CN109851996A - A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material - Google Patents

A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material Download PDF

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CN109851996A
CN109851996A CN201811574387.6A CN201811574387A CN109851996A CN 109851996 A CN109851996 A CN 109851996A CN 201811574387 A CN201811574387 A CN 201811574387A CN 109851996 A CN109851996 A CN 109851996A
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epoxy resin
molecular weight
high molecular
weight polyethylene
preparation
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石海峰
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Jiangsu Putaike New Material Technology Co Ltd
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Jiangsu Putaike New Material Technology Co Ltd
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Abstract

The invention discloses the preparation methods of a kind of carbonization silicon modified epoxy resin and its composite material, a kind of preparation method of be carbonized silicon modified epoxy resin and its composite material, raw material including following parts by weight proportion: ultra high molecular weight polyethylene fiber, 0.03-0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, silicon carbide, dehydrated alcohol, epoxy resin, 1,3- bis- (aminomethyl) benzene curing agent.Carbonization silicon modified epoxy resin prepared by the present invention, simple process, at low cost, reagent used is conventional reagent, does not need special installation, therefore have the characteristics that industrializing implementation is easy, carbonization silicon modified epoxy resin prepared by the present invention, by the way that silicon carbide is added in the epoxy, silicon carbide not only improves resin property, it can also be by playing the role of enhancing in the crossover network of resin and tannic acid, to improve interfacial adhesion.

Description

A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material
Technical field
The present invention relates to the technical field of composite materials of fiber and resin, specially a kind of carbonization silicon modified epoxy resin and The preparation method of its composite material.
Background technique
Ultra-high molecular weight polyethylene (UHMWPE) fiber is to succeed in developing the early 1980s, after carbon fiber and The third generation high-performance fiber occurred after aramid fiber is current specific strength and the highest fiber of specific modulus in the world.It has There are a series of excellent performances, such as: high specific strength, high ratio modulus, specific strength are more than ten times of same section steel wire, and specific modulus is only Inferior to superfine carbon fiber.Extension at break is low, work to break is big, with the very strong ability for absorbing energy, thus has outstanding anti- Impact and anti-cut.Fibre density is low, and density is 0.97-0.98g/cm3, can bubble through the water column.With excellent uvioresistant Beta radiation, anti-neutron and gamma-rays, specific energy absorption is high, dielectric constant is low, electromagnetic wave tansmittivity is high.Wear-resisting, resistant to chemical etching, There is longer flex life.But due to UHMWPE fiber surface non-polar group, no chemical activity, surface can be low, nonpolarity The disadvantages such as substance is difficult to infiltrate, and fusing point is low, to limit its application.Especially in terms of reinforced resin based composites, Adhesive property between resin matrix is poor, causes shock resistance low, composite material is caused to occur fibre in use The problems such as with resin matrix degumming and resin matrix cracking occur for dimension.
It is proved that fiber/epoxy resin composite material physics can be improved after epoxy resin is added in inorganic nano-particle And chemical property.Therefore, nano particle is dispersed in epoxy resin-base, for increasing substantially composite material Mechanical property has very important meaning.
Silicon carbide (SiC) has many advantages, such as, such as: fusing point, intensity and elasticity modulus are high, thermal expansion coefficient is low, chemical Stability and wearability are outstanding etc., are at present also one of the ideal additive of advanced composite material.Nanometer silicon carbide grain diameter Small, high surface activity is added into epoxy resin-base, it is easy to and the functional group of resin matrix has an effect, and is conducive to Interface adhesive strength is improved, the mobility of matrix is reduced, to make the biggish improvement of the mechanical characteristic of composite material.
And the present invention proposes a kind of new thinking, starts with from the angle of resin, silicon carbide is added in trial in the epoxy, Playing the role of nanoparticle between the fiber that resin and tannic acid are modified enhances, the cohesive force of reinforced resin and matrix, most The intensity of composite material is greatly improved eventually.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides the systems of a kind of carbonization silicon modified epoxy resin and its composite material Preparation Method has simple process and low cost, and reagent used is conventional reagent, does not need special installation, therefore have industry Change and implements the advantages that being easy.
