CN103613883B - A kind of take Graphene as Wear-resistant hard composite material of filler and preparation method thereof - Google Patents
A kind of take Graphene as Wear-resistant hard composite material of filler and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to field of polymer composite material, particularly a kind of with novel nano carbon material-Graphene Wear-resistant hard composite material that is filler and preparation method thereof.This matrix material is the rigid composite material plate be made up of polymeric matrix and Graphene melt blending, hot pressing, first Graphene is mixed with polymeric matrix and rare-earth stabilizer, block mixture is obtained again with torque rheometer melt blending, obtain hard composite sheet finally by vulcanizing press hot pressing, two-dimensional graphene nano-carbon material content is in the composite 0.1 ~ 3wt%.Be that the polymer matrix composite of filler has the features such as lightweight, easy processing, corrosion-resistant and rub resistance and has a wide range of applications in national defense industry and automotive field with Carbon Materials.The present invention can meet the requirement of the fields such as Aeronautics and Astronautics, automobile, machinery to the more and more higher tribological property of existing high performance polymer composite material, and this composite material preparation process is simple, is easy to realize commercial scale production.
Description
Technical field
The invention belongs to field of polymer composite material, particularly one take novel nano Carbon Materials-Graphene as wear-resistant rigid polymer matrix material of filler and preparation method thereof.
Background technology
Polyvinyl chloride (PVC), as one of four large-engineering materials, is a kind of general-purpose plastics be widely used.Polyvinyl chloride resin has flame retardancy, resist chemical, wear-resisting, the advantage such as good electrical insulation and higher mechanical strength, it can be adopted in the course of processing add additive and additive method produces the plastics meeting various needs, comparatively conventional as electricwire conduit, floor etc.Along with the develop rapidly of the art such as Aeronautics and Astronautics, automobile, machinery, high-performance polymer and matrix material thereof play more and more important role with the tribological property of its excellence: in national defense industry, the deck of warship, the runway of ship-board aircraft etc. need high grade PVC wear-resisting antiskid material in enormous quantities.One of key index of automobile PVC cable material is exactly wear resistance, is directly connected to the life-span of automobile electric wire.And the PVC not adding softening agent belongs to firmly crisp material, it has the susceptibility of height to notched Izod impact strength, especially under metal to-metal contact stressed condition, be easy to the generation of tiny crack and expansion occur under extrusion shearing effect, directly limit the application of PVC in the higher field of these tribological property requirements.Therefore, to improve and the wear resisting property that improves PVC has become one of function modified important development direction of PVC.
In recent years, in order to improve the abrasion resistance properties of PVC, the industrial mode generally adopted is the mode by physical blending, adds the mineral filler such as lignocellulose, glass fibre, and this mode convenient formation, operating procedure are simple.But these inorganic wear resistant filler ubiquity density are large, poor with resin compatible, easy segregation, the shortcomings such as bad dispersibility (ZhangZ, etal.CompositesParta-AppliedScienceandManufacturing, 2004 (35): 1385-1392., ChangL, etal.CompositesScienceandTechnology66, 2006:3188-3198., WangQH, etal.Materials & Design, 210 (31): 3761-3768, XiangDH, etal.JournalofReinforcedPlasticsandComposites, 2007 (26): 331-339.).The distinguishing features such as nano material is large, good with resin compatible with its lightweight, specific surface area, bonding force strong, excellent physical properties more and more cause the extensive concern of people, improve polymkeric substance abrasion resistance properties become study hotspot using nano material as filler.
At present, the filler for rub resistance wear polymer based composites mainly contains rubber elastomer and inorganic wear resistant filler (as: graphite, SiC) etc.But rubber elastomer has the shortcomings such as cost is high, complicated process of preparation, above-mentioned inorganic wear resistant filler then ubiquity density large, poor with resin compatible, easily emanate, the shortcoming such as bad dispersibility.The distinguishing features such as nano material is large, good with resin compatible with its lightweight, specific surface area, bonding force strong, excellent physical properties more and more cause the extensive concern of people, improve polymkeric substance abrasion resistance properties become study hotspot using nano material as filler.
