CN1817960A - High-abrasion-resistant modified materials of polytetrafluoroethylene and production thereof - Google Patents
High-abrasion-resistant modified materials of polytetrafluoroethylene and production thereof Download PDFInfo
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- CN1817960A CN1817960A CN 200610038328 CN200610038328A CN1817960A CN 1817960 A CN1817960 A CN 1817960A CN 200610038328 CN200610038328 CN 200610038328 CN 200610038328 A CN200610038328 A CN 200610038328A CN 1817960 A CN1817960 A CN 1817960A
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Abstract
A high-abrasive polytetrafluoroethylene modified material and its production are disclosed. The process is carried out by press forming polytetrafluoroethylene, high-temperature sintering, cooling, and ionizing radiating by electron beam or gamma ray. Granularity of polytetrafluoroethylene powder is 30um-200um and radiant dose is 50-400Kgy. Metal, metal oxide powder or non-metal oxide, carbide or other fiber fillers are added. It has fine crystal grain, better abrasive and high-temperature resistant performances and crystallinity degree. It can be used for sealed ring, bearing lining, valve, pipe and pump.
Description
Technical field
The invention belongs to the polymer modification technology, be specifically related to modified materials of polytetrafluoroethyland 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.
In field of polymer technology, be proven technique comparatively thereby utilize the ionizing radiation technology to excite, induce its change of molecular structure to change its physical and chemical performance.Under common situation, polymkeric substance is induced through high-energy radiation, has two kinds of results from structure: the one, and crosslinked, this situation will help improving its physical and chemical performance; The 2nd, cracking, this situation can make its original physical and chemical performance become poorer.Tetrafluoroethylene is considered to typical radiation degradation type superpolymer always, for example, 2003, " the polymkeric substance radiation processing " that Science Press publishes (day, favour three works in the curtain, Xu Jun etc. translate, P158-160)) clearly illustrate that tetrafluoroethylene is that extremely low dosage will cause fatal damage to radiation sensitive polymers very in the book.(Yang Changzheng etc. translate, P71-73) to hold " effect of the miserable superpolymer of ionizing rays " that also have Chinese industrial press of same insight.
1980, " RADIATION EFFECT ON POLYTETRAFLUOROETHYLENE, radiation research and radiation process journal " (1999,1) reported people's such as Sun Jiazhen achievement in research, they are in anaerobic and very narrow temperature range (335 ± 5 ℃)) specified conditions under realized realizing radiation crosslinking through gamma-ray irradiation, promptly successful under the above specified conditions radiation crosslinking tetrafluoroethylene, and obtain state award for inventions; People such as Japanese Akira in 2002 also under the above specified conditions, research radiation crosslinking tetrafluoroethylene, and the mechanical property of cross-linked polytetrafluoroethylthrough tested, when finding with stainless steel to mill, the wear resistance of cross-linked polytetrafluoroethylthrough improves nearly 10000 times of (Akira Setogawa.et.al than pure polytetrafluoroethylene, Development of crossed-linked PTFE and applied products, HITACHI CABLE REVIEW No.21,2002:83-84).So far do not find that under the normal temperature normality high energy particle such as applying electronic bundle carries out radiation to tetrafluoroethylene, the report that its antifriction polishing machine is improved.
Summary of the invention
The objective of the invention is to, at deficiency of the prior art, provide a kind of and under the normal temperature normality, polytetrafluoroethylmaterial material is carried out ionizing rays, thereby obtain the modified materials of polytetrafluoroethyland of high-wearing feature.
Purpose of the present invention realizes in the following manner.
High-abrasion-resistant modified materials of polytetrafluoroethyland of the present invention, it is characterized in that it is by after polytetrafluorethylepowder powder compression moulding, high temperature sintering and the cooling, forms through electron beam or gamma-rays ionizing rays, wherein, the granularity of polytetrafluorethylepowder powder is 30 μ m-200 μ m; Radiation dose when carrying out ionizing rays is 50-400KGy.Also can increase metal or 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, its granularity is 10 μ m-50 μ m, and content is 0%-5% (weight percentage), for example SiO
2, graphite, SiC powder etc.; Can also increase the weighting material of other fiber-like, its diameter is 8 μ m-15 μ m, and content is 0%-15% (weight percentage), for example glass fibre, carbon fiber etc.