(2) technical solution
To achieve the above object, the invention provides the following technical scheme: a kind of carbonization silicon modified epoxy resin and its compound The preparation method of material, the raw material including following parts by weight proportion: ultra high molecular weight polyethylene fiber, 0.03- 0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, silicon carbide, dehydrated alcohol, epoxy resin, bis- (ammonia of 1,3- Methyl) benzene curing agent, comprising the following steps:
1) preparation of tannic acid coating ultra high molecular weight polyethylene fiber
1. ultra high molecular weight polyethylene fiber is soaked for a period of time in ethyl alcohol, removal fiber surface is remaining organic molten Agent then takes out drying.
2. the Tris for weighing 0.03-0.5g is dissolved in 200ml water, pH value of solution=8.5 are adjusted, 0.1-0.8g is then weighed Tannic acid, 3-8gNaCl are dissolved in above-mentioned Tris solution and stir, ultra high molecular weight polyethylene fiber is immersed in this solution, 3-12h of concussion coating.
It is dried 3. afterwards taking out ultra high molecular weight polyethylene fiber, ultra-high molecular weight polyethylene is fine after being made tannic acid modified Dimension.
2) preparation of carbonization silicon modified epoxy resin
1. weighing a certain amount of silicon carbide, a certain amount of dehydrated alcohol is added as dispersing agent, while also doing epoxy resin Diluent, 1-3h of ultrasonic disperse.
2. weighing a certain amount of epoxy resin into beaker, scattered silicon carbide is added in beaker, mechanical stirring 1- 2h is completely dispersed silicon carbide in the epoxy.
3. it is added 1,3- bis- (aminomethyl) benzene curing agent, 5-10min of vacuum defoamation at 60 DEG C.
3) preparation of composite material
The ultra high molecular weight polyethylene fiber that tannic acid coats is put into mold, the epoxy resin for the Si modification that is carbonized is infused Enter in mold, demoulded after curing molding at room temperature, obtains tannic acid coating ultra high molecular weight polyethylene fiber and doping is carbonized The epoxy resin composite material of silicon.
Preferably, the mass percent of the silicon carbide and epoxy resin is 0% -10%.
Preferably, the mass ratio of the dehydrated alcohol and epoxy resin is 1:1-1:6.
Preferably, the mass ratio of the curing agent and epoxy resin is 1:1-1:6.
(3) beneficial effect
Compared with prior art, the present invention provides the preparation sides of a kind of carbonization silicon modified epoxy resin and its composite material Method, have it is following the utility model has the advantages that
1, carbonization silicon modified epoxy resin prepared by the present invention, simple process and low cost, reagent used are conventional examination Agent does not need special installation, therefore has the characteristics that industrializing implementation is easy.
2, carbonization silicon modified epoxy resin prepared by the present invention, by the way that silicon carbide is added in the epoxy, silicon carbide is not But improve resin property, it can also be by playing the role of enhancing in the crossover network of resin and tannic acid, to improve boundary Face cohesive force.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts Example, shall fall within the protection scope of the present invention.
Embodiment one
A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material, the original including following parts by weight proportion Material: ultra high molecular weight polyethylene fiber, 0.03-0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, carbonization Silicon, dehydrated alcohol, epoxy resin, 1,3- bis- (aminomethyl) benzene curing agent, comprising the following steps:
1) preparation of tannic acid coating ultra high molecular weight polyethylene fiber
1. ultra high molecular weight polyethylene fiber is soaked for a period of time in ethyl alcohol, removal fiber surface is remaining organic molten Agent then takes out drying.
