CN103319898A - Micro-nano lamellar boron nitride/rubber composite material and preparation method thereof - Google Patents
Micro-nano lamellar boron nitride/rubber composite material and preparation method thereof Download PDFInfo
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- CN103319898A CN103319898A CN2013102537331A CN201310253733A CN103319898A CN 103319898 A CN103319898 A CN 103319898A CN 2013102537331 A CN2013102537331 A CN 2013102537331A CN 201310253733 A CN201310253733 A CN 201310253733A CN 103319898 A CN103319898 A CN 103319898A
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 239
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 236
- 229920001971 elastomer Polymers 0.000 title claims abstract description 66
- 239000005060 rubber Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920002379 silicone rubber Polymers 0.000 claims abstract description 62
- 238000002156 mixing Methods 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 241000446313 Lamella Species 0.000 claims description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000013543 active substance Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000005189 flocculation Methods 0.000 claims description 9
- 230000016615 flocculation Effects 0.000 claims description 9
- NRHMKIHPTBHXPF-TUJRSCDTSA-M sodium cholate Chemical compound [Na+].C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC([O-])=O)C)[C@@]2(C)[C@@H](O)C1 NRHMKIHPTBHXPF-TUJRSCDTSA-M 0.000 claims description 9
- 235000011149 sulphuric acid Nutrition 0.000 claims description 9
- 239000001117 sulphuric acid Substances 0.000 claims description 9
- BQFCCCIRTOLPEF-UHFFFAOYSA-N chembl1976978 Chemical compound CC1=CC=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 BQFCCCIRTOLPEF-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000000975 co-precipitation Methods 0.000 claims description 6
- 229920000126 latex Polymers 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 4
- 239000004816 latex Substances 0.000 claims description 4
- 238000005987 sulfurization reaction Methods 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 230000003712 anti-aging effect Effects 0.000 claims description 2
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000011049 filling Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 230000017525 heat dissipation Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 52
- 238000005303 weighing Methods 0.000 description 45
- 239000000523 sample Substances 0.000 description 34
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 22
- 238000000748 compression moulding Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000002604 ultrasonography Methods 0.000 description 16
- 229920001206 natural gum Polymers 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 239000003963 antioxidant agent Substances 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 10
- 235000006708 antioxidants Nutrition 0.000 description 10
- 229920006173 natural rubber latex Polymers 0.000 description 10
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 9
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000013536 elastomeric material Substances 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229920002449 FKM Polymers 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 5
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 229920013649 Paracril Polymers 0.000 description 5
- 229920003052 natural elastomer Polymers 0.000 description 5
- 229920001194 natural rubber Polymers 0.000 description 5
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
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- 125000004429 atom Chemical group 0.000 description 3
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 238000005411 Van der Waals force Methods 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
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Abstract
The invention provides a micro-nano lamellar boron nitride/rubber composite material and a preparation method thereof. The preparation method comprises the following steps of: 1, placing a micrometer lamellar boron nitride raw material into a solvent, and ultrasonically stripping to prepare nanometer lamellar boron nitride; 2, mixing obtained nanometer lamellar boron nitride and the micrometer lamellar boron nitride raw material with rubber in proportion, adding a vulcanizing agent, and uniformly mixing to prepare a rubber compound; 3, vulcanizing the boron nitride/rubber rubber compound to obtain a high heat-conducting silicon rubber product. The micrometer lamellar boron nitride is difficult to aggregate and mainly plays a bridge overlapping role in the rubber, and the prepared boron nitride in a nanometer lamellar structure theoretically achieves the heat conductivity far more than that of common boron nitride. The boron nitride heat-conducting rubber prepared through the method provided by the invention has higher heat-conducting property under less filling parts and can be widely applied to positions which need heat dissipation and heat transfer in the fields of spaceflight, avigation, electron and electric appliances.
Description
Technical field
The present invention proposes a kind of preparation method and application of hexagonal nano lamella boron nitride, it mixes matrix material that the filled rubber matrix prepares and possesses higher heat conductivility with the micron boron nitride, can be widely used in needs the position of dispelling the heat and conducting heat for space flight, aviation, electronics, appliance field.
Background technology
Behind the twentieth century, entered the great development stage as the elastomeric material of the fourth-largest strategic resource, compared the materials such as traditional metal, pottery, elastomeric material has the characteristics such as light weight, high visco-elasticity, resistance to chemical attack, easily machine-shaping, anti-fatigue performance be good.But elastomeric material mostly is the poor conductor of heat, makes it need the application on the good product of thermal conductivity to be restricted.
