CN106397926B - Ultra-high molecular weight polyethylene composite material and preparation method thereof - Google Patents
Ultra-high molecular weight polyethylene composite material and preparation method thereof Download PDFInfo
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- CN106397926B CN106397926B CN201610851208.3A CN201610851208A CN106397926B CN 106397926 B CN106397926 B CN 106397926B CN 201610851208 A CN201610851208 A CN 201610851208A CN 106397926 B CN106397926 B CN 106397926B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
The present invention provides a kind of ultra-high molecular weight polyethylene composite material comprising by molybdenum disulfide and ultra-high molecular weight polyethylene under high-speed flow impact compound obtained product；Wherein, the mass percentage of molybdenum disulfide is 0.5 2.5% in the composite material.The present invention also provides a kind of preparation methods of ultra-high molecular weight polyethylene composite material.The ultra-high molecular weight polyethylene composite material of the present invention has excellent wear resistance, compares pure superhigh molecular weight polyethylene material, and wear rate reduces 34.9%, and friction coefficient reduces 23.3%.The preparation method of the present invention will not cause damages to environment without organic solvent, without any processing aid of addition, simple process and low cost.
Description
Technical field
The present invention relates to polymeric material field, especially a kind of ultra high molecular polyethylene composite material and its preparation side
Method.
Background technology
Ultra-high molecular weight polyethylene (Ultra-high molecular weight polyethylene, UHMWPE) is one
The high molecular polymer of kind line style, molecular weight is usually 1 × 106G/mol or more.Great molecular weight causes intermolecular strong
Mutual winding, bring excellent mechanical property so that it has, and good greasy property, impact resistance, wear-resistant, chemically-resistant is rotten
The performances such as erosion.But compared with Other Engineering plastics, its anti-friction wear resistance is poor, to affect its using effect and application
Range, the filler of generally use addition at present make UHMWPE improve its performance as composite material.
When preparing composite material as matrix using UHMWPE, mixed generally by by UHMWPE, filler and processing aid,
By hot-forming formation composite material.More processing aid is added involved in the preparation process, production and processing cost is higher,
Preparation process is complicated.
Invention content
A kind of the object of the present invention is to provide wear-resisting properties good, the simple ultra high molecular polyethylene composite material of preparation process
And preparation method thereof.
One aspect of the present invention provides a kind of ultra-high molecular weight polyethylene composite material comprising by molybdenum disulfide and superelevation point
Sub- weight northylen compound obtained product under high-speed flow impact；Wherein, in the composite material molybdenum disulfide quality hundred
It is 0.5-2.5% to divide content.
Another aspect of the present invention provides a kind of method preparing above-mentioned composite material, includes the following steps：By molybdenum disulfide
It is compound under high-speed flow impact after being mixed with ultra-high molecular weight polyethylene, obtain composite material.
The ultra-high molecular weight polyethylene composite material of the present invention has excellent wear resistance, compares pure superelevation
Molecular weight polyethylene material, wear rate reduce 34.9%, and friction coefficient reduces 23.3%.The super high molecular weight of the present invention is poly-
The preparation method of ethylene composite material is prepared using high-speed flow impact granule hybrid system, which utilizes high-speed motion
Rotor generate high-speed flow particle driven to do high-speed motion so that particle surface activates, and can make two sulphur in the short time
Change molybdenum and wrap up Ultra high molecular weight polyethylene particles, to form the excellent ultra-high molecular weight polyethylene composite wood of abrasion resistance properties
Material.The preparation method of the present invention will not cause damages to environment without organic solvent, be helped without the processing for adding any
Agent, simple process and low cost.
Description of the drawings
The above-mentioned and/or additional aspect and advantage of the present invention will become in the description from combination following accompanying drawings to embodiment
Obviously and it is readily appreciated that, wherein：
Fig. 1 is the SEM figures of the ultra-high molecular weight polyethylene composite material prepared in the embodiment of the present invention 2.
Fig. 2 is the SEM figures of the ultra-high molecular weight polyethylene composite material prepared in the embodiment of the present invention 3.
Fig. 3 is the SEM figures of the ultra-high molecular weight polyethylene composite material prepared in the embodiment of the present invention 4.
Fig. 4 is the SEM figures of the ultra-high molecular weight polyethylene composite material prepared in the embodiment of the present invention 5.