Wherein, the high-performance nano filler being representative with carbon nanotube and graphene oxide achieves remarkable effect (SongHJetal.JournalofNanoparticleResearch in raising polymkeric substance wear resistance etc., 2013 (15): 14331442, ShenXJ, etal, polymer, 2013 (54): 1234-1242, TaiZX, etal, TribologyLetters, 2012 (46): 55-63, PanBL, etal, Wear, 2012 (294): 395-401.).Such as: under DRY SLIDING, graphene oxide (GO) add the tribological property that can strengthen ultrahigh molecular weight polyethylene(UHMWPE) (UHMWPE), very the filling of the GO of low levels significantly can improve the tribological property of epoxy resin nano composites.But improve the abrasion resistance properties of polyvinyl chloride composite materials there is not been reported using Graphene as filler.
Summary of the invention
In order to meet the requirement of existing high performance polymer composite material tribological property more and more higher in the field application such as Aeronautics and Astronautics, automobile, machinery, the object of the invention is to propose a kind of take Graphene as Wear-resistant hard composite material of filler and preparation method thereof, and Graphene can substantially improve polymer composites abrasion resistance properties.
The technical solution used in the present invention is:
Take Graphene as a Wear-resistant hard composite material for filler, described matrix material comprises: Graphene filler, polymeric matrix and auxiliary agent, by weight percentage, Graphene 0.1 ~ 3.0wt%, auxiliary agent 0.5 ~ 10wt%, all the other are polymeric matrix; Wherein, polymeric matrix is thermoplastic granulates shape resin: one or more compounds in polyvinyl chloride, polystyrene, polyester, polyethylene and polypropylene.
Described Graphene preferred content is 0.2 ~ 2.0wt%.
In described matrix material, auxiliary agent is rare-earth stabilizer and acrylate, and by weight percentage, the content of rare-earth stabilizer is 2 ~ 8wt%, acrylate 0.5 ~ 2wt%.
Described worn composite rate scope is (0.50 ~ 1.63) × 10
-5mm
3(Nm)
-1, range of friction coefficients is 0.30 ~ 0.57.
The preparation method of the Wear-resistant hard composite material of filler that described with Graphene is, first, adopt thermoplastic granulates shape resin as polymeric matrix, Graphene is first scattered in matrix resin and mixes, obtain Wear-resistant hard composite material precursor powder; Then through melt blending, then make rigid composite material plate through hot pressing, Heating temperature be 170 ~ 280 DEG C, hot pressing time 8 ~ 15 minutes, pressure 10 ~ 20MPa.
The preparation method of the Wear-resistant hard composite material of filler that described with Graphene is, concrete steps are as follows:
(1) preparation of the dispersed mixture of Graphene and granulated polymer matrix
First rare-earth stabilizer and acrylate are joined in polymeric matrix by proportioning, then under agitation add Graphene, be the mixing machine high-speed stirring 5 ~ 10 minutes of 3000 ~ 8000rpm through rotating speed, obtain Graphene and the uniform powder of mixed with polymers;
(2) above-mentioned powder is joined in torque rheometer, under temperature 150 ~ 280 DEG C, rotating speed 50 ~ 100rpm condition mixing 3 ~ 10 minutes, obtain melting mixture, as Wear-resistant hard composite material presoma;
(3) step (2) is obtained Graphene/polymer melt mixture, press down 8 ~ 15 minutes with vulcanizing press at temperature 170 ~ 280 DEG C, pressure 10 ~ 20MPa, make hard Graphene/polymer composites plate.
The thickness of described hard Graphene/polymer composites plate is 0.5mm ~ 2.5mm.
Described Graphene can be the preparation of intercalation stripping method, graphite oxidation reduction method or additive method.