At present, the filler that improves the elastomeric material thermal conductivity mostly is metal, metal oxide, and nonmetal such as graphite, carbon black etc., the matrix material of making does not thus have good electrical insulation capability, perhaps because the filling umber of filler is larger, so that other degradation of matrix material, product performance are undesirable.Hexagonal boron nitride (h-BN) is known as white graphite, belongs to the III-V compounds of group, and hexagonal system has the laminate structure of similar graphite.Its lattice parameter is a=0.2504nm, c=0.6652nm.In addition, the same with graphite, every one deck of h-BN forms plane hexagonal ring shape structure by B atom and N atom, and along the C direction of principal axis, each layer atom pressed ABAB ... mode is arranged.The interlayer of h-BN is by the Van der Waals force combination, and the B atom in the layer, the covalent bonds of N atom are together.Although the layer inner structure of h-BN is very stable, but easily slide between layers, peel off, it can be peeled off into the boron nitride of monolithic layer or several lamellas, in theory, thermal conductivity can reach 2000W/mk in the plane of nm-class boron nitride sheet layer material, has exceeded the thermal conductivity of 300W/mk in the common boron nitride plane far away.And, compare with traditional heat conductive filler, h-BN also have many excellences characteristic such as anti-oxidant, high temperature resistant, thermal conductivity is high and chemical stability is high, the coefficient of expansion is low and frictional coefficient is low, processability good, it has clear superiority at aspects such as improving the mechanical behavior under high temperature of rubber-base composite material, thermostability, oxidation-resistance.
That the present invention relates to is a kind of preparation method of simple boron nitride/rubber composite newly, be will preparation the large nanoscale twins boron nitride of flakiness ratio and micron lamella boron nitride blending dispersion in rubber matrix, can reduce the consumption of boron nitride filler, form preferably heat conduction network, greatly improve the thermal conductivity of elastomeric material.
Summary of the invention
Purpose of the present invention: prepare the large nanoscale twins boron nitride of flakiness ratio, and with it with micron lamella boron nitride filled rubber material.Compare with traditional heat conductive filler, select micron and nanoscale twins boron nitride mixed fillers, because micron lamella boron nitride is difficult for reuniting, the main bridge snap action that rises in rubber matrix, and the boron nitride of the nano-lamellar structure that makes has the thermal conductivity that surpasses common boron nitride far away, and compares with micron lamella boron nitride and to have larger flakiness ratio, under identical filling umber, can obtain more effective heat conduction network, thereby prepare the silicon rubber composite material of high heat conduction.The method can with less heat conductive filler umber, improve the heat conductivility of elastomeric material.
A kind of micron and nanoscale twins boron nitride are mixed the preparation method of filled rubber, it is characterized in that: rubber raw materials is dried glue or emulsion form, the rubber parts by weight are 100 parts, and total boron nitride parts by weight are 50-100 part, and wherein the mass ratio of micron boron nitride and nm-class boron nitride is 1:9-9:1;
The dried glue of raw material choose:
Micron lamella boron nitride is placed solvent orange 2 A, being made into concentration is 1mg/ml-6mg/ml suspension, the ultrasonic thickness that obtains is below 10nm, flakiness ratio is the nanoscale twins boron nitride of 50-300, obtain rubber solutions with the solvent orange 2 A dissolving rubber, micron lamella boron nitride, nanoscale twins boron nitride and rubber solutions are mixed; Then evaporating solvent A; Or pour among the solvent B, this solvent B is 5-15 times of solvent orange 2 A volume, dissolves each other with solvent orange 2 A, and not sol rubber and boron nitride, make rubber and boron nitride coprecipitation out; By mixing in mill, Banbury mixer or screw extrusion press, add therein the vulcanizing agent DCP of 1wt% again, make micro-nano lamella boron nitride/silicon rubber composite material after the sulfuration;
Raw material choose latex:
Micron lamella boron nitride placed contain the deionized water that the tensio-active agent Sodium cholic acid is 0.05wt%-1wt%, being made into concentration is 1mg/ml-6mg/ml suspension, the ultrasonic thickness that obtains is below 10nm, flakiness ratio is the nanoscale twins boron nitride of 50-300, after mixing with micron lamella boron nitride, rubber latex again, dilute sulphuric acid flocculation with 1wt%, dry, in mixing roll, add the Synergist S-421 95 that comprises at least zinc oxide, stearic acid, promotor, anti-aging agent, sulphur mixing evenly, obtain micro-nano lamella boron nitride/rubber composite after the sulfuration.