Fig. 5 is the SEM figures of the ultra-high molecular weight polyethylene composite material prepared in the embodiment of the present invention 6.
Fig. 6 is ultra-high molecular weight polyethylene composite material friction coefficient curve figure prepared by embodiment 1-6.
Fig. 7 is ultra-high molecular weight polyethylene composite material wear rate curve graph prepared by embodiment 1-6.
Fig. 8 is ultra-high molecular weight polyethylene composite material crystallinity curve prepared by embodiment 1-6.
Specific implementation mode
It is special below to lift preferably to allow the preparation method of the ultra-high molecular weight polyethylene composite material of the present invention to be clearer and more comprehensible
Embodiment elaborates, and protection scope of the present invention is not limited by the following examples.The method is equal unless otherwise instructed
For conventional method.The raw material can obtain unless otherwise instructed from open commercial sources.
The present invention provides a kind of ultra-high molecular weight polyethylene composite material comprising is gathered by molybdenum disulfide and super high molecular weight
Ethylene compound obtained product under high-speed flow impact；Wherein, in the composite material molybdenum disulfide mass percentage
For 0.5-2.5%.
Molybdenum disulfide is a kind of common kollag, has good self-lubricating property, with layer structure, interlayer
Binding force is very weak, and interlayer shear easily occurs, and when rubbing with other materials, friction coefficient is low.Molybdenum disulfide is used for superelevation
Molecular weight polyethylene is filled modification, and interlayer structure mutually slides the transfer for being formed and having self-lubricating specific to molybdenum disulfide
Film, transfer membrane effectively reduce the friction coefficient of composite material, reduce abrasive wear.
In an embodiment of the present invention, the mass percentage of molybdenum disulfide is 0.5- in the composite material
2.5%.
In an embodiment of the present invention, the molecular weight of the ultra-high molecular weight polyethylene is 2~3 × 106, average grain
Diameter is 120~150 μm.
In an embodiment of the present invention, described to be complex as molybdenum disulfide and supra polymer under high-speed flow impact
Weight northylen is compound under the rotating speed of 3000-4000r/min.
In an embodiment of the present invention, the wear rate of the composite material is 2.75~4.25 × 1015/m3N-1m-1。
In an embodiment of the present invention, the crystallinity of the composite material is 45-49.5%.
Another aspect of the present invention also provides a kind of method preparing above-mentioned composite material, includes the following steps：By curing
Molybdenum is compound under high-speed flow impact after being mixed with ultra-high molecular weight polyethylene, obtains composite material.
High-speed flow impact method is a kind of method carrying out combined processing to microparticle using dry type, the method for machinery,
This method generates high-speed flow to drive particle to make high-speed motion using the rotor of high-speed motion, and particle is in impact, shear action
Under, input energy is enriched in particle surface, so that particle surface activates.Filler particles are adhered to ultra-high molecular weight polyethylene
The surface of particle can equably complete to wrap up, while can realize the homogenization and grain shape of grain diameter in a short time
Spheroidization.
The deployment conditions of filler be determine ultra-high molecular weight polyethylene composite material friction and wear behavior it is most important because
Element.Compared with common mixed method, high-speed flow impact method only relies on mechanical force in the case where not adding any additive
Effect makes filler generate combination with blapharoplast, and filler forms blapharoplast and coats, and reunites less, under lower loading
It can be achieved with the microcosmic uniform mixing of molybdenum disulfide particles and Ultra high molecular weight polyethylene particles.What therefore prepared by this method is compound
Material be a kind of filler be tightly combined, well dispersed composite material, crack propagation can be effectively hindered in friction process, is had
Conducive to the friction coefficient and wear rate of reduction composite material.
In an embodiment of the present invention, described to be complex as molybdenum disulfide and supra polymer under high-speed flow impact
Weight northylen handles 15-20min under the rotating speed of 3000-4000r/min.
In an embodiment of the present invention, the molybdenum disulfide and the ratio of ultra-high molecular weight polyethylene mixing are 0.5
~2.5：99.5~97.5.
In an embodiment of the present invention, the composite material of the preparation further comprises：Composite material is used into mould
It is molded, obtain composite material sheet.
In an embodiment of the present invention, pressure used by the compression molding is 15-20MPa, pressurizes while rising
Temperature is to 150-180 DEG C, and constant temperature 30-40min, and composite material sheet is obtained after cooling.