Its concrete production technique is as follows: mix polytetrafluorethylepowder powder and each component (1) by 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 anaerobic high temperature sintering furnace, be heated to 375 ℃ ± 5 ℃, be incubated 1-3 hour with 30 ℃ of-120 ° of temperature rise rates of C/ hour; Perhaps in heat-processed, in the time of in being heated to 250 ℃ of-320 ℃ of scopes, be incubated 1-3 time, be incubated 20-30 minute at every turn; (4) naturally cool to room temperature; When perhaps naturally cooling to 315 ± 5 ℃, be incubated 20-30 minute, and then naturally cool to room temperature; (5) tetrafluoroethylene that sinters is placed electron beam irradiation field or gamma-ray irradiation field, carry out ionizing rays, radiation dose 50-400KGy.
The preparation method of high-abrasion-resistant modified materials of polytetrafluoroethyland 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), 85%-100%,
Nonmetal oxide, carbide (granularity 10 μ m-50 μ m), 0%-5%,
Metal or 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%-15%
(2) with the coldmoulding under 40MPa pressure of above-mentioned compound, or be lower than under 250 ℃ of conditions hot-forming 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 1-3 hour with 30 ℃-120 ℃/hour temperature rise rates; Perhaps in its heat-processed, in the time of in being heated to 250 ℃ of-320 ℃ of scopes, be incubated 1-3 time, be incubated 20-30 minute at every turn;
(4) naturally cool to room temperature, when perhaps naturally cooling to 315 ± 5 ℃, be incubated 20-30 minute, and then naturally cool to room temperature, get work in-process;
(5) work in-process that sinter are placed electron beam irradiation field or gamma-ray irradiation field, carry out ionizing rays, radiation dose 50-400KGy gets finished product.
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, graphite, SiC powder, glass fibre, carbon fiber etc. to be to strengthen its corresponding performance, satisfies actual service requirements.
High-abrasion-resistant modified materials of polytetrafluoroethyland of the present invention in the irradiation process, has improved degree of crystallinity, refinement crystal grain, strengthened the Young's modulus of material, increased the friction transfer film at sticking power to the flour milling surface, reduce the generation of new friction transfer film, thereby improved its wear resistance greatly.Actual measurement shows, the material modified radiation modification not compared of the present invention, its wear resistance improves above 100 times, but also has improved thermotolerance and mechanical behavior under high temperature, therefore adopts the material modified product of making of the present invention to use under than the higher temperature of former tetrafluoroethylene.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.
Embodiment
Be further described below by embodiment.
Embodiment 1
(1) 10% (weight percentage) carbon fiber (diameter 10 μ m) and 90% polytetrafluorethylepowder powder (granularity 50 μ m) being put into the stirring of high speed agitator the inside mixed it in 10 minutes.(2) with the compression moulding under 40MPa pressure, room temperature of gained mixture, (3) this compression moulding part is put into sintering oven, temperature rise rate with 100 ℃/hour under the oxygen barrier environment 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 ° of temperature rise rates of C/ hour again, be incubated 30 minutes, be heated to 375 ℃ ± 5 ℃ with 30 ℃/hour temperature rise rate again, be incubated 2 hours.(4) first naturally cooling is cooled to 315 ℃ in the temperature-fall period, is incubated 30 minutes, naturally cools to room temperature again.(5) above-mentioned product is placed the electron beam irradiation field, with the 1.185KGy/ dose rate of second, total radiation dose 200KGy gets finished product.Present embodiment is applicable to the material of thickness less than 1 centimetre different shape.
Embodiment 2
3% (weight percentage) copper powder (the about 60 μ m of granularity), 5% graphite (200 order) are put into the stirring of high speed agitator the inside with 92% 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 the oxygen barrier environment is heated to 375 ℃ ± 5 ℃, is incubated 2 hours; Naturally cool to room temperature then.Sample is placed the electron beam irradiation field, with the 1.05KGy/ dose rate of second, total radiation dose 100KGy gets finished product again.This example is applicable to the surface modification of various size product.