Further, used solvent is alcohol, ketone, alkane or tetrahydrofuran (THF).
Further, ultrasonic power is 200-1500W, and ultrasonic time is 2-12h, and the flakiness ratio of the nanoscale twins boron nitride of acquisition is 50-250.
Further, the mass ratio of micron lamella boron nitride and prepared nanoscale twins boron nitride is 3:7-5:5.
Further, the mass ratio of micron lamella boron nitride and prepared nanoscale twins boron nitride is 3:7.
Micro-nano boron nitride/the rubber composite of the present invention's preparation can select different elastomeric materials to do matrix according to the difference of purposes.Goods can be selected different rubber matrixs according to the difference (such as temperature, pressure, the solvent that contacts etc.) of environment for use.Make film, sheet material, sheet material etc. according to the difference of using needs.
The micro-nano lamella boron nitride/rubber composite of the present invention preparation can be used for space flight, aviation, electronics, appliance field and need the position of dispelling the heat and conducting heat, can reach and reduce thermal contact resistance between the interface, and have good processing characteristics, toughness and higher mechanical property, so that the requirement of the minim gap between filling interface.
Description of drawings
Fig. 1: the SEM of raw material six side's lamella boron nitride
Fig. 2: the TEM of nanoscale twins boron nitride
Fig. 3: it is 3.6nm that the AFM(of nm-class boron nitride characterizes thickness, and flakiness ratio is 287)
Fig. 4 a: the HR-TEM of micro-nano lamella boron nitride/silicon rubber composite material section (embodiment 1); Fig. 4 b: the HR-TEM of micro-nano lamella boron nitride/native rubber composite material section (embodiment 11)
Below in conjunction with embodiment effect of the present invention is described further.
Embodiment
Embodiment 1: 100 parts in silicon rubber, 1 part of micron lamella boron nitride, 9 parts of nanoscale twins boron nitride, preparation micro-nano lamella boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 1g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1000ml propanol solution, carry out ultrasonic with ultrasonic instrument, ultrasonic power 200W, ultrasonic time is 12h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/propanol suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml propanol solution, 75 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 0.1g micron lamella boron nitride joins in the propanol solution of having dissolved silicon rubber with the propanol solution that contains 0.9g nanoscale twins boron nitride and mixes, behind the evaporating solvent, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned over again in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=1:9) boron nitride quality per-cent is the heat-conducting silicon rubber finished product of 9.1wt% to obtain micro-nano.
Embodiment 2: 100 parts in silicon rubber, 90 parts of micron lamella boron nitride, 10 parts of nanoscale twins boron nitride, preparation micro-nano lamella boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 2500ml propanol solution, carry out ultrasonic with ultrasonic instrument, ultrasonic power 1000W, ultrasonic time is 3h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/propanol suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml propanol solution, 75 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 9g micron lamella boron nitride joins in the propanol solution of having dissolved silicon rubber with the propanol solution that contains 1g nanoscale twins boron nitride and mixes, behind the evaporating solvent, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned over again in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=9:1) boron nitride quality per-cent is 50wt% heat-conducting silicon rubber finished product to obtain micro-nano.
Embodiment 3: 100 parts in silicon rubber, 20 parts of micron lamella boron nitride, 80 parts of nanoscale twins boron nitride, preparation micro-nano lamella boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 2000ml acetone soln, carry out ultrasonic with ultrasound probe, ultrasonic power 1500W, ultrasonic time is 2h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/acetone suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml acetone soln, 35 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 2g micron lamella boron nitride joins in the acetone soln that has dissolved silicon rubber with the acetone soln that contains 8g nanoscale twins boron nitride and mixes, behind the evaporating solvent, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned over again in the rubber mold, pressure exhaust in the compression molding instrument, pressure is 100kg/cm2, temperature is 150 ℃, suppress after 10 minutes, mould is taken out the taking-up sample, and (mass ratio=2:8) boron nitride quality per-cent is the heat-conducting silicon rubber finished product of 50wt% to obtain micro-nano.