Design philosophy of the present invention is:
Matrix material of the present invention is the rigid composite material plate be made up of polymeric matrix thermoplastic granulates shape resins such as (as:, granularity is 50 ~ 250 μm) polyvinyl chloride, polystyrene, polyester, polyethylene and polypropylene and Graphene melt blending, hot pressing.First Graphene is mixed with polymkeric substance and rare-earth stabilizer, then obtain block mixture with torque rheometer melt blending, obtain hard composite sheet finally by vulcanizing press hot pressing.Two-dimensional graphene nano-carbon material content is in the composite 0.1 ~ 3wt%.The Graphene of wrapped configuration has the flexibility of high specific surface area and height, can guarantee to form more interface cohesion with polymeric matrix, matrix material is made to need to consume more energy in destructive process, thus contribute to the toughness and the resistance to crack extension ability thereof that improve PVC, and easily viscous deformation occurs in the process engaged with rigidity friction pair in metal to-metal contact slip, thus friction resistance is reduced.Further, the oilness that Graphene self has, also can make this composite material exhibits go out lower frictional force and frictional coefficient, illustrates that Graphene can improve the rub resistance ability of this matrix material.
Advantage of the present invention and beneficial effect are:
1. matrix material of the present invention is that have good abrasion resistance properties, wear rate is higher than pure PVC reduces by 56%, and frictional coefficient can be low to moderate 0.3 by the hard Graphene/polymer composites plate of polymkeric substance and Graphene melt blending, hot pressing.
2. the present invention is using Carbon Materials as the filler of polymer matrix composite, and therefore this matrix material has the features such as lightweight, easy processing, corrosion-resistant and rub resistance, and has a wide range of applications in national defense industry and automotive field.
3. the present invention prepares that the technique of hard Graphene/polymer composites is simple, production efficiency is high, is easy to realize commercial scale production.Meanwhile, the present invention be Graphene batch application indicate direction.
In a word, compared with prior art, the present invention has following advantage, and the technique first preparing matrix material is simple, and does not use poisonous and hazardous chemical reagent, therefore can not to environment.And the present invention proposes to use Graphene filled polymer based composites to improve its wear resistance first.Graphene is compared with other carbon materials, there is excellent mechanical property (Young's modulus is up to 1TPa) and the feature of high-specific surface area, therefore can effectively stop passivation crackle, the final crack growth that stops for destructive cracking, thus enhancing, toughness reinforcing modifying function are played to polymeric matrix, significantly improve the wear resistance of polymkeric substance.
Embodiment
The present invention is by polymer-modified with Graphene, and the Graphene/polymer composites of acquisition possesses higher wear resistance.Wear-resistant hard Graphene/polymer matrix composite sheet material, be characterized in first by Graphene and polymer matrix resin particles solid phase mixing, then make graphene uniform be distributed in polymeric matrix through melt blending, obtain anti abrasive hard Graphene/polymer matrix composite finally by hot-forming.
The preparation method of the anti abrasive hard Graphene/polymer matrix composite of the present invention, its feature comprises following process:
(1) preparation of powder that mixes with polymer matrix resin particles of Graphene
First appropriate rare-earth stabilizer and acrylate are mixed with polymer matrix resin particles, then under agitation slowly add Graphene in batches, through high-speed stirring 5 ~ 10 minutes, obtain the powder that Graphene mixes with polymeric matrix.Wherein, acrylate role is accelerate the plasticizing process of PVC, improves the rheological of PVC fluid and improves the visual appearance etc. of PVC product.
(2) above-mentioned powder is joined in torque rheometer, under temperature 150 ~ 280 DEG C, rotating speed 50 ~ 100rpm condition mixing 3 ~ 10 minutes, obtain melting mixture, as Wear-resistant hard composite material presoma;
(3) step (2) is obtained the block mixture of Graphene/polymeric matrix, within 8 ~ 15 minutes, just can be made into tabular hard Graphene/polymer matrix composite with vulcanizing press hot pressing under temperature 170 ~ 280 DEG C, pressure 10 ~ 20MPa.Described worn composite rate scope is (0.50 ~ 1.63) × 10
-5mm
3(Nm)
-1, range of friction coefficients is 0.30 ~ 0.57.Preferably, described worn composite rate scope is (0.50 ~ 1.20) × 10
-5mm
3(Nm)
-1, range of friction coefficients is 0.30 ~ 0.45.The frictional coefficient of this matrix material under DRY SLIDING is minimum is 0.3, and wear rate is higher than pure PVC reduces by 56%, and such wearability can meet the needs of rigid polymer matrix for high-abrasive material.