Embodiment 3
With pure polytetrafluorethylepowder powder (granularity 120 μ m) in 40MPa pressure, 120 ℃ of following compression mouldings, then the compression moulding part is put into sintering oven, temperature rise rate with 50 ℃/hour under the secluding air environment is heated to 315 ℃, be incubated 30 minutes, be heated to 375 ℃ ± 5 ℃ with 30 ℃/hour temperature rise rate again, be incubated 2 hours.First naturally cooling is cooled to 315 ℃ in the temperature-fall period, is incubated 30 minutes, naturally cools to room temperature again.At last sample is placed the electron beam irradiation field, with the 0.95KGy/ dose rate of second, total radiation dose 300KGy gets finished product.This example is applicable to the surface modification of various size product.
After testing, more than 3 routine example gained materials with compare without the tetrafluoroethylene that carries out ionizing rays in the radiation field, its wear resisting property all improves and surpasses 100 times, heatproof can be up to more than 300 ℃.
Following table has provided the performance variation situation after the radiation that work in-process among the embodiment 3 use various dose.Can find out that from table along with the increasing of irradiation dose, its wear resisting property also improves thereupon.
| Irradiation dose (KGy) | Average abrasion amount (mm 3) | Unit wear rate * 10 5(mm 3/N-m) | Young's modulus (MPa) |
| 0 | 526.14 | 89.18 | 310.21 |
| 50 | 277.05 | 46.89 | 345.34 |
| 100 | 66.11 | 11.20 | 416.19 |
| 200 | 5.81 | 0.99 | 394.71 |
| 300 | 2.74 | 0.46 | 475.71 |
Claims (9)
1. high-abrasion-resistant modified materials of polytetrafluoroethyland, it is characterized in that it is by after polytetrafluorethylepowder powder compression moulding, high temperature sintering and the cooling, forms through electron beam or gamma-rays ionizing rays, wherein, the granularity of polytetrafluorethylepowder powder is 30 μ m-200 μ m; Radiation dose when carrying out ionizing rays is 50-400KGy.
2. high-abrasion-resistant modified materials of polytetrafluoroethyland as claimed in claim 1 is characterized in that, metal or metal oxide powder are arranged in its component, and its granularity is 10 μ m-50 μ m, and weight percentage is 0%-5%.
3. high-abrasion-resistant modified materials of polytetrafluoroethyland as claimed in claim 1 is characterized in that, nonmetal oxide, carbide are arranged in its component, and its granularity is 10 μ m-50 μ m, and weight percentage is 0%-5%.
4. high-abrasion-resistant modified materials of polytetrafluoroethyland as claimed in claim 1 is characterized in that, the weighting material of other fiber-like is arranged in its component, and its diameter is 8 μ m-15 μ m, and weight percentage is 0%-15%.
5. the preparation method of the described high-abrasion-resistant modified materials of polytetrafluoroethyland of claim 1 is characterized in that, its preparation process is:
(1) at first, the each component by following calculated amount mixes as required, and stirs:
Granularity is the polytetrafluorethylepowder powder of 30 μ m-200 μ m, and weight percentage is 85%-100%,
Granularity is 10 μ m-50 μ m nonmetal oxides, carbide, and weight percentage is 0%-5%,
Granularity is 10 μ m-50 μ m metal or metal oxide powders, and weight percentage is 0%-5%,
Diameter is the weighting material of 8 other fiber-like of μ m-15 μ m, and weight percentage is 0%-15%;
(2) above-mentioned compound was kept 5-10 minute in coldmoulding under the 40MPa pressure and under 40MPa pressure;
(3) sample of compression moulding is inserted in the high temperature sintering furnace, be heated to 375 ℃ ± 5 ℃, be incubated 1-3 hour with 30 ℃-120 ℃/hour temperature rise rates;
(4) naturally cool to room temperature, get work in-process;
(5) work in-process that sinter are placed the electron beam irradiation field, carry out ionizing rays, radiation dose 50-400KGy gets finished product.
6. the preparation method of high-abrasion-resistant modified materials of polytetrafluoroethyland as claimed in claim 5 is characterized in that, described compound be lower than under 250 ℃ of conditions hot-forming and under 40MPa pressure, kept 5-10 minute.
7. the preparation method of high-abrasion-resistant modified materials of polytetrafluoroethyland as claimed in claim 5, it is characterized in that described sample with compression moulding is inserted in the high temperature sintering furnace heat-processed, in the time of in being heated to 250 ℃ of-320 ℃ of scopes, be incubated 1-3 time, be incubated 20-30 minute at every turn.
