then drips oxalic acid adjustment PH to 6, leaves standstill 25 minutes, then weigh 14g four acicular type zinc oxide crystal whisker and be placed in above-mentioned solution, to stirring 6 hours at 58 DEG C of temperature, then suction filtration, that dry out solvent obtains modification four acicular type zinc oxide crystal whisker is for subsequent use, aramid fiber needs to carry out following pre-treatment: aramid fiber is soaked 10 hours in acetone, then in water and ethanol, boils 3 hours respectively, dry for standby, glass fibre needs to carry out modification in accordance with the following methods: weigh 1.2g silane coupling agent and be dissolved in 50 ml acetone, then weighs 10g glass fibre and is placed in above-mentioned solution, to stirring 1 hour at 30 DEG C of temperature, and then 75 DEG C of dryings 3 hours, for subsequent use after 1.5 hours 112 DEG C of activation, nano titanium oxide needs to carry out modification in accordance with the following methods: take 1.5g silane coupling agent and be blended in 120g water, nano titanium oxide and trolamine are according to mass ratio 1:1 mixed grinding, take abrasive 20g to be distributed in the above-mentioned water body containing silane coupling agent, regulate PH to 8.8, stirs 4 hours, then suction filtration, that oven dry obtains modified nano-titanium dioxide is for subsequent use, the concrete preparation process of matrix material is as follows:
(1), by modification or pretreated four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide mix under high velocity agitation, then add polytetrafluorethylepowder powder ball milling and obtain batch mixing in 30 minutes;
(2), by mixture constant voltage coldmoulding in 40 minutes under 50MPa condition that batch mixing will obtain again, carry out sintering curing more shaping, time below 180 DEG C, temperature rise rate controls is 72 DEG C/h, more than 200 DEG C is 58 DEG C/h, finally 385 DEG C of insulations 5 hours, is then cooled to 200 DEG C with the rate of temperature fall of 55 DEG C/h, less than 200 DEG C rate of temperature fall are 70 DEG C/h, finally be cooled to room temperature, by sample polishing processing, namely obtain ptfe composite goods.
Embodiment 3
A kind of preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material, matrices of composite material is tetrafluoroethylene, fill ion and comprise four acicular type zinc oxide crystal whisker, aramid fiber and glass fiber and nano titanium oxide, wherein four acicular type zinc oxide crystal whisker, aramid fiber, the quality of glass fibre and nano titanium oxide accounts for 10% of polytetrafluorethylepowder powder quality respectively, 7%, 4% and 2%, tetrafluoroethylene is 150 object polytetrafluorethylepowder powders, described four acicular type zinc oxide crystal whisker length 12 μm, base diameter 5 μm, aramid fiber length is 2mm, filament diameter 10 μm, glass fibre is 140 object glass fibre powder, nano titanium oxide particle diameter is 30nm, four acicular type zinc oxide crystal whisker needs to carry out modification in accordance with the following methods: weigh 0.8 g silane coupling agent and be dissolved in 70ml acetone, then drips oxalic acid adjustment PH to 6, leaves standstill 20 minutes, then weigh 12g four acicular type zinc oxide crystal whisker and be placed in above-mentioned solution, to stirring 6 hours at 58 DEG C of temperature, then suction filtration, that dry out solvent obtains modification four acicular type zinc oxide crystal whisker is for subsequent use, described aramid fiber needs to carry out following pre-treatment: aramid fiber is soaked 8 hours in acetone, then in water and ethanol, boils 2 hours respectively, dry for standby, described glass fibre needs to carry out modification in accordance with the following methods: weigh 1g silane coupling agent and be dissolved in 40 ml acetone, then weighs 8g glass fibre and is placed in above-mentioned solution, to stirring 0.5 hour at 25 DEG C of temperature, and then 75 DEG C of dryings 3 hours, for subsequent use after 1.5 hours 110 DEG C of activation, nano titanium oxide