In the present invention, rare-earth stabilizer is Novel non-toxic thermo-stabilizer conventional during PVC produces.As: rare-earth stearate, fatty acid rare earth, Whitfield's ointment rare earth, citric acid rare earth, isooctoate of rare earth metal, epoxidation rare earth, mono laurate rare earth, rare earth dilaurate or oxysuccinic acid rare earth etc., its granularity is 200 ~ 500 μm.
The following examples further illustrate of the present invention, instead of limit the scope of the invention.
Embodiment 1
Weigh the polyvinyl chloride (PVC of 69g, mean particle size is about 140 μm), the acrylate (ACR) of 1.03g, the rare-earth stearate stablizer (powder size is about 280 μm) of 4.83g, three is mixed and utilizes homogenizer (rotating speed 5000rpm) to stir, then the graphene powder weighing 0.15g joins in above-mentioned mixed powder and recycles homogenizer (rotating speed 5000rpm) and stir, and finally obtains the powder that Graphene mixes with polymeric matrix.Above-mentioned mixed powder is joined in torque rheometer, is warmed up to 165 DEG C, be under the condition of 60rpm mixing 5 minutes at rotating speed, obtain block compound material.Above-mentioned material is hot-forming on the vulcanizing press being preheating to 185 DEG C, and pressurize 10 minutes under the condition of pressure 15MPa, obtained hard Graphene/PVC composite board, the thickness of this composite panel is 1.0mm.
Sample from sheet material and carry out frictional wear experiment at friction wear testing machine, the wear rate that result records this matrix material is 1.16085 × 10
-5mm
3(Nm)
-1, frictional coefficient is 0.38.
Embodiment 2
The PVC(granularity weighing 69g is about 140 μm), 1.03g ACR, the fatty acid rare earth stablizer (powder size is 350 μm) of 4.83g, three is mixed and utilizes homogenizer (rotating speed 6000rpm) to stir, then the graphene powder weighing 0.828g joins mixed powder and utilizes homogenizer (rotating speed 6000rpm) to stir, and obtains the powder that Graphene mixes with polymeric matrix.Joining in torque rheometer by the mixed powder mixed, be warmed up to 165 DEG C, is under the condition of 60rpm mixing 5 minutes at rotating speed, stop mixing after, block compound material is taken out from torque rheometer and cool to room temperature.Then block compound material is hot-forming on the vulcanizing press being preheating to 185 DEG C, and pressurize 10 minutes under the condition of pressure 15MPa, be cooled to room temperature afterwards, obtained hard Graphene/PVC composite board, the thickness of hard Graphene/polymer matrix composite plate is 1.5mm.
Sample from sheet material and carry out frictional wear experiment at friction wear testing machine, the wear rate that result records this matrix material is 0.71864 × 10
-5mm
3(Nm)
-1, frictional coefficient is 0.46.
Embodiment 3
The PVC(granularity weighing 69g is about 140 μm), 1.03g ACR, the citric acid rare-earth stabilizer (powder size is 300 μm) of 4.83g, three is mixed and utilizes homogenizer (rotating speed 8000rpm) to stir, then the graphene powder weighing 1.38g joins mixed powder and utilizes homogenizer (rotating speed 8000rpm) to stir, and obtains the powder that Graphene mixes with polymeric matrix.Joining in torque rheometer by the mixed powder mixed, be warmed up to 165 DEG C, is carry out mixing 5 minutes under the condition of 60rpm at rotating speed, stop mixing after, block compound material to be taken out from torque rheometer and cool to room temperature.Then block compound material is hot-forming on the vulcanizing press being preheating to 185 DEG C, and pressurize 10 minutes under the condition of pressure 15MPa, be cooled to room temperature afterwards, obtained hard Graphene/PVC composite board, the thickness of hard Graphene/polymer matrix composite plate is 2.0mm.
Sample from sheet material and carry out frictional wear experiment at friction wear testing machine, the wear rate that result records this matrix material is 0.95357 × 10
-5mm
3(Nm)
-1, frictional coefficient is 0.43.
