CN1990538A - High-wearing polytetrafluoroethylene composite material and preparing method thereof - Google Patents
High-wearing polytetrafluoroethylene composite material and preparing method thereof Download PDFInfo
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Abstract
The invention relates to polytetrafluoroethylene composite material and the method for preparing the same, belonging to polymer material modification field. Said polytetrafluoroethylene composite material with strong wear- resistant property is prepared through following steps: mixing polytetrafluoroethylene with polyacrylonitrile powder, pressing and shaping, and sintering at high temperature. The granule rate of said polytetrafluoroethylene powder is 30- 200 um, and the content is 50- 70%; the granule rate of polyacrylonitrile powder is 30- 100 um, and content is 30- 50%. The metal, metal oxidant, non-metal oxidant, carbide and other fiber packing material can be selectively filled into the component, which can dramatically increase the wear- resistant performance by over 100 times, heat- resistant performance and high temperature mechanical properties. The composite material is suited to be used to prepare wear- resistant, high temperature resistant, chemical product resistant, low- friction coefficient sealing ring, valve, pipeline and pump. The method is characterized by simple process and low production cost.
Description
Technical field
The invention belongs to the polymer modification art, be specifically related to ptfe composite and preparation method.
Background technology:
Tetrafluoroethylene is widely used in various fields because of its excellent chemical stability, high temperature resistant and low frictional coefficient, yet it wears no resistance and the cost height has restricted its use range.The friction and wear behavior with metal filled modified Teflon was once introduced by China's " polymer material science and engineering " (1999 the 15th the 1st phases of volume, the 68th page to 72 pages).Increase metal charge and can improve 1-2 order of magnitude of tetrafluoroethylene polishing machine, but owing to lack consistency, be easy to generate and be separated, and these metallicss can make flour milling is produced wearing and tearing, make the frictional coefficient increase of material with tetrafluoroethylene.China's " Materials Science and Engineering journal " (2003 the 21st the 6th phases of volume, the 851st page to 854 pages) also once introduced and used polybenzoate, the filling-modified tetrafluoroethylene friction and wear behavior of polyimide respectively, obtained good effect, but the adding of above-mentioned filler makes the preparation cost increase at double of ptfe composite, and this has just limited its use range.
Institute of Chemistry, Academia Sinica uses PAN-based carbon fiber to come the reinforced TFE sealing material in the CN85100880A patent, and this can improve the resistance to elevated temperatures and the work-ing life of polytetrafluoroethylmaterial material.But this PAN-based carbon fiber cloth is limited to the effect of the wearability of raising polytetrafluoroethylmaterial material, is only adding obvious its abrasion resistance properties that improves of ability under the metallic element situation.And because PAN-based carbon fiber course of processing complexity is unfavorable for formed product after its cloth and tetrafluoroethylene are compound.
Summary of the invention:
The objective of the invention is to, at deficiency of the prior art, provide a kind of high-wearing polytetrafluoroethylcomposite composite material, its preparation method is simple, and production cost is low and applied widely.
Purpose of the present invention realizes in the following manner.
High-wearing polytetrafluoroethylcomposite composite material of the present invention, it is characterized in that, it is by after tetrafluoroethylene and the polyacrylonitrile powder mixes, repressed moulding, high temperature sintering form, wherein, the granularity of polytetrafluorethylepowder powder is 30 μ m-200 μ m, and content is 50%-70% (weight percentage); The granularity of polyacrylonitrile powder is 30 μ m-100 μ m, and content is 30%-50% (weight percentage); Also can increase metal and metal oxide powder in its component, its granularity is 10 μ m-50 μ m, and content is for example copper, copper alloy, iron powder, Al of 0%-5% (weight percentage)
2O
3, TiO
2, ZnO powder etc.; Also can increase nonmetal oxide, carbide, granularity is granularity 10 μ m-50 μ m, and content is 0%-5% (weight percentage), for example SiO
2, the SiC powder; Can also increase the weighting material of other fiber-like, its diameter is 8 μ m-15 μ m, and content is 0%-5% (weight percentage), for example glass fibre, carbon fiber etc.