needs to carry out modification in accordance with the following methods: take 1.5g silane coupling agent and be blended in 120g water, nano titanium oxide and trolamine are according to mass ratio 1:0.5 mixed grinding, take abrasive 20g to be distributed in the above-mentioned water body containing silane coupling agent, regulate PH to 8.5, stirs 4 hours, then suction filtration, that oven dry obtains modified nano-titanium dioxide is for subsequent use, fill ion and also comprise silicon carbide, it accounts for the 2-3% of polytetrafluorethylepowder powder quality, silicon carbide selects mean particle size to be the α-SiC particle of 17 μm, need to carry out following pre-treatment before the mixing of α-SiC particle: (1), chlorohydric acid pickling: SiC particle is joined in the hydrochloric acid of massfraction 18%, and soak 5 hours at 30 DEG C, filtering and washing SiC particle to PH is 7, for subsequent use after drying, (2), high temperature oxidation: be oxidized 5 hours at step (2) being dried the SiC particle 980 DEG C obtained, cooling is rear for subsequent use, (3), nitrate sensitization: step (3) is cooled the SiC particle obtained and soak 3 hours in the magnesium nitrate solution of massfraction 20-22%, then in 3 hours with till the ammonia water titration solution PH of massfraction 20% most 9.2, filter and at 420 DEG C dry for standby, the concrete preparation process of matrix material is as follows:
(1), by modification or pretreated four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre, nano titanium oxide, silicon carbide mix under high velocity agitation, then add polytetrafluorethylepowder powder ball milling and obtain batch mixing in 25 minutes;
(2), by mixture constant voltage coldmoulding in 40 minutes under 40MPa condition that batch mixing will obtain again, carry out sintering curing more shaping, time below 180 DEG C, temperature rise rate controls is 72 DEG C/h, more than 200 DEG C is 58 DEG C/h, finally 385 DEG C of insulations 5 hours, is then cooled to 200 DEG C with the rate of temperature fall of 50 DEG C/h, less than 200 DEG C rate of temperature fall are 65 DEG C/h, finally be cooled to room temperature, by sample polishing processing, namely obtain ptfe composite goods.
Embodiment 4
A kind of preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material, matrices of composite material is tetrafluoroethylene, fill ion and comprise four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide, wherein four acicular type zinc oxide crystal whisker, aramid fiber, the quality of glass fibre and nano titanium oxide accounts for 10% of polytetrafluorethylepowder powder quality respectively, 5%, 3% and 3%, tetrafluoroethylene is 150 object polytetrafluorethylepowder powders, four acicular type zinc oxide crystal whisker length 14 μm, base diameter 5 μm, aramid fiber length is 2mm, filament diameter 10 μm, glass fibre is 140 object glass fibre powder, nano titanium oxide particle diameter is 15nm, four acicular type zinc oxide crystal whisker needs to carry out modification in accordance with the following methods: weigh 0.8 g silane coupling agent and be dissolved in 60ml acetone, then drips oxalic acid adjustment PH to 6, leaves standstill 25 minutes, then weigh 14g four acicular type zinc oxide crystal whisker and be placed in above-mentioned solution, to stirring 5 hours at 58 DEG C of temperature, then suction filtration, that dry out solvent obtains modification four acicular type zinc oxide crystal whisker is for subsequent use, aramid fiber needs to carry out following pre-treatment: aramid fiber is soaked 10 hours in acetone, then in water and ethanol, boils 2 hours respectively, dry for standby, glass fibre needs to carry out modification in accordance with the following methods: weigh 1.2g silane coupling agent and be dissolved in 50 ml acetone, then weighs 8g glass fibre and is placed in above-mentioned solution, to stirring 0.5 hour at 30 DEG C of temperature, and then 75 DEG C of dryings 3 hours, for subsequent use after 1.5 hours 110 DEG C of activation, nano titanium oxide needs to carry out modification