Embodiment 4
Weigh the polystyrene (PS of 70g, granularity is about 150 μm), the acrylate (ACR) of 1.25g, the rare-earth stearate stablizer (powder size is 200 μm) of 4.30g, three is mixed and utilizes homogenizer (rotating speed 5000rpm) to stir, then the graphene powder weighing 0.45g joins mixed powder and utilizes homogenizer (rotating speed 5000rpm) to stir, and obtains the powder that Graphene mixes with polymeric matrix.Joining in torque rheometer by the mixed powder mixed, be warmed up to 245 DEG C, is under the condition of 90rpm mixing 6 minutes at rotating speed.Stop mixing after, block compound material to be taken out from torque rheometer and cool to room temperature.Then block compound material is hot-forming on the vulcanizing press being preheating to 245 DEG C, and pressurize 8 minutes under the condition of pressure 16MPa, be cooled to room temperature afterwards, obtained hard Graphene/PVC composite board, the thickness of hard Graphene/polymer matrix composite plate is 1.0mm.
Sample from sheet material and carry out frictional wear experiment at friction wear testing machine, the wear rate that result records this matrix material is 1.17052 × 10
-5mm
3(Nm)
-1, frictional coefficient is 0.41.
Embodiment 5
Weigh the polyethylene terephthalate (PET of 70g, granularity is about 170 μm), 1.16g ACR, the fatty acid rare earth stablizer (powder size is 400 μm) of 3.75g, three is mixed and utilizes homogenizer (rotating speed 6000rpm) to stir, then the graphene powder weighing 1.09g joins mixed powder and utilizes homogenizer (rotating speed 6000rpm) to stir, and obtains the powder that Graphene mixes with polymeric matrix.Joining in torque rheometer by the mixed powder mixed, be warmed up to 260 DEG C, is carry out mixing 8 minutes under the condition of 80rpm at rotating speed, stop mixing after, block compound material to be taken out from torque rheometer and cool to room temperature.Then block compound material is hot-forming on the vulcanizing press being preheating to 260 DEG C, and pressurize 12 minutes under the condition of pressure 10MPa, be cooled to room temperature afterwards, obtained hard Graphene/PVC composite board, the thickness of hard Graphene/polymer matrix composite plate is 2.5mm.
Sample from sheet material and carry out frictional wear experiment at friction wear testing machine, the wear rate that result records this matrix material is 0.91884 × 10
-5mm
3(Nm)
-1, frictional coefficient is 0.49.
Embodiment 6
Weigh the polypropylene (PP of 70g, granularity is about 160 μm), the ACR of 0.38g, the citric acid rare-earth stabilizer (powder size is about 200 μm) of 4.05g, three is mixed and utilizes homogenizer (rotating speed 8000rpm) to stir, then the graphene powder weighing 0.57g joins mixed powder and utilizes homogenizer (rotating speed 8000rpm) to stir, and obtains the powder that Graphene mixes with polymeric matrix.Joining in torque rheometer by the mixed powder mixed, be warmed up to 170 DEG C, is carry out mixing 10 minutes under the condition of 70rpm at rotating speed, stop mixing after, block compound material to be taken out from torque rheometer and cool to room temperature.Then block compound material is hot-forming on the vulcanizing press being preheating to 170 DEG C, and pressurize 15 minutes under the condition of pressure 12MPa, be cooled to room temperature afterwards, obtained hard Graphene/PVC composite board, the thickness of hard Graphene/polymer matrix composite plate is 2.0mm.
Sample from sheet material and carry out frictional wear experiment at friction wear testing machine, the wear rate that result records this matrix material is 0.96241 × 10
-5mm
3(Nm)
-1, frictional coefficient is 0.41.