Embodiment 4: 100 parts in silicon rubber, 40 parts of micron lamella boron nitride, 60 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml tetrahydrofuran solution, carry out ultrasonic with ultrasound probe, ultrasonic power 800W, ultrasonic time is 6h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/tetrahydrofuran (THF) suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml tetrahydrofuran solution, 75 ℃ of stirring and dissolving of heating in water bath.Take by weighing 4g micron lamella boron nitride with the tetrahydrofuran solution that contains 6g nanoscale twins boron nitride join mix in the tetrahydrofuran solution that has dissolved silicon rubber after, mixture is poured in the 8L water, at the uniform velocity stir, because tetrahydrofuran (THF) and water dissolve each other, and silicon rubber and boron nitride are all water insoluble, when the ratio of water during considerably beyond the ratio of tetrahydrofuran (THF), silicon rubber and boron nitride coprecipitation are out, obtain boron nitride/silicon rubber composite material, to be dried after, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm again
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=4:6) boron nitride quality per-cent is the heat-conducting silicon rubber finished product of 50wt% to obtain micro-nano.
Embodiment 5: 100 parts in silicon rubber, 12 parts of micron lamella boron nitride, 28 parts of nanoscale twins boron nitride nitrogen boron, preparation micro-nano boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml acetone soln, carry out ultrasonic with ultrasound probe, ultrasonic power 900W, ultrasonic time is 7h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/acetone suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml acetone soln, 75 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 1.2 microns boron nitride joins in the acetone soln that has dissolved silicon rubber with the acetone soln that contains the 2.8g nm-class boron nitride and mixes, mixture is poured in the 8L water, at the uniform velocity stir, because acetone and water dissolve each other, and silicon rubber and boron nitride are all water insoluble, when the ratio of water during considerably beyond the ratio of acetone, silicon rubber and boron nitride coprecipitation are out, obtain boron nitride/silicon rubber composite material, to be dried after, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm again
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=3:7) boron nitride quality per-cent is the heat-conducting silicon rubber finished product of 28.6wt% to obtain micro-nano.
Embodiment 6: 100 parts in silicon rubber, 15 parts of micron lamellas, 35 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml acetone soln, carry out ultrasonic with ultrasound probe, ultrasonic power 1400W, ultrasonic time is 2.5h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/acetone suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml acetone soln, 75 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 1.5g micron lamella boron nitride joins in the acetone soln that has dissolved silicon rubber with the acetone soln that contains 3.5g nanoscale twins boron nitride and mixes, mixture is poured in the 10L water, at the uniform velocity stir, because acetone and water dissolve each other, and silicon rubber and boron nitride are all water insoluble, when the ratio of water during considerably beyond the ratio of acetone, silicon rubber and boron nitride coprecipitation are out, obtain boron nitride/silicon rubber composite material, to be dried after, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm again
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=3:7) boron nitride quality per-cent is the heat-conducting silicon rubber finished product of 33.3wt% to obtain micro-nano.
Embodiment 7: 100 parts in silicon rubber, 18 parts of micron lamella boron nitride, 42 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1900ml propanol solution, carry out ultrasonic with ultrasound probe, ultrasonic power 1000W, ultrasonic time is 5h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/propanol suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml propanol solution, 75 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 1.8g micron lamella boron nitride joins in the propanol solution of having dissolved silicon rubber with the propanol solution that contains 4.2g nanoscale twins boron nitride and mixes, behind the evaporating solvent, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned over again in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=3:7) boron nitride quality per-cent is the heat-conducting silicon rubber finished product of 37.5wt% to obtain micro-nano.
Embodiment 8: 100 parts in silicon rubber, 24 parts of micron lamella boron nitride, 56 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml propanol solution, carry out ultrasonic with ultrasound probe, ultrasonic power 1200W, ultrasonic time is 3h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/propanol suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml propanol solution, 75 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 2.4g micron lamella boron nitride joins in the propanol solution of having dissolved silicon rubber with the propanol solution that contains 5.6g nanoscale twins boron nitride and mixes, behind the evaporating solvent, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned over again in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=3:7) boron nitride quality per-cent is the heat-conducting silicon rubber finished product of 44.4wt% to obtain micro-nano.
Embodiment 9: 100 parts in silicon rubber, 30 parts of micron lamella boron nitride, 70 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/silicon rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml acetone soln, carry out ultrasonic with ultrasound probe, ultrasonic power 600W, ultrasonic time is 10h, obtains thickness below 10nm, and flakiness ratio is the nanoscale twins boron nitride/acetone suspension between the 50-300.