in accordance with the following methods: take 1.5g silane coupling agent and be blended in 80g water, nano titanium oxide and trolamine are according to mass ratio 1:1 mixed grinding, take abrasive 20g to be distributed in the above-mentioned water body containing silane coupling agent, regulate PH to 8.5, stirs 4 hours, then suction filtration, that oven dry obtains modified nano-titanium dioxide is for subsequent use, fill ion and also comprise silicon carbide, it accounts for 3% of polytetrafluorethylepowder powder quality, silicon carbide selects mean particle size to be the α-SiC particle of 17 μm, need to carry out following pre-treatment before the mixing of α-SiC particle: (1), chlorohydric acid pickling: SiC particle is joined in the hydrochloric acid of massfraction 18%, and 4-5 hour is soaked at 30 DEG C, filtering and washing SiC particle to PH is 6, for subsequent use after drying, (2), high temperature oxidation: be oxidized 5 hours at step (2) being dried the SiC particle 950 DEG C obtained, cooling is rear for subsequent use, (3), nitrate sensitization: step (3) is cooled the SiC particle obtained and soak 3 hours in the magnesium nitrate solution of massfraction 22%, then in 3 hours with till the ammonia water titration solution PH of massfraction 10% most 9.2, filter and at 420 DEG C dry for standby, the concrete preparation process of matrix material is as follows:
(1), by modification or pretreated four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre, nano titanium oxide and silicon carbide mix under high velocity agitation, then add polytetrafluorethylepowder powder ball milling and obtain batch mixing in 30 minutes;
(2), by mixture constant voltage coldmoulding in 30 minutes under 50MPa condition that batch mixing will obtain again, carry out sintering curing more shaping, time below 180 DEG C, temperature rise rate controls is 72 DEG C/h, more than 200 DEG C is 58 DEG C/h, finally 385 DEG C of insulations 4 hours, is then cooled to 200 DEG C with the rate of temperature fall of 55 DEG C/h, less than 200 DEG C rate of temperature fall are 70 DEG C/h, finally be cooled to room temperature, by sample polishing processing, namely obtain ptfe composite goods.
In order to improve the dispersiveness of filler ion in polymer P TFE matrix, and with the avidity of PTFE, the filler ion of embodiment 1-4 adopts coupling agent to carry out surface modification, improves the connection tightness of filler ion and polymeric matrix; The silane coupling agent of four acicular type zinc oxide crystal whisker modification is KH-570, and the silane coupling agent of glass fibre modification is KH-550; Nano-titanium dioxide modified silane coupling agent is KH-560.
Test proves, friction coefficient of composite material prepared by embodiment 1-4 is 0.20-0.24, and wear rate is 0.12-0.14 × 10
-6cm
3/ Nm, and the frictional coefficient of pure PTFE is about 0.18, wear rate is about 9 × 10
-6cm
3/ Nm, compares known, and the frictional coefficient of this material is close with pure PTFE, but wear resistance significantly improves, and abrasion loss reduces greatly.The thermal conductivity of matrix material is 0.65-0.73 W/m*K, compared with the thermal conductivity 0.25-0.3W/m*K of pure PTFE, is doubled many; The average mechanical performance index of this matrix material are simultaneously: tensile strength 36.2Mpa, shock strength 27.4kj/cm
2, hardness 65.4HRL, improves 98%, 54% and 51% than pure PTFE respectively, by above contrast, the mechanical property of this matrix material increases substantially, the every mechanical property of matrix material especially good (tensile strength 38.8Mpa, the shock strength 28.9kj/cm of especially embodiment 3 and 4 preparation
2, hardness 69.3HRL).Matrix material machinery performance prepared by the present invention is high, thermal expansivity is low, there is good thermal conductivity and wear-resistant wear resistance, and prepare than being easier to, the low and wild phase (filler ion) of cost Dispersed precipitate and there is isotropy in matrix, be applicable to various complex stress condition.