Its concrete production technique is as follows: (1) will mix by the each component of calculated amount and stir; (2) with compound in coldmoulding under the 40MPa pressure or be lower than under 250 ℃ of conditions hot-formingly, and under 40MPa pressure, kept 5-10 minute; (3) sample of compression moulding is inserted in the high temperature sintering furnace, be heated to 375 ℃ ± 5 ℃, be incubated 2 hours with 30 ℃-100 ℃/hour temperature rise rates; Be preferably in and be heated to the interior insulation of 270 ℃ of-315 ℃ of scopes 1-2 time, be incubated 20-30 minute at every turn; (4) naturally cool to room temperature; Be preferably in when being cooled to 315 ℃ and be incubated 20-30 minute, and then naturally cool to room temperature.Described polyacrylonitrile also can be that elder generation's pre-oxidation treatment under 370 ℃ of temperature is mixed with polytetrafluorethylepowder powder after 2 hours again.
The preparation method of high-wearing polytetrafluoroethylcomposite composite material of the present invention is characterized in that, its preparation process for (1) at first by the mixing of the each component of following calculated amount (being weight percentage) and stir:
Polytetrafluorethylepowder powder (granularity 30 μ m-200 μ m), 50%-70%,
Polyacrylonitrile powder (granularity 30 μ m-100 μ m), 30%-50%,
Nonmetal oxide, carbide (granularity 10 μ m-50 μ m), 0%-5%,
Metal and metal oxide powder (granularity 10 μ m-50 μ m), 0%-5%,
The weighting material of other fiber-like (diameter 8 μ m-15 μ m) 0%-5%
(2) with compound in coldmoulding under the 40MPa pressure or be lower than under 250 ℃ of conditions hot-formingly, and under 40MPa pressure, kept 5-10 minute;
(3) sample of compression moulding is inserted in the high temperature sintering furnace, be heated to 375 ℃ ± 5 ℃, be incubated 2 hours with 30 ℃-100 ℃/hour temperature rise rates; Be preferably in to be heated in 270 ℃ of-315 ℃ of scopes and be incubated each 20-30 minute 1-2 time;
(4) naturally cool to room temperature, be preferably in when being cooled to 315 ℃ and be incubated 20-30 minute, and then naturally cool to room temperature, get finished product.
Described polyacrylonitrile also can be that elder generation's pre-oxidation treatment under 370 ℃ of temperature is mixed with polytetrafluorethylepowder powder after 2 hours again, this will help reducing polyacrylonitrile in sintering process because of the negative impact of chemical reaction to material takes place, in actual use, can select to add metal and metal oxide, for example copper, copper alloy, iron powder, Al according to the actual product needs
2O
3, TiO
2, ZnO powder etc.; Select to add the particles such as weighting material of nonmetal oxide, carbide and other fiber-like, for example SiO
2, SiC powder, glass fibre, carbon fiber etc. to be to strengthen its corresponding performance, satisfies actual service requirements.
High-wearing polytetrafluoroethylcomposite composite material of the present invention, in polyacrylonitrile and the tetrafluoroethylene mixing material high temperature sintering moulding process, the preoxidation reaction can take place in polyacrylonitrile, form trapezoidal-structure through cyclisation, these ladder-shaper structures form skeleton, the friction transfer film that has strengthened matrix material has reduced the generation of new friction transfer film at the sticking power to the face surface of rubbing, thereby improves its wear resistance greatly.Actual measurement shows, matrix material of the present invention is compared and is not used modified polyacrylonitrile, its wear resistance significantly improves, the raising that has above 100 times, but also improved thermotolerance and mechanical behavior under high temperature, therefore the product that adopts matrix material of the present invention to make can use under than the higher temperature of former tetrafluoroethylene.Particularly, matrix material of the present invention also keeps very high storage modulus in molten state, has high temperature use properties preferably.Material of the present invention can be used as impregnating material, sealing material and high-abrasive material, is fit to require that wear resistance is good, frictional coefficient is little, high temperature resistant, chemical resistant sealing-ring, bearing lining, valve, pipeline, pump etc.
The preparation method of high-wearing polytetrafluoroethylcomposite composite material of the present invention, because tetrafluoroethylene and polyacrylonitrile have good consistency, so polyacrylonitrile powder and polytetrafluorethylepowder powder can directly adopt mechanically mixing, and be less demanding to production unit, technology is simple, and production cost is low.
Be further described below by embodiment.