Composite manufacture: take by weighing 10g silicon rubber and join in the 400ml acetone soln, 75 ℃ of stirring and dissolving of heating in water bath.Taking by weighing 3g micron lamella boron nitride joins in the acetone soln that has dissolved silicon rubber with the acetone soln that contains 7g nanoscale twins boron nitride and mixes, mixture is poured in the 10L water, at the uniform velocity stir, because acetone and water dissolve each other, and silicon rubber and boron nitride are all water insoluble, when the ratio of water during considerably beyond the ratio of acetone, silicon rubber and boron nitride coprecipitation are out, obtain boron nitride/silicon rubber composite material, to be dried after, in mixing roll, add 0.1g vulcanizing agent (DCP), mixing even, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm again
2, temperature is 150 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=3:7) boron nitride per-cent is the heat-conducting silicon rubber finished product of 50wt% to obtain micro-nano.
Embodiment 10: 100 parts of natural rubbers, 4 parts of micron lamella boron nitride, 36 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/native rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml deionized water, (contain 0.1wt% tensio-active agent Sodium cholic acid), carry out ultrasonic with ultrasound probe, ultrasonic power 1000W, ultrasonic time is 3h, obtains thickness below 10nm, and flakiness ratio is the suspension of the nanoscale twins boron nitride/water between the 50-300.
Composite manufacture: take by weighing 24.19g natural rubber latex (solid content 0.62, the actual natural gum 15g that contains).With 0.6g micron lamella boron nitride with contain the aqueous solution of 5.4g nanoscale twins boron nitride and after natural rubber latex mixes, be poured into (dilute sulphuric acid of 1wt%) in the flocculation agent, boron nitride/natural gum flocculates, put into baking oven oven dry (60 ℃), in mixing roll, add Synergist S-421 95 (5 parts in zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, promotor TT0.1 part, 1 part of antioxidant 4010,2 parts in sulphur) place 24h after, again back mixing in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 143 ℃, suppresses after 7 minutes, and mould is taken out the taking-up sample, (mass ratio=1:9) boron nitride quality per-cent is the heat conduction natural gum finished product of 28.6wt% to obtain micro-nano.
Embodiment 11: 100 parts of natural rubbers, 4 parts of micron lamella boron nitride, 36 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/native rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml deionized water, (contain 0.1wt% tensio-active agent Sodium cholic acid), carry out ultrasonic with ultrasound probe, ultrasonic power 1000W, ultrasonic time is 3h, obtains thickness below 10nm, and flakiness ratio is the suspension of the nanoscale twins boron nitride/water between the 50-300.
Composite manufacture: take by weighing 24.19g natural rubber latex (solid content 0.62, the actual natural gum 15g that contains).With 0.6g micron lamella boron nitride with contain the aqueous solution of 5.4g nanoscale twins boron nitride and after natural rubber latex mixes, be poured into (dilute sulphuric acid of 1wt%) in the flocculation agent, micro-nano boron nitride/natural gum flocculates, put into baking oven oven dry (60 ℃), in mixing roll, add Synergist S-421 95 (5 parts in zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, promotor TT0.1 part, 1 part of antioxidant 4010,2 parts in sulphur) place 24h after, again back mixing in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 143 ℃, suppresses after 7 minutes, and mould is taken out the taking-up sample, (mass ratio=1:9) boron nitride quality per-cent is the heat conduction natural gum finished product of 28.6wt% to obtain micro-nano.
Embodiment 12: 100 parts of natural rubbers, 18 parts of micron lamella boron nitride, 42 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/native rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 1800ml deionized water, (contain 0.05wt% tensio-active agent Sodium cholic acid), carry out ultrasonic with ultrasound probe, ultrasonic power 1500W, ultrasonic time is 2h, obtains thickness below 10nm, and flakiness ratio is the suspension of the nanoscale twins boron nitride/water between the 50-300.
