CN1191230A - Method for preparing special material for extrusion and injection grade super-high molecular weight polyethylene - Google Patents
Method for preparing special material for extrusion and injection grade super-high molecular weight polyethylene Download PDFInfo
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- CN1191230A CN1191230A CN98100960A CN98100960A CN1191230A CN 1191230 A CN1191230 A CN 1191230A CN 98100960 A CN98100960 A CN 98100960A CN 98100960 A CN98100960 A CN 98100960A CN 1191230 A CN1191230 A CN 1191230A
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- 238000002347 injection Methods 0.000 title claims abstract description 11
- 239000007924 injection Substances 0.000 title claims abstract description 11
- 238000001125 extrusion Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims description 8
- 239000004705 High-molecular-weight polyethylene Substances 0.000 title claims description 6
- 239000000463 material Substances 0.000 title description 4
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 4
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 4
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 15
- 229920000106 Liquid crystal polymer Polymers 0.000 claims description 12
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 5
- 239000008116 calcium stearate Substances 0.000 claims description 5
- 235000013539 calcium stearate Nutrition 0.000 claims description 5
- 238000007906 compression Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 5
- 238000005453 pelletization Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 abstract description 10
- -1 polyethylene Polymers 0.000 abstract description 8
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract 1
- 239000004973 liquid crystal related substance Substances 0.000 abstract 1
- 238000012545 processing Methods 0.000 description 11
- 238000001746 injection moulding Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 3
- 229920006351 engineering plastic Polymers 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 210000003709 heart valve Anatomy 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000473 propyl gallate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
Abstract
A process for preparing extrusion and injection class of superhigh-molecular polyethylene includes mixing superhigh-molecular polyethylene with high-molecular liquid crystal, antioxidant and additive proportionally, and drying. The flowability of superhigh-molecular polyethylene is greatly improved, so it is possible to manufacture high-quality tubes or other products of superhigh-molecular polyethylene by means of ordinary extruder and injection forming apparatus.
Description
The present invention relates to a kind of preparation method who extrudes with the injection grade super-high molecular weight polyethylene PP Pipe Compound, belong to the forming processing technology field of superpolymer.
Ultrahigh molecular weight polyethylene(UHMWPE) (to call UHMW-PE in the following text) is a kind of thermoplastic engineering plastic of excellent combination property.Low (its kinetic friction coefficient is 0.10~0.22 because of it has outstanding wear resistance (than wear-resisting 8~9 times of iron and steel), excellent in impact resistance (being 2 times of polycarbonate, 5 times of ABS, 15 times of polyoxymethylene), frictional coefficient, can compare favourably with polytetrafluoroethylene, be the ideal lubricant), fabulous advantages such as chemical proofing, lower temperature resistance and noise reduction, thereby worldwide extremely people's favor, its range of application is very extensive.
But since ultrahigh molecular weight polyethylene(UHMWPE) to add the melt viscosity in man-hour high, up to 10
9Pa.s, mobile extreme difference, its melt flow index is almost nil, so be difficult to directly extrude or injection molding.This be because:
(1) viscosity is high during the ultrahigh molecular weight polyethylene(UHMWPE) fusion, does not become viscous state, but is in high viscoelastic attitude.Therefore, on the conventional screw forcing machine, add man-hour, be difficult to advance, rotate together, be absorbed in the state that to extrude, form " material plug " but encase screw rod along screw channel;
(2) frictional coefficient of ultrahigh molecular weight polyethylene(UHMWPE) is extremely low, and powder is very easily skidded in fill process, is difficult for charging;
(3) critical shear rate of ultrahigh molecular weight polyethylene(UHMWPE) is very low, and about 10
-2/ S.When carrying out extrusion moulding, can cause melt fracture, crackle appears in product surface.When carrying out injection molding, cause pore and delamination owing to the injection stream state occurring;
(4) mold temperature narrow range, very easily oxidative degradation.
Because there is above-mentioned processing difficulties in ultrahigh molecular weight polyethylene(UHMWPE), mainly be the sheet material and the bar of simple shape so present processing technology can only adopt intermittent type molding sintering moulding process goods.The forcing machine and the injector of design special construction though abroad begin one's study recently, as its injection pressure of high-voltage high-speed injector of Mitsui company development up to 290Mpa, though can inject small-sized goods, the equipment price costliness, main engine power is very big, the energy consumption height.