2. the Tris for weighing 0.121g are dissolved in 200ml water, pH value of solution=8.5 are adjusted, 0.4g tannic acid is then weighed, 3gNaCl is dissolved in above-mentioned Tris solution and stirs, ultra high molecular weight polyethylene fiber is immersed in this solution, concussion coating 3h。
It is dried 3. afterwards taking out ultra high molecular weight polyethylene fiber, ultra-high molecular weight polyethylene is fine after being made tannic acid modified Dimension.
2) preparation of carbonization silicon modified epoxy resin
1. weighing a certain amount of silicon carbide, the mass percent for controlling silicon carbide and epoxy resin is 0.5%, is added certain The dehydrated alcohol of amount also makees the diluent of epoxy resin as dispersing agent, controls the quality of dehydrated alcohol and epoxy resin Than for 1:3, ultrasonic disperse 1h.
2. weighing a certain amount of epoxy resin into beaker, scattered silicon carbide is added in beaker, mechanical stirring 1h, It is completely dispersed silicon carbide in the epoxy.
3. being added 1,3- bis- (aminomethyl) benzene curing agent, the mass ratio for controlling curing agent and epoxy resin is 1:3, at 60 DEG C Lower vacuum defoamation 5min.
3) preparation of composite material
The ultra high molecular weight polyethylene fiber that tannic acid coats is put into mold, the epoxy resin for the Si modification that is carbonized is infused Enter in mold, demoulded after curing molding at room temperature, obtains tannic acid coating ultra high molecular weight polyethylene fiber and doping is carbonized The epoxy resin composite material of silicon.
Embodiment two
A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material, the original including following parts by weight proportion Material: ultra high molecular weight polyethylene fiber, 0.03-0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, carbonization Silicon, dehydrated alcohol, epoxy resin, 1,3- bis- (aminomethyl) benzene curing agent, comprising the following steps:
1) preparation of tannic acid coating ultra high molecular weight polyethylene fiber
1. ultra high molecular weight polyethylene fiber is soaked for a period of time in ethyl alcohol, removal fiber surface is remaining organic molten Agent then takes out drying.
2. the Tris for weighing 0.242g are dissolved in 200ml water, pH value of solution=8.5 are adjusted, 0.5g tannic acid is then weighed, 4gNaCl is dissolved in above-mentioned Tris solution and stirs, ultra high molecular weight polyethylene fiber is immersed in this solution, concussion coating 6h。
It is dried 3. afterwards taking out ultra high molecular weight polyethylene fiber, ultra-high molecular weight polyethylene is fine after being made tannic acid modified Dimension.
2) preparation of carbonization silicon modified epoxy resin
1. weighing a certain amount of silicon carbide, the mass percent for controlling silicon carbide and epoxy resin is 1.0%, is added certain The dehydrated alcohol of amount also makees the diluent of epoxy resin as dispersing agent, controls the quality of dehydrated alcohol and epoxy resin Than for 1:4, ultrasonic disperse 1.5h.
2. weighing a certain amount of epoxy resin into beaker, scattered silicon carbide is added in beaker, mechanical stirring 1.5h is completely dispersed silicon carbide in the epoxy.
3. being added 1,3- bis- (aminomethyl) benzene curing agent, the mass ratio for controlling curing agent and epoxy resin is 1:4, at 60 DEG C Lower vacuum defoamation 5min.
3) preparation of composite material
The ultra high molecular weight polyethylene fiber that tannic acid coats is put into mold, the epoxy resin for the Si modification that is carbonized is infused Enter in mold, demoulded after curing molding at room temperature, obtains tannic acid coating ultra high molecular weight polyethylene fiber and doping is carbonized The epoxy resin composite material of silicon.
Embodiment three
A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material, the original including following parts by weight proportion Material: ultra high molecular weight polyethylene fiber, 0.03-0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, carbonization Silicon, dehydrated alcohol, epoxy resin, 1,3- bis- (aminomethyl) benzene curing agent, comprising the following steps:
1) preparation of tannic acid coating ultra high molecular weight polyethylene fiber
1. ultra high molecular weight polyethylene fiber is soaked for a period of time in ethyl alcohol, removal fiber surface is remaining organic molten Agent then takes out drying.