Composite manufacture: take by weighing 24.19g natural rubber latex (solid content 0.62, the actual natural gum 15g that contains).With 2.7g micron lamella boron nitride with contain the aqueous solution of 6.3g nanoscale twins boron nitride and after natural rubber latex mixes, be poured into (dilute sulphuric acid of 1wt%) in the flocculation agent, micro-nano boron nitride/natural gum flocculates, put into baking oven oven dry (60 ℃), in mixing roll, add Synergist S-421 95 (5 parts in zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, promotor TT0.1 part, 1 part of antioxidant 4010,2 parts in sulphur) place 24h after, again back mixing in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 143 ℃, suppresses after 7 minutes, and mould is taken out the taking-up sample, (mass ratio=3:7) boron nitride quality per-cent is the heat conduction natural gum finished product of 37.5wt% to obtain micro-nano.
Embodiment 13: 100 parts of natural rubbers, 24 parts of micron lamella boron nitride, 56 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/native rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 20g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 3800ml deionized water, (contain 0.5wt% tensio-active agent Sodium cholic acid), carry out ultrasonic with ultrasound probe, ultrasonic power 1200W, ultrasonic time is 2.5h, obtains thickness below 10nm, and flakiness ratio is the suspension of the nanoscale twins boron nitride/water between the 50-300.
Composite manufacture: take by weighing 16.12g natural rubber latex (solid content 0.62, the actual natural gum 10g that contains).With 2.4g micron lamella boron nitride with contain the aqueous solution of 5.6g nanoscale twins boron nitride and after natural rubber latex mixes, be poured into (dilute sulphuric acid of 1wt%) in the flocculation agent, micro-nano boron nitride/natural gum flocculates, put into baking oven oven dry (60 ℃), in mixing roll, add Synergist S-421 95 (5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part vulkacit D, 0.5 part altax, 0.1 part promotor TT, 1 part of antioxidant 4010,2 parts of sulphur) place 24h after, again back mixing in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure is 100kg/cm2, temperature is 143 ℃, suppress after 7 minutes, mould is taken out the taking-up sample, and (mass ratio=3:7) boron nitride quality per-cent is the heat conduction natural gum finished product of 44.4wt% to obtain micro-nano.
Embodiment 14: 100 parts of natural rubbers, 30 parts of micron lamella boron nitride, 70 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/native rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 20g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 4000ml deionized water, (contain 0.1wt% tensio-active agent Sodium cholic acid), carry out ultrasonic with ultrasound probe, ultrasonic power 600W, ultrasonic time is 8h, obtains thickness below 10nm, and flakiness ratio is the suspension of the nanoscale twins boron nitride/water between the 50-300.
Composite manufacture: take by weighing 16.12g natural rubber latex (solid content 0.62, the actual natural gum 10g that contains).With 3g micron lamella boron nitride with contain the aqueous solution of 7g nanoscale twins boron nitride and after natural rubber latex mixes, be poured into (dilute sulphuric acid of 1wt%) in the flocculation agent, micro-nano boron nitride/natural gum flocculates, put into baking oven oven dry (60 ℃), in mixing roll, add Synergist S-421 95 (5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part vulkacit D, 0.5 part altax, 0.1 part promotor TT, 1 part of antioxidant 4010,2 parts of sulphur) place 24h after, again anti-refining in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 143 ℃, suppresses after 7 minutes, and mould is taken out the taking-up sample, (mass ratio=3:7) boron nitride quality per-cent is the heat conduction natural gum finished product of 50wt% to obtain micro-nano.
Embodiment 15: 100 parts of paracrils, 10 parts of micron lamella boron nitride, 40 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/nitile-butadiene rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 2000ml deionized water, (contain 0.8wt% tensio-active agent Sodium cholic acid), carry out ultrasonic with ultrasound probe, ultrasonic power 1000W, ultrasonic time is 3.5h, obtains thickness below 10nm, and flakiness ratio is the suspension of the nanoscale twins boron nitride/water between the 50-300.
Composite manufacture: take by weighing 33.33g nitrile rubber (solid content 0.45, the actual paracril 15g that contains).With 1.5g micron lamella boron nitride with contain the aqueous solution of 6g nanoscale twins boron nitride and after nitrile rubber mixes, be poured into (dilute sulphuric acid of 1wt%) in the flocculation agent, micro-nano boron nitride/butadiene-acrylonitrile rubber flocculates, put into baking oven oven dry (60 ℃), in mixing roll, add Synergist S-421 95 (5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part vulkacit D, 0.5 part altax, 0.1 part promotor TT, 1 part of antioxidant 4010,2 parts of sulphur) place 24h after, again back mixing in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 170 ℃, suppresses after 16 minutes, and mould is taken out the taking-up sample, (mass ratio=2:8) boron nitride quality per-cent is the heat conduction butadiene-acrylonitrile rubber finished product of 33.3wt% to obtain micro-nano.