Claims (4)
1. the preparation method of a modified filler ion enhanced polytetrafluoroethylene matrix material, it is characterized in that, matrices of composite material is tetrafluoroethylene, filler ion comprises four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide, described tetrafluoroethylene is 120-150 object polytetrafluorethylepowder powder, wherein four acicular type zinc oxide crystal whisker, aramid fiber, the quality of glass fibre and nano titanium oxide accounts for the 10-12% of polytetrafluorethylepowder powder quality respectively, 5-7%, 3-4% and 2-3%, described four acicular type zinc oxide crystal whisker length 12-14 μm, base diameter 3-5 μm, described aramid fiber length is 2-2.5mm, filament diameter 8-10 μm, described glass fibre is 120-140 object glass fibre powder, described nano titanium oxide particle diameter is 15-30nm, described four acicular type zinc oxide crystal whisker needs to carry out modification in accordance with the following methods: weigh 0.5-0.8 g silane coupling agent and be dissolved in 60-70ml acetone, then drip careless acid for adjusting pH to 5 ~ 6, leave standstill 20-25 minute, then weigh 12-14g four acicular type zinc oxide crystal whisker and be placed in above-mentioned solution, at 55-58 DEG C of temperature, stir 5-6 hour, then suction filtration, that dry out solvent obtains modification four acicular type zinc oxide crystal whisker is for subsequent use, described aramid fiber needs to carry out following pre-treatment: aramid fiber is soaked 8-10 hour in acetone, then in water and ethanol, boils 2-3 hour respectively, dry for standby, described glass fibre needs to carry out modification in accordance with the following methods: weigh 1-1.2g silane coupling agent and be dissolved in 40-50 ml acetone, then weighs 8-10g glass fibre and is placed in above-mentioned solution, to stirring 0.5-1 hour at 25-30 DEG C of temperature, then at 70-75 DEG C of dry 2-3 hour, for subsequent use after 1-1.5 hour 110-112 DEG C of activation, described nano titanium oxide needs to carry out modification in accordance with the following methods: take 1-1.5g silane coupling agent and be blended in 80-120g water, nano titanium oxide and trolamine are according to mass ratio 1:0.5-1 mixed grinding, take abrasive 15-20g to be distributed in the above-mentioned water body containing silane coupling agent, regulate pH to 8.5-8.8, stir 3-4 hour, then suction filtration, dry that to obtain modified nano-titanium dioxide for subsequent use, the concrete preparation process of matrix material is as follows:
(1), by modification or pretreated four acicular type zinc oxide crystal whisker, aramid fiber, glass fibre and nano titanium oxide mix under high velocity agitation, then add polytetrafluorethylepowder powder ball milling and obtain batch mixing in 25-30 minute;
(2), by batch mixing coldmoulding in constant voltage 30-40 minute under 40-50MPa condition, carry out sintering curing more shaping, time below 180 DEG C, temperature rise rate controls as 65-72 DEG C/h, more than 200 DEG C is 55-58 DEG C/h, finally at 385 DEG C of insulation 4-5 hour, is then cooled to 200 DEG C with the rate of temperature fall of 50-55 DEG C/h, less than 200 DEG C rate of temperature fall are 65-70 DEG C/h, finally be cooled to room temperature, by sample polishing processing, namely obtain ptfe composite goods.
2. the preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material according to claim 1, it is characterized in that, described filler ion also comprises silicon carbide, and it accounts for the 2-3% of polytetrafluorethylepowder powder quality; Described silicon carbide selects mean particle size to be the α-SiC particle of 16-17 μm, its in step (1) with other filler Ar ion mixings.
3. the preparation method of modified filler ion enhanced polytetrafluoroethylene matrix material according to claim 2, it is characterized in that, need to carry out following pre-treatment before described α-SiC particle mixing: (1), chlorohydric acid pickling: SiC particle is joined in the hydrochloric acid of massfraction 15-18%, and 4-5 hour is soaked at 28-30 DEG C, filter and wash SiC particle to pH is 6-7, for subsequent use after drying; (2), high temperature oxidation: be oxidized 5 hours at step (2) being dried SiC particle 950-980 DEG C obtained, cooling is rear for subsequent use; (3), nitrate sensitization: step (3) is cooled the SiC particle obtained and soak 3 hours in the magnesium nitrate solution of massfraction 20-22%, then in 3 hours with the ammonia water titration pH value of solution to 9.2 of massfraction 10-20%, filter and at 420 DEG C dry for standby.