Embodiment:
Embodiment 1
40% (weight percentage) polyacrylonitrile powder (granularity 30 μ m) and 60% polytetrafluorethylepowder powder (granularity 50 μ m) are put into the stirring of high speed agitator the inside mixed it in 10 minutes.Again with mixture compression moulding under 40MPa pressure, room temperature, then the compression moulding part is put into sintering oven, temperature rise rate with 100 ℃/hour under air ambient is heated to 150 ℃, be heated to 270 ℃ with 50 ℃/hour temperature rise rate again, be incubated 30 minutes, be heated to 315 ℃ with 40 ℃/hour temperature rise rate again, be incubated 30 minutes, be heated to 375 ℃ ± 5 ℃ with 30 ℃/hour temperature rise rate again, be incubated 2 hours.First rate of temperature fall with 50 ℃/hour is cooled to 315 ℃ in the temperature-fall period, is incubated 30 minutes, naturally cools to room temperature again, gets finished product.This embodiment is applicable to the material of thickness less than 1 centimetre different shape.
Embodiment 2
Polyacrylonitrile powder (granularity 50 μ m) is heated to 370 ℃ in air ambient, and is incubated 2 hours.30% (weight percentage) put into the stirring of high speed agitator the inside through the polyacrylonitrile powder of heat treated and 70% polytetrafluorethylepowder powder (granularity 80 μ m) mixed it in 10 minutes.With mixture compression moulding under 40MPa pressure, room temperature, then the compression moulding part is put into sintering oven again, the temperature rise rate with 40 ℃/hour under air ambient is heated to 375 ℃ ± 5 ℃, is incubated 2 hours; Naturally cool to room temperature then, get finished product.This example is applicable to the product of various size.
Embodiment 3
Polyacrylonitrile powder (granularity 80 μ m) is heated to 370 ℃ of insulations 2 hours in air ambient.50% (weight percentage) put into the stirring of high speed agitator the inside through the polyacrylonitrile powder of heat treated and 50% polytetrafluorethylepowder powder (granularity 120 μ m) mixed it in 10 minutes.Again with mixture in 40MPa pressure, 200 ℃ of following compression mouldings, then the compression moulding part is put into sintering oven, the temperature rise rate with 50 ℃/hour under the air ambient is heated to 315 ℃, is incubated 30 minutes, be heated to 375 ℃ ± 5 ℃ with 30 ℃/hour temperature rise rate again, be incubated 2 hours.First rate of temperature fall with 50 ℃/hour is cooled to 315 ℃ in the temperature-fall period, is incubated 30 minutes, naturally cools to room temperature again, gets finished product.This example is applicable to the product of various size.
Embodiment 4
Polyacrylonitrile powder (granularity 40 μ m) and 50% polytetrafluorethylepowder powder (granularity 150 μ m) and 2%SiO with 45% (weight percentage)
2(granularity 20 μ m) and 3%Al
2O
3(granularity 20 μ m) powder is put into the stirring of high speed agitator the inside mixed it in 10 minutes.Again with mixture in 40MPa pressure, 250 ℃ of following compression mouldings, then the compression moulding part is put into sintering oven, temperature rise rate with 30 ℃/hour under air ambient is heated to 270 ℃, be incubated 30 minutes, be heated to 315 ℃ with 40 ℃/hour temperature rise rate again, be incubated 30 minutes, be heated to 375 ℃ ± 5 ℃ with 30 ℃/hour temperature rise rate again, be incubated 2 hours.Naturally cool to room temperature at last, get finished product.This example is applicable to that thickness is less than 1 centimetre product.
Embodiment 5
Polyacrylonitrile powder (granularity 80 μ m) is heated to 370 ℃ of insulations 2 hours in air ambient.Stirring mixed it in 10 minutes inside 35% (weight percentage) put into high speed agitator through the polyacrylonitrile powder of heat treated and 55% polytetrafluorethylepowder powder (granularity 200 μ m) and 5%SiC (granularity 40 μ m) and 5%ZnO (granularity 40 μ m) powder.Again with mixture in 40MPa pressure, 250 ℃ of following compression mouldings, then the compression moulding part is put into sintering oven, be heated to 375 ℃ ± 5 ℃ at the following temperature rise rate of air ambient with 50 ℃/hour, be incubated 2 hours.First rate of temperature fall with 50 ℃/hour is cooled to 315 ℃ in the temperature-fall period, is incubated 30 minutes, naturally cools to room temperature again, gets finished product.This example is applicable to the product of various size.