Embodiment 16: 100 parts in styrene-butadiene rubber(SBR), 7 parts of micron lamella boron nitride, 63 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/styrene-butadiene rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 2000ml deionized water, (contain 1wt% tensio-active agent Sodium cholic acid), carry out ultrasonic with ultrasound probe, ultrasonic power 1000W, ultrasonic time is 3h, obtains thickness below 10nm, and the chi flakiness ratio is the suspension of the nanoscale twins boron nitride/water between the 50-300.
Composite manufacture: take by weighing 52.63g styrene-butadiene latex (solid content 0.19, the actual styrene-butadiene rubber(SBR) 10g that contains).With 0.7g micron lamella boron nitride with contain the aqueous solution of 6.3g nanoscale twins boron nitride and after styrene-butadiene latex mixes, be poured into (dilute sulphuric acid of 1wt%) in the flocculation agent, micro-nano boron nitride/butadiene-styrene rubber flocculates, put into baking oven oven dry (60 ℃), in mixing roll, add Synergist S-421 95 (5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part vulkacit D, 0.5 part altax, 0.1 part promotor TT, 1 part of antioxidant 4010,2 parts of sulphur) place 24h after, again anti-refining in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 150 ℃, suppresses after 17 minutes, and mould is taken out the taking-up sample, (mass ratio=1:9) boron nitride quality per-cent is the heat conduction butadiene-styrene rubber finished product of 41.2wt% to obtain micro-nano.
Embodiment 17: 100 parts of viton, 20 parts of micron lamella boron nitride, 30 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/viton matrix material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 2000ml propyl alcohol, carry out ultrasonic with ultrasound probe, ultrasonic power 1100W, ultrasonic time is 3.5h, obtains thickness after the drying below 10nm, and flakiness ratio is the nanoscale twins boron nitride between the 50-300.
Composite manufacture: take by weighing the 15g viton, 3g micron lamella boron nitride and 4.5g nanoscale twins boron nitride and viton are mixed in mixing roll, then add 3 parts of MgO, 6 parts of gCa (OH) 2 and all kinds of Synergist S-421 95 (5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part vulkacit D, 0.5 part altax, 0.1 part promotor TT, 1 part of antioxidant 4010,2 parts of sulphur), add 0.15g two-25 as linking agent, mix rear placement 24h, again back mixing in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 170 ℃, suppresses after 10 minutes, and mould is taken out the taking-up sample, (mass ratio=4:6) boron nitride quality per-cent is the heat conduction viton finished product of 33.3wt% to obtain micro-nano.
Embodiment 18: 100 parts of paracrils, 25 parts of micron lamella boron nitride, 25 parts of nanoscale twins boron nitride, preparation micro-nano boron nitride/nitile-butadiene rubber composite material.
At first prepare the nanoscale twins boron nitride: (thickness is about 1.5 μ m to take by weighing 10g raw material boron nitride, lateral dimension is about 20 μ m, flakiness ratio is about 13) in the 2000ml propyl alcohol, carry out ultrasonic with ultrasound probe, ultrasonic power 1100W, ultrasonic time is 3.5h, obtains thickness after the drying below 10nm, and flakiness ratio is the nanoscale twins boron nitride between the 50-300.
Composite manufacture: take by weighing the 15g paracril, 3.75g micron lamella boron nitride and 3.75g nanoscale twins boron nitride and paracril are mixed in mixing roll, then add Synergist S-421 95 (5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of vulkacit D, 0.5 part of altax, 0.1 part of promotor TT, 1 part of antioxidant 4010,2 parts of sulphur), mix rear placement 24h, again back mixing in mill, be positioned in the rubber mold, pressure exhaust in the compression molding instrument, pressure are 100kg/cm
2, temperature is 170 ℃, suppresses after 15 minutes, and mould is taken out the taking-up sample, (mass ratio=5:5) boron nitride quality per-cent is the heat conduction butadiene-acrylonitrile rubber finished product of 33.3wt% to obtain micro-nano.
The performance data of embodiment sees Table one.