4. according to the preparation method of the arbitrary described modified filler ion enhanced polytetrafluoroethylene matrix material of claim 1-3, it is characterized in that, the silane coupling agent of described four acicular type zinc oxide crystal whisker modification is KH-570, and the silane coupling agent of described glass fibre modification is KH-550; Described nano-titanium dioxide modified silane coupling agent is KH-560.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255669.0A CN103275448B (en) | 2013-06-25 | 2013-06-25 | Preparation method of modified packing ion enhanced polytetrafluoroethylene composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255669.0A CN103275448B (en) | 2013-06-25 | 2013-06-25 | Preparation method of modified packing ion enhanced polytetrafluoroethylene composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103275448A CN103275448A (en) | 2013-09-04 |
| CN103275448B true CN103275448B (en) | 2015-05-06 |
Family
ID=49058083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310255669.0A Expired - Fee Related CN103275448B (en) | 2013-06-25 | 2013-06-25 | Preparation method of modified packing ion enhanced polytetrafluoroethylene composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103275448B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603088A (en) * | 2017-08-16 | 2018-01-19 | 宁波伏龙同步带有限公司 | A kind of preparation method of timing belt molding sulfuration capsule |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106009665A (en) * | 2016-04-13 | 2016-10-12 | 安徽鑫柏格电子股份有限公司 | Polyimide film with low thermal expansion coefficient and preparation method thereof |
| CN106082743B (en) * | 2016-06-03 | 2017-12-05 | 西南石油大学 | Four acicular type zinc oxide crystal whisker toughener for well-cementing cement toughness reinforcing |
| CN106381537B (en) * | 2016-08-29 | 2018-11-13 | 常州万容新材料科技有限公司 | A kind of manufacturing method of the short fibres of PTFE |
| CN106700351A (en) * | 2016-11-09 | 2017-05-24 | 嘉科（安徽）密封技术有限公司 | High-strength and high-toughness wear-resistant polytetrafluoroethylene composite material |
| CN108264714A (en) * | 2018-01-15 | 2018-07-10 | 芜湖航天特种电缆厂股份有限公司 | High-weatherability cable cover(ing) and preparation method thereof |
| CN113214581B (en) * | 2021-05-12 | 2022-06-14 | 九江市磐泰复合材料有限公司 | Preparation method of high-flexibility folding-resistant polytetrafluoroethylene glass fiber material |
| CN113921877A (en) * | 2021-10-08 | 2022-01-11 | 安徽元琛环保科技股份有限公司 | Preparation method of composite proton exchange membrane and prepared composite proton exchange membrane |
| CN114605760A (en) * | 2022-03-29 | 2022-06-10 | 江苏博诚新科技材料有限公司 | Process for preparing polytetrafluoroethylene glass fiber breathable varnished cloth |
| CN116102837A (en) * | 2022-12-30 | 2023-05-12 | 浙江松华新材股份有限公司 | Preparation method and device of modified polytetrafluoroethylene composite material |
| CN116715928A (en) * | 2023-07-28 | 2023-09-08 | 浙江松华新材股份有限公司 | Modified PFA with high strength and wear resistance and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4386633B2 (en) * | 2002-12-27 | 2009-12-16 | 三井・デュポンフロロケミカル株式会社 | Fluoro resin composition |
| CN100564474C (en) * | 2007-04-30 | 2009-12-02 | 北京市天山新材料技术公司 | Teflon seal tape and complete processing thereof and storage belting |
| CN102731941A (en) * | 2012-06-13 | 2012-10-17 | 浙江大学 | Preparation method of teflon composite material |
-
2013
- 2013-06-25 CN CN201310255669.0A patent/CN103275448B/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107603088A (en) * | 2017-08-16 | 2018-01-19 | 宁波伏龙同步带有限公司 | A kind of preparation method of timing belt molding sulfuration capsule |
| CN107603088B (en) * | 2017-08-16 | 2019-07-26 | 宁波伏龙同步带有限公司 | A kind of preparation method of synchronous belt molding sulfuration capsule |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103275448A (en) | 2013-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103275448B (en) | Preparation method of modified packing ion enhanced polytetrafluoroethylene composite | |
| CN103333442B (en) | TiO 2the preparation method of-SiC-fibre filling polytetrafluoroethyland matrix material | |
| CN102675819B (en) | Wear resistant self-lubricating polyformaldehyde and preparation method thereof | |
| CN101735554B (en) | Polyetheretherketone composite material, preparation method and application thereof | |