Embodiment 6
The Cu powder of the polyacrylonitrile powder (granularity 60 μ m) of 40% (weight percentage) and 58% polytetrafluorethylepowder powder (granularity 100 μ m) and 2% or Fe powder (granularity 10 μ m) are put into the high speed agitator the inside to be stirred and it was mixed in 10 minutes.Again with mixture in 40MPa pressure, 250 ℃ of following compression mouldings, then the compression moulding part is put into sintering oven, temperature rise rate with 100 ℃/hour under air ambient is heated to 270 ℃, be incubated 20 minutes, be heated to 315 ℃ with 40 ℃/hour temperature rise rate again, be incubated 30 minutes, be heated to 375 ℃ ± 5 ℃ with 30 ℃/hour temperature rise rate again, be incubated 2 hours.First rate of temperature fall with 30 ℃/hour is cooled to 315 ℃ in the temperature-fall period, is incubated 30 minutes, naturally cools to room temperature again, gets finished product.This example is applicable to that thickness is less than 1 centimetre product.
Embodiment 7
Polyacrylonitrile powder (granularity 30 μ m) is heated to 370 ℃ of insulations 2 hours in air ambient.46% (weight percentage) put into the stirring of high speed agitator the inside through the polyacrylonitrile powder of heat treated and 50% polytetrafluorethylepowder powder (granularity 70 μ m) and weighting material 4% glass fibre (granularity 10 μ m) mixed it in 10 minutes.Again with mixture in 40MPa pressure, 250 ℃ of following compression mouldings, then the compression moulding part is put into sintering oven, the temperature rise rate with 100 ℃/hour under air ambient is heated to 315 ℃, is incubated 30 minutes, be heated to 375 ℃ ± 5 ℃ with 50 ℃/hour temperature rise rate again, be incubated 2 hours.First rate of temperature fall with 50 ℃/hour is cooled to 315 ℃ in the temperature-fall period, is incubated 30 minutes, naturally cools to room temperature again, gets finished product.This example is applicable to the product of various size.
After testing, more than 7 routine example gained materials compare with pure tetrafluoroethylene, its wear resisting property significantly improves, the raising that has surpass 100 times, heatproof can make product cost reduce 30%-40% up to more than 300 ℃ simultaneously.
Claims (8)
1. a high-wearing polytetrafluoroethylcomposite composite material is characterized in that, it is by after tetrafluoroethylene and the polyacrylonitrile powder mixes, repressed moulding, high temperature sintering form, wherein, the granularity of polytetrafluorethylepowder powder is 30 μ m-200 μ m, and content is 50%-70%; The granularity of polyacrylonitrile powder is 30 μ m-100 μ m, and content is 30%-50%.
2. ptfe composite as claimed in claim 1 is characterized in that, increases in its component that metal and metal oxide powder, its granularity are arranged is 10 μ m-50 μ m, and content is 0%-5%.
3. ptfe composite as claimed in claim 1 is characterized in that, increases in its component that nonmetal oxide, carbide powder, granularity are arranged is granularity 10 μ m-50 μ m, and content is 0%-5%.
4. ptfe composite as claimed in claim 1 is characterized in that, also increases the weighting material that other fiber-like are arranged in its component, and its diameter is 8 μ m-15 μ m, and content is 0%-5%.
5. the preparation method of high-wearing polytetrafluoroethylcomposite composite material as claimed in claim 1 is characterized in that, its preparation process for (1) at first by the mixing of the each component of following calculated amount (being weight percentage) and stir:
Polytetrafluorethylepowder powder (granularity 30 μ m-200 μ m), 50%-70%,
Polyacrylonitrile powder (granularity 30 μ m-100 μ m), 30%-50%,
Nonmetal oxide, carbide (granularity 10 μ m-50 μ m), 0%-5%,
Metal and metal oxide powder (granularity 10 μ m-50 μ m), 0%-5%,
The weighting material of other fiber-like (diameter 8 μ m-15 μ m) 0%-5%.
(2) with compound in coldmoulding under the 40MPa pressure or be lower than under 250 ℃ of conditions hot-formingly, and under 40MPa pressure, kept 5-10 minute;
(3) sample of compression moulding is inserted in the high temperature sintering furnace, be heated to 375 ℃ ± 5 ℃, be incubated 2 hours with 30 ℃-100 ℃/hour temperature rise rates
(4) naturally cool to room temperature, get finished product.