In an embodiment of the present invention, the compression molding further includes that composite material is placed in inclined-plane mold,
With the pressure of 15~20Mpa under hot press, composite material sheet is obtained after 150~180 DEG C of hot pressing 30Min, natural cooling,
In, a composite material sheet wherein surface for the formation tilts along unified direction or is parallel to surface, and another surface is inclined
Tilted direction is just opposite.The lower composite material of the unidirectional friction coefficient of single side is prepared by heat pressing process in the present invention.The party
Composite material prepared by method, all exposed curing molybdenum sheets on surface have the consistent tendentiousness in the opposite surface, can make two
Vulcanization molybdenum sheet effectively enhances wearability in composite material surface while reducing friction coefficient.
In an embodiment of the present invention, the composite material is further arranged in hot roller, passes through heat at 180 DEG C
Roller obtains composite material sheet, wherein upper drum rotation speed is 40r/min, and bottom roll rotating speed is 20r/min.The present invention uses
Speed change roll processes, are prepared thinner, curing molybdenum sheet along the higher composite material of the plate surface degree of orientation, prepared
Composite material have lower friction coefficient.
Embodiment 1
By ultra-high molecular weight polyethylene powder at 180 DEG C, 15MPa, hot pressing 30min obtains the poly- second of pure ultra-high molecular mass
Alkene material.
Embodiment 2
It weighs 0.5g molybdenum disulfide powders and high-speed flow impact set composite is added with 99.5g ultra-high molecular weight polyethylenes,
Combined processing 20min is carried out under the rotating speed of 3000r/min, obtains ultra-high molecular weight polyethylene/molybdenum disulfide composite material；It will
For ultra-high molecular weight polyethylene/molybdenum disulfide composite material at 180 DEG C, 15MPa, hot pressing 30min obtains superhigh molecular weight polyethylene
Alkene/molybdenum disulfide composite material.
Embodiment 3
It weighs 1g molybdenum disulfide powders and high-speed flow impact set composite is added with 99g ultra-high molecular weight polyethylenes,
Combined processing 15min is carried out under the rotating speed of 4000r/min, obtains ultra-high molecular weight polyethylene/molybdenum disulfide composite material；It will surpass
For High molecular weight polyethylene/molybdenum disulfide composite material at 150 DEG C, 20MPa, hot pressing 40min obtains superhigh molecular weight polyethylene
Alkene/molybdenum disulfide composite material.
Embodiment 4
It weighs 1.5g molybdenum disulfide powders and high-speed flow impact set composite is added with 98.5g ultra-high molecular weight polyethylenes,
Combined processing 15min is carried out under the rotating speed of 4000r/min, obtains ultra-high molecular weight polyethylene/molybdenum disulfide composite material；It will
For ultra-high molecular weight polyethylene/molybdenum disulfide composite material at 160 DEG C, 19MPa, hot pressing 40min obtains superhigh molecular weight polyethylene
Alkene/molybdenum disulfide composite material.
Embodiment 5
It weighs 2g molybdenum disulfide powders and high-speed flow impact set composite is added with 98g ultra-high molecular weight polyethylenes,
Combined processing 20min is carried out under the rotating speed of 3000r/min, obtains ultra-high molecular weight polyethylene/molybdenum disulfide composite material；It will surpass
For High molecular weight polyethylene/molybdenum disulfide composite material at 170 DEG C, 18MPa, hot pressing 30min obtains superhigh molecular weight polyethylene
Alkene/molybdenum disulfide composite material.
Embodiment 6
It weighs 2.5g molybdenum disulfide powders and high-speed flow impact set composite is added with 97.5g ultra-high molecular weight polyethylenes,
Combined processing 15min is carried out under the rotating speed of 3000r/min, obtains ultra-high molecular weight polyethylene/molybdenum disulfide composite material；It will
For ultra-high molecular weight polyethylene/molybdenum disulfide composite material at 150 DEG C, 17MPa, hot pressing 30min obtains superhigh molecular weight polyethylene
Alkene/molybdenum disulfide composite material.
Embodiment 7
The ultra-high molecular weight polyethylene composite material that complex method preparation will be impacted by high-speed flow is placed in internal diameter and is
In the inclined-plane mold of 25mm, with the pressure of 15~20MPa under hot press, hot pressing 30min at 150~180 DEG C, after natural cooling
Obtain composite material sheet.Wherein, the composite material of a formation wherein surface tilts or is parallel to surface along unified direction,
Another surface inclined direction is just opposite.