2. the Tris for weighing 0.363g are dissolved in 200ml water, pH value of solution=8.5 are adjusted, 0.6g tannic acid is then weighed, 5gNaCl is dissolved in above-mentioned Tris solution and stirs, ultra high molecular weight polyethylene fiber is immersed in this solution, concussion coating 9h。
It is dried 3. afterwards taking out ultra high molecular weight polyethylene fiber, ultra-high molecular weight polyethylene is fine after being made tannic acid modified Dimension.
2) preparation of carbonization silicon modified epoxy resin
1. weighing a certain amount of silicon carbide, the mass percent for controlling silicon carbide and epoxy resin is 1.5%, is added certain The dehydrated alcohol of amount also makees the diluent of epoxy resin as dispersing agent, controls the quality of dehydrated alcohol and epoxy resin Than for 1:5, ultrasonic disperse 2h.
2. weighing a certain amount of epoxy resin into beaker, scattered silicon carbide is added in beaker, mechanical stirring 2h, It is completely dispersed silicon carbide in the epoxy.
3. being added 1,3- bis- (aminomethyl) benzene curing agent, the mass ratio for controlling curing agent and epoxy resin is 1:5, at 60 DEG C Lower vacuum defoamation 5min.
3) preparation of composite material
The ultra high molecular weight polyethylene fiber that tannic acid coats is put into mold, the epoxy resin for the Si modification that is carbonized is infused Enter in mold, demoulded after curing molding at room temperature, obtains tannic acid coating ultra high molecular weight polyethylene fiber and doping is carbonized The epoxy resin composite material of silicon.
Example IV
A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material, the original including following parts by weight proportion Material: ultra high molecular weight polyethylene fiber, 0.03-0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, carbonization Silicon, dehydrated alcohol, epoxy resin, 1,3- bis- (aminomethyl) benzene curing agent, comprising the following steps:
1) preparation of tannic acid coating ultra high molecular weight polyethylene fiber
1. ultra high molecular weight polyethylene fiber is soaked for a period of time in ethyl alcohol, removal fiber surface is remaining organic molten Agent then takes out drying.
2. the Tris for weighing 0.484g are dissolved in 200ml water, pH value of solution=8.5 are adjusted, 0.7g tannic acid is then weighed, 6gNaCl is dissolved in above-mentioned Tris solution and stirs, ultra high molecular weight polyethylene fiber is immersed in this solution, concussion coating 10h。
It is dried 3. afterwards taking out ultra high molecular weight polyethylene fiber, ultra-high molecular weight polyethylene is fine after being made tannic acid modified Dimension.
2) preparation of carbonization silicon modified epoxy resin
1. weighing a certain amount of silicon carbide, the mass percent for controlling silicon carbide and epoxy resin is 2%, is added a certain amount of Dehydrated alcohol as dispersing agent, while also making the diluent of epoxy resin, control the mass ratio of dehydrated alcohol and epoxy resin For 1:5, ultrasonic disperse 2.5h.
2. weighing a certain amount of epoxy resin into beaker, scattered silicon carbide is added in beaker, mechanical stirring 2h, It is completely dispersed silicon carbide in the epoxy.
3. being added 1,3- bis- (aminomethyl) benzene curing agent, the mass ratio for controlling curing agent and epoxy resin is 1:5, at 60 DEG C Lower vacuum defoamation 5min.
3) preparation of composite material
The ultra high molecular weight polyethylene fiber that tannic acid coats is put into mold, the epoxy resin for the Si modification that is carbonized is infused Enter in mold, demoulded after curing molding at room temperature, obtains tannic acid coating ultra high molecular weight polyethylene fiber and doping is carbonized The epoxy resin composite material of silicon.