Comparative example 1
Weigh the PVC powder of 69g, 1.03g ACR, the rare-earth stabilizer (and by rare-earth stabilizer grind into powder of sheet) of 4.83g, three is mixed and utilizes homogenizer (rotating speed 5000rpm) to mix, then the mixed powder mixed is joined in torque rheometer, being warmed up to 165 DEG C, is carry out mixed refining process 5 minutes under the condition of 60rpm at rotating speed.Mixing complete after, block compound material to be taken out from torque rheometer and cool to room temperature.Then block compound material is hot-forming on the vulcanizing press being preheating to 185 DEG C, pressurize 10 minutes under the condition of pressure 15MPa, the obtained pure PVC composite board of hard.Sample from sheet material and carry out frictional wear experiment at friction wear testing machine, the wear rate that result records this matrix material is 1.62039 × 10
-5mm
3(Nm)
-1, frictional coefficient is about 0.56.
Embodiment and comparative example show, the present invention take Graphene as the new complex method that rigid polymer based composites prepared by filler, Graphene is first mixed through high-speed stirring with polymeric matrix, then mixed powder is used torque rheometer melt blending, finally the matrix material block after melt blending is made composite board through vulcanizing press hot pressing.The frictional coefficient of above-mentioned composite board under DRY SLIDING is minimum is 0.3, and wear rate is higher than pure PVC reduces by 56%.This composite material preparation process is simple, is applicable to commercial scale production.
Claims (6)
1. be a Wear-resistant hard composite material for filler with Graphene, it is characterized in that, described matrix material comprises: Graphene filler, polymeric matrix and auxiliary agent, by weight percentage, Graphene 0.1 ~ 3.0wt%, auxiliary agent 0.5 ~ 10wt%, all the other are polymeric matrix; Wherein, polymeric matrix is thermoplastic granulates shape resin: one or more compounds in polyvinyl chloride, polystyrene, polyester, polyethylene and polypropylene;
In described matrix material, auxiliary agent is rare-earth stabilizer and acrylate, and by weight percentage, the content of rare-earth stabilizer is 2 ~ 8wt%, acrylate 0.5 ~ 2wt%;
Described worn composite rate scope is (0.50 ~ 1.63) × 10
-5mm
3(Nm)
-1, range of friction coefficients is 0.30 ~ 0.57.
2. according to according to claim 1 take Graphene as the Wear-resistant hard composite material of filler, it is characterized in that, described Graphene preferred content is 0.2 ~ 2.0wt%.
3. one kind according to claim 1 take Graphene as the preparation method of the Wear-resistant hard composite material of filler, it is characterized in that, first, adopt thermoplastic granulates shape resin as polymeric matrix, then rare-earth stabilizer and acrylate are joined in polymeric matrix by proportioning, under agitation add Graphene, obtain Wear-resistant hard composite material precursor powder; Then through melt blending, then make rigid composite material plate through hot pressing, Heating temperature be 170 ~ 280 DEG C, hot pressing time 8 ~ 15 minutes, pressure 10 ~ 20MPa.
4. according to according to claim 3 take Graphene as the preparation method of the Wear-resistant hard composite material of filler, it is characterized in that, concrete steps are as follows:
(1) preparation of the dispersed mixture of Graphene and granulated polymer matrix
First rare-earth stabilizer and acrylate are joined in polymeric matrix by proportioning, then under agitation add Graphene, be the mixing machine high-speed stirring 5 ~ 10 minutes of 3000 ~ 8000rpm through rotating speed, obtain Graphene and the uniform powder of mixed with polymers;
(2) above-mentioned powder is joined in torque rheometer, under temperature 150 ~ 280 DEG C, rotating speed 50 ~ 100rpm condition mixing 3 ~ 10 minutes, obtain melting mixture, as Wear-resistant hard composite material presoma;
(3) step (2) is obtained Graphene/polymer melt mixture, press down 8 ~ 15 minutes with vulcanizing press at temperature 170 ~ 280 DEG C, pressure 10 ~ 20MPa, make hard Graphene/polymer composites plate.
5. according to according to claim 3 take Graphene as the preparation method of the Wear-resistant hard composite material of filler, it is characterized in that, the thickness of hard Graphene/polymer composites plate is 0.5mm ~ 2.5mm.
6. according to according to claim 3 take Graphene as the preparation method of the Wear-resistant hard composite material of filler, it is characterized in that, described Graphene can be the preparation of intercalation stripping method, graphite oxidation reduction method or additive method.
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