Embodiment 8
The ultra-high molecular weight polyethylene composite material of complex method preparation will be impacted by high-speed flow at 120 degrees Celsius
At a temperature of preheat 20min, hot roller is heated to 180 degrees Celsius, wherein upper drum rotation speed is adjusted to 40r/min, bottom roll rotating speed
For 20r/min.By preheated ultra-high molecular weight polyethylene composite material through overheating roller, composite material sheet is obtained, nature
It is cooled and shaped.
Embodiment 9
Above-described embodiment 1-6 ultra-high molecular weight polyethylene composite materials prepared are tested for the property.
Referring to Fig. 1-5, the SEM of ultra-high molecular weight polyethylene composite material schemes Electronic Speculum Shape measure result, Fig. 1-5 generations respectively
Table molybdenum disulfide content is 0.5%, 1%, 1.5%, 2% and 2.5%.It can be seen that from Fig. 1-5 with molybdenum disulfide content
Increase, Ultra high molecular weight polyethylene particles surface becomes coarse from smooth.This illustrates Ultra high molecular weight polyethylene particles surface
It bonds and has inlayed a large amount of molybdenum disulfide lamellas, when molybdenum disulfide content reaches 2.5%, molybdenum disulfide has almost wrapped up superelevation
Molecular weight polyethylene particle surface, as shown in Figure 6.SEM the result shows that under high-speed flow percussion, molybdenum disulfide bond and
It is embedded in Ultra high molecular weight polyethylene particles surface, has reached preferable package effect.
Frictional behaviour test uses the polishing machine of friction and wear test instrument (HSR-2M) test compound material.Pass through test
Instrument measures friction coefficient, measures eroded area cross-sectional area by surface profiler, and calculate wear rate.
Wear rate calculation formula is：
K (m in formula3N-1m-1) it is material wear rate, S is eroded area cross-sectional area, and L is eroded area length, and F is to apply
Load, D is total abrasion distance.
Referring to Fig. 6, friction coefficient curve can be seen that when molybdenum disulfide content is 2.5% from Fig. 6, composite material
Friction coefficient reduce 23.3% than pure ultra-high molecular mass polyethylene.This is because molybdenum disulfide have interlayer structure, by
It can be easily separated between layers because binding force is weak when shear action, the layer of molybdenum-disulfide separated can play good in friction
Self-lubricating function.And good dispersion of the molybdenum disulfide in ultra-high molecular weight polyethylene then ensure that with friction into
Row, molybdenum disulfide is constantly because shear action is to mill material transfer.With the increase of molybdenum disulfide content, this self-lubricating is made
With also more apparent, the transfer membrane formed by shear action is also thicker, therefore friction coefficient can be with the content of molybdenum disulfide
Increase is decreased obviously.
Referring to Fig. 7, from Fig. 7 wear rate curve can be seen that ultra-high molecular weight polyethylene composite material of the present invention with
The increase of molybdenum disulfide content, wear rate reduce.When the content of molybdenum disulfide is 2%, the wear rate of composite material is super than pure
High molecular weight polyethylene material reduces 34.9%.But when content continues to improve, wear rate transfers to rise.This is because
When molybdenum disulfide content is smaller, the presence of transfer membrane can reduce wear rate, but when molybdenum disulfide content is more than 2%, friction
There is thicker transfer membrane in interface, generate a large amount of abrasive dust, and the mixing of ultra-high molecular weight polyethylene/molybdenum disulfide composite material
Abrasive dust hardness is more than pure ultra-high molecular mass polyethylene, plays the role of unstable wear, therefore friction coefficient can be caused to increase.Together
When, when molybdenum disulfide content is excessively high, excessive molybdenum disulfide hinders the combination between Ultra high molecular weight polyethylene particles, causes multiple
It is destructurized between condensation material particle, cause wear rate to increase.