6. preparation method as claimed in claim 5 is characterized in that, described sample with compression moulding is inserted when heating up in the high temperature sintering furnace, and insulation is 1-2 time in being heated to 270 ℃ of-315 ℃ of scopes, each 20-30 minute, and then continue to heat up.
7. preparation method as claimed in claim 5 is characterized in that, describedly will finish agglomerating product when cooling, and insulation is 20-30 minute when being cooled to 315 ℃, and then naturally cools to room temperature,
8. preparation method as claimed in claim 5 is characterized in that, described polyacrylonitrile is that elder generation's pre-oxidation treatment under 370 ℃ of temperature is mixed with polytetrafluorethylepowder powder after 2 hours again.
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| CN103724894A (en) * | 2013-12-12 | 2014-04-16 | 安徽凯特泵业有限公司 | High-temperature resistant polyphenylene ether-modified polytetrafluoroethylene material for pumps and valves |
| CN103756210A (en) * | 2013-12-18 | 2014-04-30 | 安徽南方化工泵业有限公司 | High heat resistant modified polytetrafluoroethylene material for pumps and valves |
| CN103925227A (en) * | 2013-01-15 | 2014-07-16 | 陈存东 | Composite base ceramic pump |
| CN104033639A (en) * | 2013-03-04 | 2014-09-10 | 陈存东 | Composite ceramic valve body |
| CN104723567A (en) * | 2015-02-25 | 2015-06-24 | 中昊晨光化工研究院有限公司 | Forming method for modified polytetrafluoroethylene plastic product |
| CN107474449A (en) * | 2017-07-06 | 2017-12-15 | 无为华兴高分子材料有限公司 | A kind of cheap fluoroplastics of cost |
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| CN116082772A (en) * | 2022-12-05 | 2023-05-09 | 江苏美奥新材料有限公司 | High-temperature-resistant high-strength engineering plastic and preparation method thereof |
| CN116731458A (en) * | 2023-08-16 | 2023-09-12 | 山东森荣新材料股份有限公司 | Polytetrafluoroethylene sealing gasket and preparation method thereof |
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| CN103925227A (en) * | 2013-01-15 | 2014-07-16 | 陈存东 | Composite base ceramic pump |
| CN104033639A (en) * | 2013-03-04 | 2014-09-10 | 陈存东 | Composite ceramic valve body |
| CN103724894A (en) * | 2013-12-12 | 2014-04-16 | 安徽凯特泵业有限公司 | High-temperature resistant polyphenylene ether-modified polytetrafluoroethylene material for pumps and valves |
| CN103724894B (en) * | 2013-12-12 | 2016-01-20 | 安徽凯特泵业有限公司 | The high temperature resistant polyphenyl ether modified polytetrafluoroethylmaterial material of a kind of pump valve |
| CN103756210A (en) * | 2013-12-18 | 2014-04-30 | 安徽南方化工泵业有限公司 | High heat resistant modified polytetrafluoroethylene material for pumps and valves |
| CN104723567A (en) * | 2015-02-25 | 2015-06-24 | 中昊晨光化工研究院有限公司 | Forming method for modified polytetrafluoroethylene plastic product |
| CN107474449A (en) * | 2017-07-06 | 2017-12-15 | 无为华兴高分子材料有限公司 | A kind of cheap fluoroplastics of cost |
| CN111087746A (en) * | 2019-12-23 | 2020-05-01 | 浙江普利特新材料有限公司 | Light low-noise ABS composite material for automobile and preparation method thereof |
| CN114769093A (en) * | 2022-05-05 | 2022-07-22 | 江苏龙山管件有限公司 | Preparation process of wear-resistant pressure-resistant bent pipe |
| CN114769093B (en) * | 2022-05-05 | 2023-08-22 | 江苏龙山管件有限公司 | Preparation process of wear-resistant pressure-resistant bent pipe |
| CN116082772A (en) * | 2022-12-05 | 2023-05-09 | 江苏美奥新材料有限公司 | High-temperature-resistant high-strength engineering plastic and preparation method thereof |
| CN116731458A (en) * | 2023-08-16 | 2023-09-12 | 山东森荣新材料股份有限公司 | Polytetrafluoroethylene sealing gasket and preparation method thereof |
| CN116731458B (en) * | 2023-08-16 | 2023-10-24 | 山东森荣新材料股份有限公司 | Polytetrafluoroethylene sealing gasket and preparation method thereof |
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