Embodiment five
A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material, the original including following parts by weight proportion Material: ultra high molecular weight polyethylene fiber, 0.03-0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, carbonization Silicon, dehydrated alcohol, epoxy resin, 1,3- bis- (aminomethyl) benzene curing agent, comprising the following steps:
1) preparation of tannic acid coating ultra high molecular weight polyethylene fiber
1. ultra high molecular weight polyethylene fiber is soaked for a period of time in ethyl alcohol, removal fiber surface is remaining organic molten Agent then takes out drying.
2. the Tris for weighing 0.5g are dissolved in 200ml water, pH value of solution=8.5 are adjusted, 0.8g tannic acid is then weighed, 8gNaCl is dissolved in above-mentioned Tris solution and stirs, ultra high molecular weight polyethylene fiber is immersed in this solution, concussion coating 12h。
It is dried 3. afterwards taking out ultra high molecular weight polyethylene fiber, ultra-high molecular weight polyethylene is fine after being made tannic acid modified Dimension.
2) preparation of carbonization silicon modified epoxy resin
1. weighing a certain amount of silicon carbide, the mass percent for controlling silicon carbide and epoxy resin is 8%, is added a certain amount of Dehydrated alcohol as dispersing agent, while also making the diluent of epoxy resin, control the mass ratio of dehydrated alcohol and epoxy resin For 1:6, ultrasonic disperse 3h.
2. weighing a certain amount of epoxy resin into beaker, scattered silicon carbide is added in beaker, mechanical stirring 2h, It is completely dispersed silicon carbide in the epoxy.
3. being added 1,3- bis- (aminomethyl) benzene curing agent, the mass ratio for controlling curing agent and epoxy resin is 1:6, at 60 DEG C Lower vacuum defoamation 10min.
3) preparation of composite material
The ultra high molecular weight polyethylene fiber that tannic acid coats is put into mold, the epoxy resin for the Si modification that is carbonized is infused Enter in mold, demoulded after curing molding at room temperature, obtains tannic acid coating ultra high molecular weight polyethylene fiber and doping is carbonized The epoxy resin composite material of silicon.
In conclusion carbonization silicon modified epoxy resin prepared by the present invention, simple process and low cost, reagent used are equal For conventional reagent, special installation is not needed, therefore has the characteristics that industrializing implementation is easy, carbonization Si modification prepared by the present invention Epoxy resin, by the way that silicon carbide is added in the epoxy, silicon carbide not only improves resin property, can also by resin and Play the role of enhancing in the crossover network of tannic acid, to improve interfacial adhesion.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding And modification, the scope of the present invention is defined by the appended.

Claims (4)

1. the preparation method of a kind of carbonization silicon modified epoxy resin and its composite material, the original including following parts by weight proportion Material: ultra high molecular weight polyethylene fiber, 0.03-0.5gTris, 200ml water, 0.1-0.8g tannic acid, 3-8gNaCl, carbonization Silicon, dehydrated alcohol, epoxy resin, 1,3- bis- (aminomethyl) benzene curing agent, which comprises the following steps:
1) preparation of tannic acid coating ultra high molecular weight polyethylene fiber
1. ultra high molecular weight polyethylene fiber is soaked for a period of time in ethyl alcohol, the remaining organic solvent of fiber surface is removed, Then take out drying;
2. the Tris for weighing 0.03-0.5g is dissolved in 200ml water, pH value of solution=8.5 are adjusted, 0.1-0.8g tannin is then weighed Acid, 3-8gNaCl are dissolved in above-mentioned Tris solution and stir, ultra high molecular weight polyethylene fiber is immersed in this solution, concussion Coat 3-12h;
It is dried 3. afterwards taking out ultra high molecular weight polyethylene fiber, ultra high molecular weight polyethylene fiber after being made tannic acid modified;
2) preparation of carbonization silicon modified epoxy resin
1. weighing a certain amount of silicon carbide, a certain amount of dehydrated alcohol is added as dispersing agent, while being also the dilute of epoxy resin Release agent, 1-3h of ultrasonic disperse;
2. weighing a certain amount of epoxy resin into beaker, scattered silicon carbide is added in beaker, 1-2h of mechanical stirring, It is completely dispersed silicon carbide in the epoxy;
3. it is added 1,3- bis- (aminomethyl) benzene curing agent, 5-10min of vacuum defoamation at 60 DEG C;
3) preparation of composite material
The ultra high molecular weight polyethylene fiber that tannic acid coats is put into mold, the epoxy resin for the Si modification that is carbonized is injected into mould It in tool, is demoulded after curing molding at room temperature, obtains tannic acid coating ultra high molecular weight polyethylene fiber and doped silicon carbide Epoxy resin composite material.
2. the preparation method of a kind of carbonization silicon modified epoxy resin according to claim 1 and its composite material, feature It is, the mass percent of the silicon carbide and epoxy resin is 0% -10%.
3. the preparation method of a kind of carbonization silicon modified epoxy resin according to claim 1 and its composite material, feature It is, the mass ratio of the dehydrated alcohol and epoxy resin is 1:1-1:6.
4. the preparation method of a kind of carbonization silicon modified epoxy resin according to claim 1 and its composite material, feature It is, the mass ratio of the curing agent and epoxy resin is 1:1-1:6.
CN201811574387.6A 2018-12-21 2018-12-21 A kind of preparation method of be carbonized silicon modified epoxy resin and its composite material Pending CN109851996A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778605A (en) * 2020-12-30 2021-05-11 南京逸科景润科技有限公司 Enhanced carbon fiber ultra-high molecular weight polyethylene fiber composite fiber material and preparation method thereof
CN114808446A (en) * 2022-06-06 2022-07-29 江南大学 Environment-friendly explosion-proof modified ultrahigh molecular weight polyethylene fiber and preparation method thereof
CN115216119A (en) * 2022-07-05 2022-10-21 上海冷盟精密电机有限公司 Epoxy resin composite material and preparation method thereof

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CN104497491A (en) * 2014-12-23 2015-04-08 安徽助成信息科技有限公司 Method for improving thermal conductivity of epoxy resin based on nanometer silicon carbide
CN104673160A (en) * 2014-06-30 2015-06-03 广东丹邦科技有限公司 Filled surface modified silicon carbide isotropic thermal conduction adhesive and preparation method thereof
CN106220892A (en) * 2016-08-16 2016-12-14 谭国权 Epoxy resin cure coating and preparation method thereof
CN108395675A (en) * 2018-03-09 2018-08-14 天津工业大学 A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
CN104673160A (en) * 2014-06-30 2015-06-03 广东丹邦科技有限公司 Filled surface modified silicon carbide isotropic thermal conduction adhesive and preparation method thereof
CN104497491A (en) * 2014-12-23 2015-04-08 安徽助成信息科技有限公司 Method for improving thermal conductivity of epoxy resin based on nanometer silicon carbide
CN106220892A (en) * 2016-08-16 2016-12-14 谭国权 Epoxy resin cure coating and preparation method thereof
CN108395675A (en) * 2018-03-09 2018-08-14 天津工业大学 A kind of tannic acid modified superhigh molecular weight polyethylene fibers and its composite material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112778605A (en) * 2020-12-30 2021-05-11 南京逸科景润科技有限公司 Enhanced carbon fiber ultra-high molecular weight polyethylene fiber composite fiber material and preparation method thereof
CN112778605B (en) * 2020-12-30 2022-09-09 广东冠豪新材料研发有限公司 Enhanced carbon fiber ultra-high molecular weight polyethylene fiber composite fiber material and preparation method thereof
CN114808446A (en) * 2022-06-06 2022-07-29 江南大学 Environment-friendly explosion-proof modified ultrahigh molecular weight polyethylene fiber and preparation method thereof
CN115216119A (en) * 2022-07-05 2022-10-21 上海冷盟精密电机有限公司 Epoxy resin composite material and preparation method thereof

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Application publication date: 20190607