Claims (5)
1. a micron and nanoscale twins boron nitride are mixed the preparation method of filled rubber, it is characterized in that: rubber raw materials is dried glue or emulsion form, the rubber parts by weight are 100 parts, total boron nitride parts by weight are 50-100 part, and wherein the mass ratio of micron boron nitride and nm-class boron nitride is 1:9-9:1;
The dried glue of raw material choose:
Micron lamella boron nitride is placed solvent orange 2 A, being made into concentration is 1mg/ml-6mg/ml suspension, the ultrasonic thickness that obtains is below 10nm, flakiness ratio is the nanoscale twins boron nitride of 50-300, obtain rubber solutions with the solvent orange 2 A dissolving rubber, micron lamella boron nitride, nanoscale twins boron nitride and rubber solutions are mixed; Then evaporating solvent A; Or pour among the solvent B, this solvent B is 5-15 times of solvent orange 2 A volume, dissolves each other with solvent orange 2 A, and not sol rubber and boron nitride, make rubber and boron nitride coprecipitation out; By mixing in mill, Banbury mixer or screw extrusion press, add therein the vulcanizing agent DCP of 1wt% again, make micro-nano lamella boron nitride/silicon rubber composite material after the sulfuration;
Raw material choose latex:
Micron lamella boron nitride placed contain the deionized water that the tensio-active agent Sodium cholic acid is 0.05wt%-1wt%, being made into concentration is 1mg/ml-6mg/ml suspension, the ultrasonic thickness that obtains is below 10nm, flakiness ratio is the nanoscale twins boron nitride of 50-300, after mixing with micron lamella boron nitride, rubber latex again, dilute sulphuric acid flocculation with 1wt%, dry, in mixing roll, add the Synergist S-421 95 that comprises at least zinc oxide, stearic acid, promotor, anti-aging agent, sulphur mixing evenly, obtain micro-nano lamella boron nitride/rubber composite after the sulfuration.
2. micron according to claim 1 and nanoscale twins boron nitride are mixed the preparation method of filled rubber, it is characterized in that: used solvent is alcohol, ketone, alkane or tetrahydrofuran (THF).
3. micron according to claim 1 and nanoscale twins boron nitride are mixed the preparation method of filled rubber, and it is characterized in that: ultrasonic power is 200-1500W, and ultrasonic time is 2-12h, and the flakiness ratio of the nanoscale twins boron nitride of acquisition is 50-250.
4. micron according to claim 1 and nanoscale twins boron nitride are mixed the preparation method of filled rubber, it is characterized in that: the mass ratio of micron lamella boron nitride and prepared nanoscale twins boron nitride is 3:7-5:5.
5. micron according to claim 4 and nanoscale twins boron nitride are mixed the preparation method of filled rubber, it is characterized in that: the mass ratio of micron lamella boron nitride and prepared nanoscale twins boron nitride is 3:7.
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| CN110734642A (en) * | 2019-06-27 | 2020-01-31 | 上海大学 | insulating high-strength nano composite material and preparation method thereof |
| CN112373148A (en) * | 2020-11-11 | 2021-02-19 | 中山大学 | Polyimide double-sided flexible heat-conducting copper-clad plate and preparation method and application thereof |
| CN113736150A (en) * | 2021-07-30 | 2021-12-03 | 山东华勤橡胶科技有限公司 | High-performance tread rubber composite material and preparation method and application thereof |
| CN114230947A (en) * | 2022-02-07 | 2022-03-25 | 仇连彩 | Super-elastic wear-resistant rubber material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110734642A (en) * | 2019-06-27 | 2020-01-31 | 上海大学 | insulating high-strength nano composite material and preparation method thereof |
| CN110734642B (en) * | 2019-06-27 | 2022-04-15 | 上海大学 | Insulating high-strength nano composite material and preparation method thereof |
| CN112373148A (en) * | 2020-11-11 | 2021-02-19 | 中山大学 | Polyimide double-sided flexible heat-conducting copper-clad plate and preparation method and application thereof |
| CN113736150A (en) * | 2021-07-30 | 2021-12-03 | 山东华勤橡胶科技有限公司 | High-performance tread rubber composite material and preparation method and application thereof |
| CN113736150B (en) * | 2021-07-30 | 2023-11-07 | 山东华勤橡胶科技有限公司 | High-performance tread rubber composite material and preparation method and application thereof |
| CN114230947A (en) * | 2022-02-07 | 2022-03-25 | 仇连彩 | Super-elastic wear-resistant rubber material and preparation method thereof |
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