The objective of the invention is to study a kind of preparation method who is used to the ultrahigh molecular weight polyethylene(UHMWPE) extruding and inject, adopt a kind of high performance polymer properties-correcting agent and ultrahigh molecular weight polyethylene(UHMWPE) of uniqueness to carry out blend, produce the ultrahigh molecular weight polyethylene(UHMWPE) PP Pipe Compound that directly to extrude and to inject.This PP Pipe Compound is greatly improved the processing fluidity of ultrahigh molecular weight polyethylene(UHMWPE), uses common extruding with injection forming equipment just can extrude or injection molding it easily, to produce high performance ultrahigh molecular weight polyethylene tubing and injection-molded item.
The present invention research extrude preparation method with the injection grade super-high molecular weight polyethylene PP Pipe Compound, comprise the following steps:
(1) with raw material with following weight percent mixing:
Ultrahigh molecular weight polyethylene(UHMWPE): 40~90%
Liquid crystal polymer: 3~50%, granularity is 20 orders~60 orders.
Antioxidant: 0.1~2.5%
Additive: 0.2~5%
(2) said mixture is following dry 3~6 hours at 100~120 ℃;
(3) above-mentioned dried raw material is carried out extruding pelletization, its extrusion temperature is: feeding section: 120~260 ℃, and the compression section: 220~280 ℃, homogenizing zone: 230~300 ℃, outlet: 160~260 ℃.
Extrude or add macromolecule modifier during injection molding at ultrahigh molecular weight polyethylene(UHMWPE), can greatly improve the processing fluidity of ultrahigh molecular weight polyethylene(UHMWPE).Macromolecule modifier used in the present invention is liquid crystal polymer (to call LCP in the following text).It has many outstanding advantages:
(1) You Yi mechanical property can reach 130~260MPa as tensile strength, and is higher 1~3 times than direct labor engineering plastics, is 4 times of PET, and modulus in flexure is 5 times of PET, and notched Izod impact strength can reach 25 times of PET;
(2) outstanding wear resistance, frictional coefficient is little, kinetic friction coefficient is 0.15~0.25, the surface hardness height, and wear loss is low, and wear factor is 1.2 * 10
-5(mm/km)/(kg/cm2), be 1/6000 of PTFE;
(3) minimum linear expansivity than the low order of magnitude of general engineering plastics, is worked as with metal and ceramic phase, near quartzy;
(4) melt viscosity is low, the forming process good fluidity.
Liquid crystal polymer is the main chain polyester type, and its add-on is generally 3%~50% of total amount, and along with the increase of liquid crystal polymer add-on, the melt viscosity index [MI] of system will significantly reduce, and see Table 1.
Melting index during the different proportioning of table 1
LCP/UHMW-PE | ?0/100 | ??3/97 | ??10/90 | ?20/80 | ??30/70 |
MI(g/10min) | ?0 | ??0.010 | ??0.020 | ?8.07 | ??24.74 |
Table is annotated: load 12.5kg, port mould diameter 2.05mm, 260 ℃ of probe temperatures.
The oxidation inhibitor that the present invention added is antioxidant 1010, phenolic antioxidants such as oxidation inhibitor B215, and the amount that is added is generally 0.1%~2.5% of raw material blending ingredients total amount.
The additive that the present invention added is a calcium stearate, and the amount that is added is 0.2%~5% of a raw material blending ingredients.Its effect is the processing fluidity that increases polyethylene special-purpose material, improves the surface smoothness of goods.
Utilize the ultra high molecular polyethylene of method preparation of the present invention, its processing fluidity is greatly improved, and obtains unusual effect.Experimental results show that, the extruding-injection class super-high molecular weight polyethylene PP Pipe Compound that the present invention is prepared, adopt general-purpose equipment just can carry out the forming process of UHMW-PE easily, not only keep higher draw tensile strength and shock strength, and wear resisting property also improves a lot (comparing with pure UHMW-PE), can produce high-performance, high-quality ultra-high molecular weight polyethylene product.Compare with original intermittent type moulding sintering process and can save facility investment, cut down the consumption of energy, shorten the production cycle, enhance productivity, have obvious social and economic benefits.Utilize PP Pipe Compound of the present invention can produce high abrasion plastic pipe (wear resistance is 7~8 times of steel pipe) and be widely used in electric power, waterpower, grain processing, chemical industry, coal, ore dressing field.Originally used steel pipe when carrying the flyash waste residue, because electrochemical reaction is very easily given birth to dirt in the course of conveying as the fuel-burning power plant, just almost stop up through four months pipelines, must clear up, maintenance cost is expensive more than 1,000,000, and wasting time and energy, is hard nut to crack anxious to be solved during power plant produces.Adopt abrasion-proof ultrahigh molecular weight polyethylene tubing, because of not producing electrochemical reaction, and tubing is smooth, and frictional coefficient is very low, is difficult for giving birth to dirt, solves above-mentioned difficulties effectively, can prolong the cleaning maintenance cycle, the saving maintenance cost.In addition, adopt PP Pipe Compound of the present invention can also produce injection-molded item, be used on the textile manufacturing machine picker stick, junctor, sweep line rod, buffer block, eccentric block, rod sleeve, oscillating back rest, gear, cam, picker part etc., the pump housing on the chemical machinery, valve, strainer, bolt, axle sleeve etc., the star wheel on the food machinery, cylinder, sprocket wheel, guide wheel, handle, roller etc.; Medical aspect can be made into heart valve, orthopedics's part, joint prosthesis, artificial bone acetabular bone or the like.
Introduce embodiments of the invention below:
Example 1: with 90 parts of molecular weight X7G liquid crystal polymer and 0.5 part of antioxidant 1010 in the ultrahigh molecular weight polyethylene(UHMWPE) more than 2,000,000 and 10 parts of U.S. Yi Si Man productions, 1 part calcium stearate mixes, dry more than 4 hours under 105 ℃, carry out granulation with single screw rod or twin screw extruder again.Fervent or the pelletizing after water-cooled of batten.Processing condition are as shown in table 2.
Table 2 UHMW-PE PP Pipe Compound extrusion temperature
(I) feeding section (℃) | (II) compression section (℃) | (III) homogenizing zone (℃) | (IV) outlet (℃) |
????180 | ????280 | ????270 | ????200 |
Gained PP Pipe Compound performance: tensile strength 18.9MPa, notched Izod impact strength 25.4kJ/m
2, wear rate 0.32%.
Example 2: with 80 portions of ultrahigh molecular weight polyethylene(UHMWPE)s and 20 parts of LC-5000 liquid crystal polymer and 0.5 part of oxidation inhibitor B215 that Japan outstanding Buddhist nun's contract card company produces, 1 part calcium stearate mixes, dry more than 4 hours under 105 ℃, carry out granulation with single screw rod or twin screw extruder again.Fervent or the pelletizing after water-cooled of batten.Processing condition are as shown in table 3.
Table 3 UHMW-PE PP Pipe Compound extrusion temperature
(I) feeding section (℃) | (II) compression section (℃) | (III) homogenizing zone (℃) | (IV) outlet (℃) |
?????180 | ?????270 | ?????270 | ?????200 |
Gained PP Pipe Compound performance: tensile strength 28.6MPa, notched Izod impact strength 74.6kJ/m
2, wear rate 0.2%.
Example 3: 70 portions of ultrahigh molecular weight polyethylene(UHMWPE)s and 30 parts of Japanese rhizoma sparganic are changed into E310 liquid crystal polymer and 0.2 part of antioxidant 1010 that company produces, 1 part calcium stearate mixes, dry more than 4 hours under 105 ℃, carry out granulation with single screw rod or twin screw extruder again.Fervent or the pelletizing after water-cooled of batten.Processing condition are as shown in table 4.
Table 4 UHMW-PE PP Pipe Compound extrusion temperature
(I) feeding section (℃) | (II) compression section (℃) | (III) homogenizing zone (℃) | (IV) outlet (℃) |
?????180 | ?????260 | ?????270 | ?????200 |
Gained PP Pipe Compound performance: tensile strength 14.3MPa, notched Izod impact strength 20.4kg/m
2, wear rate 0.4%.
Claims (4)
1, a kind of preparation method who extrudes with the injection grade super-high molecular weight polyethylene PP Pipe Compound is characterized in that this method comprises the following steps:
(1) with raw material with following weight percent mixing:
Ultrahigh molecular weight polyethylene(UHMWPE): 40~90%
Liquid crystal polymer: 3~50%, granularity is 20 orders~60 orders
Antioxidant: 0.1~2.5%
Additive: 0.2~5%
(2) said mixture is following dry 3~6 hours at 100~120 ℃;
(3) above-mentioned dried raw material is carried out extruding pelletization, its extrusion temperature is: feeding section: 120~260 ℃, and the compression section: 220~280 ℃, homogenizing zone: 230~300 ℃, outlet: 160~260 ℃.
2: preparation method as claimed in claim 1 is characterized in that wherein said liquid crystal polymer is a main chain polyester type liquid crystal polymer.
3, preparation method as claimed in claim 1 is characterized in that wherein said antioxidant is a phenolic antioxidant.
4, preparation method as claimed in claim 1 is characterized in that wherein said additive is a calcium stearate.
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CN98100960A CN1070888C (en) | 1998-03-27 | 1998-03-27 | Method for preparing special material for extrusion and injection grade super-high molecular weight polyethylene |
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CN98100960A CN1070888C (en) | 1998-03-27 | 1998-03-27 | Method for preparing special material for extrusion and injection grade super-high molecular weight polyethylene |
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CN1191230A true CN1191230A (en) | 1998-08-26 |
CN1070888C CN1070888C (en) | 2001-09-12 |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100422399C (en) * | 2002-04-01 | 2008-10-01 | 闫镇达 | Method for spinning ultra -high strength ultra-high modules polyethylene fibre |
CN101381017B (en) * | 2008-08-05 | 2010-06-09 | 江苏明昊新材料科技有限公司 | Silica gel tank material and method for producing silica gel tank and silica gel tank obtained therefrom |
CN101962820A (en) * | 2010-10-14 | 2011-02-02 | 刘阜东 | Superhigh molecular weight polyethylene monofilament and hot drawing processing method thereof |
CN101519810B (en) * | 2004-01-01 | 2011-04-06 | 帝斯曼知识产权资产管理有限公司 | Method for preparing high-performance polyethylene multifilament yarn |
CN102061029A (en) * | 2010-12-11 | 2011-05-18 | 镇江大洋星鑫工程管道有限公司 | Ultrahigh molecular weight polyethylene tube |
CN102850627A (en) * | 2012-09-10 | 2013-01-02 | 重庆可益荧新材料有限公司 | Injection molding-grade carbon fiber reinforced ultra-high molecular weight polyethylene and preparation method thereof |
CN104884530A (en) * | 2012-12-13 | 2015-09-02 | 瑞来斯实业公司 | Easily processable ultrahigh molecular weight polyethylene and a process for preparation thereof |
CN106279862A (en) * | 2015-05-19 | 2017-01-04 | 镇江荣诚管业有限公司 | A kind of antibacterial pipeline of self-lubricating ultrahigh molecular weight polyethylene abrasion-proof |
CN109280245A (en) * | 2018-09-19 | 2019-01-29 | 茹佰裕 | Modified ultra-high molecular weight polyethylene material and its be used as railroad tie plate |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1039815C (en) * | 1993-11-04 | 1998-09-16 | 成都科技大学 | Method for preparation of uncrimping chain contg. polyethylene |
-
1998
- 1998-03-27 CN CN98100960A patent/CN1070888C/en not_active Expired - Fee Related
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100422399C (en) * | 2002-04-01 | 2008-10-01 | 闫镇达 | Method for spinning ultra -high strength ultra-high modules polyethylene fibre |
CN101519810B (en) * | 2004-01-01 | 2011-04-06 | 帝斯曼知识产权资产管理有限公司 | Method for preparing high-performance polyethylene multifilament yarn |
CN101381017B (en) * | 2008-08-05 | 2010-06-09 | 江苏明昊新材料科技有限公司 | Silica gel tank material and method for producing silica gel tank and silica gel tank obtained therefrom |
CN101962820A (en) * | 2010-10-14 | 2011-02-02 | 刘阜东 | Superhigh molecular weight polyethylene monofilament and hot drawing processing method thereof |
CN102061029A (en) * | 2010-12-11 | 2011-05-18 | 镇江大洋星鑫工程管道有限公司 | Ultrahigh molecular weight polyethylene tube |
CN102850627A (en) * | 2012-09-10 | 2013-01-02 | 重庆可益荧新材料有限公司 | Injection molding-grade carbon fiber reinforced ultra-high molecular weight polyethylene and preparation method thereof |
CN102850627B (en) * | 2012-09-10 | 2014-03-26 | 重庆可益荧新材料有限公司 | Injection molding-grade carbon fiber reinforced ultra-high molecular weight polyethylene and preparation method thereof |
CN104884530A (en) * | 2012-12-13 | 2015-09-02 | 瑞来斯实业公司 | Easily processable ultrahigh molecular weight polyethylene and a process for preparation thereof |
CN104884530B (en) * | 2012-12-13 | 2018-08-14 | 瑞来斯实业公司 | Ultra-high molecular weight polyethylene of easy processing and preparation method thereof |
CN106279862A (en) * | 2015-05-19 | 2017-01-04 | 镇江荣诚管业有限公司 | A kind of antibacterial pipeline of self-lubricating ultrahigh molecular weight polyethylene abrasion-proof |
CN109280245A (en) * | 2018-09-19 | 2019-01-29 | 茹佰裕 | Modified ultra-high molecular weight polyethylene material and its be used as railroad tie plate |
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