8. the preparation method of high-abrasion-resistant modified materials of polytetrafluoroethyland as claimed in claim 5 is characterized in that, described sinter when naturally cooling to 315 ± 5 ℃, is incubated 20-30 minute, and then naturally cools to room temperature in process of cooling, gets work in-process.
9. the preparation method of high-abrasion-resistant modified materials of polytetrafluoroethyland as claimed in claim 5 is characterized in that, the described work in-process that sinter place the gamma-ray irradiation field, carry out ionizing rays, and radiation dose 50-400KGy gets finished product.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197084A (en) * | 2008-11-17 | 2011-09-21 | 佛罗里达大学研究基金会公司 | Inert wear resistant fluoropolymer-based solid lubricants, methods of making, and methods of use |
| 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 |
| CN105149357A (en) * | 2015-08-05 | 2015-12-16 | 山东森荣塑业科技有限公司 | Seamless steel tube sizing mill roll sliding plate and preparing method thereof |
| CN105275592A (en) * | 2014-07-18 | 2016-01-27 | 王耀庭 | Method for manufacturing sealing ring of sliding sealing cover of electric-control pressure release valve of gasoline engine pressurizer |
| CN108730383A (en) * | 2017-04-21 | 2018-11-02 | 南京肯特复合材料股份有限公司 | The preparation method of high ferro braking system brake head brake pad |
| CN108784298A (en) * | 2018-06-28 | 2018-11-13 | 浦北县金洋电厨具有限公司 | A kind of preparation method of wear-resisting electric frying pan |
| CN110041646A (en) * | 2018-01-17 | 2019-07-23 | 杨家义 | Ptfe composite, its production method and the inclusion seal circle using the material |
| CN111430594A (en) * | 2020-04-02 | 2020-07-17 | 龙岩高格微扣科技有限公司 | High-temperature-resistant button battery and manufacturing process thereof |
| CN111716853A (en) * | 2020-06-22 | 2020-09-29 | 株洲时代新材料科技股份有限公司 | Wear-resistant heat-insulating composite material and preparation method thereof |
| CN113912968A (en) * | 2021-11-02 | 2022-01-11 | 中国科学院长春应用化学研究所 | Heat-resistant modified PTFE (polytetrafluoroethylene) heat-shrinkable material as well as preparation method and application thereof |
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2006
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102197084A (en) * | 2008-11-17 | 2011-09-21 | 佛罗里达大学研究基金会公司 | Inert wear resistant fluoropolymer-based solid lubricants, methods of making, and methods of use |
| 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 |
| CN105275592A (en) * | 2014-07-18 | 2016-01-27 | 王耀庭 | Method for manufacturing sealing ring of sliding sealing cover of electric-control pressure release valve of gasoline engine pressurizer |
| 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 |
| CN105149357A (en) * | 2015-08-05 | 2015-12-16 | 山东森荣塑业科技有限公司 | Seamless steel tube sizing mill roll sliding plate and preparing method thereof |
| CN108730383A (en) * | 2017-04-21 | 2018-11-02 | 南京肯特复合材料股份有限公司 | The preparation method of high ferro braking system brake head brake pad |
| CN110041646A (en) * | 2018-01-17 | 2019-07-23 | 杨家义 | Ptfe composite, its production method and the inclusion seal circle using the material |
| CN108784298A (en) * | 2018-06-28 | 2018-11-13 | 浦北县金洋电厨具有限公司 | A kind of preparation method of wear-resisting electric frying pan |
| CN111430594A (en) * | 2020-04-02 | 2020-07-17 | 龙岩高格微扣科技有限公司 | High-temperature-resistant button battery and manufacturing process thereof |
| CN111716853A (en) * | 2020-06-22 | 2020-09-29 | 株洲时代新材料科技股份有限公司 | Wear-resistant heat-insulating composite material and preparation method thereof |
| CN113912968A (en) * | 2021-11-02 | 2022-01-11 | 中国科学院长春应用化学研究所 | Heat-resistant modified PTFE (polytetrafluoroethylene) heat-shrinkable material as well as preparation method and application thereof |
| CN113912968B (en) * | 2021-11-02 | 2022-12-20 | 中国科学院长春应用化学研究所 | Heat-resistant modified PTFE (polytetrafluoroethylene) heat-shrinkable material as well as preparation method and application thereof |
| CN115651459A (en) * | 2022-11-09 | 2023-01-31 | 兰州空间技术物理研究所 | Lubricating coating, and preparation method and application thereof |
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