Crystallinity is tested using differential scanning calorimetry.As a result referring to Fig. 8, from Fig. 8 crystallinity curve can be seen that with
The increase of molybdenum disulfide content, the crystallinity of ultra-high molecular weight polyethylene composite material of the present invention also gradually increases, when two sulphur
When change molybdenum content reaches 2%, crystallinity declines instead, this is just the opposite with the wear rate variation tendency of Fig. 7.This illustrates curing
Molybdenum promotes the crosslinking of ultra-high molecular weight polyethylene molecular physics and tangles, but when molybdenum disulfide content is excessively high, preferable to disperse
Effect hinders the combination between Ultra high molecular weight polyethylene particles instead so that crystallinity reduces.Crystallinity reduces so that superelevation
Molecular weight polyethylene amorphous domain area increases, and reduces the mechanical property of composite material, therefore wear rate increases.
The above-described embodiments are merely illustrative of preferred embodiments of the present invention, not to the model of the present invention
It encloses and is defined, under the premise of not departing from design spirit of the present invention, this field ordinary engineering and technical personnel is to the technology of the present invention
The various modifications and improvement that scheme is made should all be fallen into the protection domain of claims of the present invention determination.
Claims (12)
1. a kind of ultra-high molecular weight polyethylene composite material is impacted by molybdenum disulfide and ultra-high molecular weight polyethylene in high-speed flow
Under it is compound obtain product composition；Wherein, the mass percentage of molybdenum disulfide is 0.5-2.5% in the composite material.
2. composite material as described in claim 1, which is characterized in that the quality percentage of molybdenum disulfide contains in the composite material
Amount is 2%.
3. composite material as described in claim 1, which is characterized in that the molecular weight of the ultra-high molecular weight polyethylene is 2~3
×106, average grain diameter is 120~150 μm.
4. composite material as described in claim 1, which is characterized in that described to be complex as curing under high-speed flow impact
Molybdenum is compound under the rotating speed of 3000-4000r/min with ultra-high molecular weight polyethylene.
5. composite material as described in claim 1, which is characterized in that the wear rate of the composite material be 2.75~4.25 ×
1015/m3n-1m-1。
6. composite material as described in claim 1, which is characterized in that the crystallinity of the composite material is 45-49.5%.
7. a kind of method preparing composite material described in claim 1, includes the following steps：By molybdenum disulfide and supra polymer
It is compound under high-speed flow impact after weight northylen mixing, obtain composite material.
8. the method for claim 7, which is characterized in that it is described high-speed flow impact under be complex as by molybdenum disulfide with
Ultra-high molecular weight polyethylene handles 15-20min under the rotating speed of 3000-4000r/min.
9. the method for claim 7, which is characterized in that the ratio of the molybdenum disulfide and ultra-high molecular weight polyethylene mixing
Example is 0.5~2.5：99.5~97.5.
10. the method for claim 7, which is characterized in that by the further compression molding of the composite material, obtain compound
Material sheet, pressure used by the compression molding are 15~20MPa, pressurize while being warming up to 150~180 DEG C, and constant temperature
30~40min obtains composite material sheet after cooling.
11. method as claimed in claim 10, which is characterized in that the compression molding further includes that composite material is placed in inclined-plane
In mold, with the pressure of 15~20Mpa under hot press, composite wood is obtained after 150~180 DEG C of hot pressing 30Min, natural cooling
Media sheet, wherein the composite material sheet of a formation wherein surface tilts along unified direction or is parallel to surface, separately
One surface inclined direction is just opposite.
12. the method for claim 7, which is characterized in that the composite material is further arranged in hot roller, 180
By hot roller at DEG C, composite material sheet is obtained, wherein upper drum rotation speed is 40r/min, and bottom roll rotating speed is 20r/min.
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| CN104592614A (en) * | 2015-01-26 | 2015-05-06 | 清华大学深圳研究生院 | Ultra-high molecular weight polyethylene composite material and preparation method thereof |
| CN105001487A (en) * | 2015-06-29 | 2015-10-28 | 上海化工研究院 | Preparation method of multipurpose injection molding-grade ultrahigh molecular weight polyethylene functional composite materials |
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| KR100454587B1 (en) * | 2001-07-10 | 2004-11-03 | 학교법인고려중앙학원 | Ultra-High Molecular Weight Polyethylene with Carbon Nanotube and Method the Same |
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| CN104592614A (en) * | 2015-01-26 | 2015-05-06 | 清华大学深圳研究生院 | Ultra-high molecular weight polyethylene composite material and preparation method thereof |
| CN105001487A (en) * | 2015-06-29 | 2015-10-28 | 上海化工研究院 | Preparation method of multipurpose injection molding-grade ultrahigh molecular weight polyethylene functional composite materials |
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