| CN103319824B (en) | Method for preparing modified and enhanced polytetrafluoroethylene composite material | |
| CN102010593B (en) | Mineral and long glass fiber reinforced nylon 6 composite material and preparation method thereof | |
| CN1301298C (en) | Self-lubricating bearing material, and preparation method | |
| CN103242641B (en) | Polyaryletherketone-based abrasion-resistant composite material and preparation method thereof | |
| CN103613883B (en) | A kind of take Graphene as Wear-resistant hard composite material of filler and preparation method thereof | |
| CN103087468A (en) | Polyether-ether-ketone composite material with high heat resistance and high wear resistance and preparation process thereof | |
| CN102250446B (en) | High-dimension-stability and friction-resistant polyether-ether-ketone composite material and preparation method thereof | |
| CN103450631B (en) | Polyether-ether-ketone cable material and preparation method thereof | |
| CN102010547A (en) | Mineral/long glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN102093716A (en) | Polyphenylene sulfide/polyether sulfone-based compound material and preparation method thereof as well as wear-resistant part prepared from polyphenylene sulfide/polyether sulfone-based compound material | |
| CN101831173A (en) | Bi-phthalonitrile resin glass fiber composite material toughened by poly(arylene ether nitrile) and preparation method thereof | |
| CN104629324A (en) | High-strength toughened functionalized PC/ABS alloy material | |
| JPS58160346A (en) | Resin composition | |
| CN102206391A (en) | Polytetrafluoroethylene self-reinforced composite material and preparation method thereof | |
| CN108264758A (en) | A kind of high dielectric property and wear-resisting nylon composite materials and preparation method thereof | |
| CN109294032B (en) | Multi-element composite filling particle modified heat-conducting PE composite material and preparation method thereof | |
| CN101555348A (en) | Composite material of polycarylene ether nitrile fiberglass and preparation method thereof | |
| CN104448825A (en) | Polyphenylene sulfide composite material and preparation method thereof | |
| CN103396643A (en) | Modifier-containing polyacrylate grafted vinyl chloride composite resin composition | |
| CN109467790A (en) | A kind of ultra-high molecular weight polyethylene product | |
| CN106189122A (en) | A kind of PBT PP alloy and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: LI YIFAN Free format text: FORMER OWNER: MENG HONGLIN Effective date: 20150402 |
|
| CB03 | Change of inventor or designer information |
Inventor after: Li Yifan Inventor before: Meng Honglin |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: MENG HONGLIN TO: LI YIFAN Free format text: CORRECT: ADDRESS; FROM: 257091 DONGYING, SHANDONG PROVINCE TO: 454650 JIAOZUO, HENAN PROVINCE |
|
| TA01 | Transfer of patent application right |
Effective date of registration: 20150402 Address after: 454650 Henan city of Jiaozuo province Jiyuan Qinyuan office the Yellow River Road Light District No. 3 Building 2 unit 401 Applicant after: Li Yifan Address before: 257091 Shandong Province, Dongying city Dongying District Dongcheng Trade City No. 2 section of A section of Dongpu center four floor Applicant before: Meng Honglin |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180403 Address after: The town of Nanhai District, Guangdong city of Foshan Province, 528225 Haruki Dugang Bai shop floor No. 5-11 South row. Patentee after: Ming Yang wire factory, Nanhai District, Foshan Address before: 510000 Guangdong Province, Guangzhou high tech Industrial Development Zone, No. 233 science road 231 floor B1B2 building one layer, two layer, three layer, four layer Patentee before: BOAO ZONGHENG NETWORK TECHNOLOGY Co.,Ltd. Effective date of registration: 20180403 Address after: 510000 Guangdong Province, Guangzhou high tech Industrial Development Zone, No. 233 science road 231 floor B1B2 building one layer, two layer, three layer, four layer Patentee after: BOAO ZONGHENG NETWORK TECHNOLOGY Co.,Ltd. Address before: 454650 Henan city of Jiaozuo province Jiyuan Qinyuan office the Yellow River Road Light District No. 3 Building 2 unit 401 Patentee before: Li Yifan |
|
| TR01 | Transfer of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150506 Termination date: 20190625 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |