CN103602042B - A kind of Liquid crystal epoxy resin-carbon fiber composite material and preparation method thereof - Google Patents
A kind of Liquid crystal epoxy resin-carbon fiber composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to shape memory high molecule material preparation field, specifically disclose a kind of Liquid crystal epoxy resin-carbon fiber composite material with shape-memory properties and preparation method thereof.The preparation method of Liquid crystal epoxy resin-carbon fiber composite material provided by the invention comprises three steps: (1) surface treatment of carbon fibers; (2) preparation of composite material mixture; (3) curing molding.The present invention uses the branched epoxy resin by using liquid crystal of carbon fiber modifying, can reduce costs, and improves the thermomechanical property of material; Liquid crystal epoxy resin-carbon fiber composite material prepared by the present invention has shape-memory properties, and the speed of response is high, recovery stress is high, can be applied to the science and technology field such as bio-medical, aerospace.
Description
Technical field
The invention belongs to shape memory high molecule material preparation field, be specifically related to a kind of preparation method of Liquid crystal epoxy resin-carbon fiber composite material.
Background technology
The appearance of shape-memory material is the great leap in Materials science history in this century, it discloses the special essence of material inherence, for the innovation of material processing technique and the exploitation of product innovation provide brand-new approach.Since finding Ni-Ti shape memory alloy from 1964, shape-memory material has caused countries in the world to pay close attention to widely and has achieved huge progress.Since the eighties, the shape memory high molecule material of sudden emergence has become a kind of noticeable active material with the over-all properties of its excellence.Compared with shape memory alloy, shape memory high molecule material has that lightweight, corrosion-resistant, easy formed machining, memory recovery temperature wide ranges, deformation quantity are large, insulation and the advantage such as good insulation preformance, low price.Therefore it has potential using value and application prospect widely in a lot of field, be used widely in the fields such as medical treatment, manufacture, packaging, building and AGRICULTURAL ENERGY as steel tubing in different shapes grafting material, surgical operation immobilization material, cushioning material, wrapping material, fire alarm equipment and coating etc. at present and developed, its economic benefit and social effect significantly, are research and develop field the most active in current shape-memory material.
In recent years, mesomorphic unit is incorporated in shape-memory material especially noticeable.The introducing of mesomorphic unit improves the recovery stress of shape-memory polymer, improves reply effect, is expected to obtain potential application in aerospace and bio-medical field.PattrickT.Mather etc. have synthesized a kind of smectic C type liquid crystal elastic body with shape memory effect first.Hiraoka etc. report the twin shaft shape memory effect of the liquid crystal elastic body of single domain chiral smectic phase.At home, Li Deli, Zhou Qifeng etc. have studied the shape memory effect of crust type liquid crystal polymer fibre.Application number be 201110305569.5 Chinese invention patent and application number be 201010203910.1 Chinese invention patent application disclose branched epoxy resin by using liquid crystal and biphenyl type epoxy resin by using liquid crystal and have studied its shape memory effect, its product has better thermomechanical property and shape-memory properties.
But it is higher to see that shape memory epoxy resin by using liquid crystal exists cost from research at present, the shortcomings such as the weak link of mechanical property.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, the object of the present invention is to provide a kind of preparation method with the Liquid crystal epoxy resin-carbon fiber composite material of shape-memory properties;
Another object of the present invention is to provide the Liquid crystal epoxy resin-carbon fiber composite material prepared by aforesaid method.
Object of the present invention is achieved through the following technical solutions:
A preparation method for Liquid crystal epoxy resin-carbon fiber composite material, comprises the steps:
(1) surface treatment of carbon fibers: by carbon fiber soaking and washing 100 ~ 140h in methylene dichloride, then take out carbon fiber be placed in distilled water soak 36 ~ 48h, then take out carbon fiber in 80 ~ 100 DEG C of vacuum-drying 24 ~ 36h, obtain process after carbon fiber;
(2) composite material mixture preparation: take branched epoxy resin by using liquid crystal and solidifying agent that mol ratio is 2:1, be dissolved in methylene dichloride, obtain mixed solution; Add the carbon fiber after step (1) process again, ultrasonic vibration makes carbon fiber dispersed in mixed solution, obtains composite material mixture;
(3) curing molding: composite material mixture poured in mould, is evacuated to constant weight under normal temperature, and treat that solvent evaporates is complete, stage curing, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Surface treatment of carbon fibers described in step (1) also can be: by carbon fiber soaking and washing 100 ~ 140h in methylene dichloride, then take out carbon fiber be placed in distilled water soak 36 ~ 48h, then take out carbon fiber in 80 ~ 100 DEG C of vacuum-drying 24 ~ 36h; The carbon fiber taken out after vacuum-drying is placed in the acetone soln dispersion treatment containing 1 ~ 10% massfraction amine epoxy resin solidifying agent, again carbon fiber is taken out the retort furnace putting into 500 ~ 600 DEG C and stop 30 ~ 40s, take out carbon fiber acetone soln to wash, drying, obtains the carbon fiber after processing; Wherein, described amine epoxy resin solidifying agent is more than one of aliphatics amine curing agent and aromatic amine solidifying agent, be preferably 4,4-diaminodiphenyl-methane (DDM), 4-aminophenyiamino sulfone (SAA), 4, more than one of 4-diaminodiphenyl oxide (DDE), 4,4-diamino-phenyl sulfoxides (DDS), methylresorcinol diamines (DAT) and quadrol.
Surface treatment of carbon fibers described in step (1) also can be: by carbon fiber soaking and washing 100 ~ 140h in methylene dichloride, then take out carbon fiber be placed in distilled water soak 36 ~ 48h, then take out carbon fiber in 80 ~ 100 DEG C of vacuum-drying 24 ~ 36h; Dried carbon fiber is placed in concentrated nitric acid stirring and refluxing 1 ~ 2h at 100 ~ 110 DEG C, the carbon fiber filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the carbon fiber washing that obtains at 100 DEG C vacuum-drying 24h; Then the carbon fiber after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide reflux 2 ~ 3h, filters and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the carbon fiber that solid trapped substance is chloride; The tetrahydrofuran solution put into by the carbon fiber of chloride containing the epoxy curing agent of the DMAP of massfraction 0.5 ~ 1%, the triethylamine of massfraction 20 ~ 30% and massfraction 5 ~ 10% reacts 24h again, then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, vacuum-drying 24h at 100 DEG C again, obtains the carbon fiber after processing; Wherein, described epoxy curing agent is more than one of aliphatics amine curing agent or aromatic amine solidifying agent, be preferably 4,4-diaminodiphenyl-methane (DDM), 4-aminophenyiamino sulfone (SAA), 4, more than one of 4-diaminodiphenyl oxide (DDE), 4,4-diamino-phenyl sulfoxides (DDS), methylresorcinol diamines (DAT) and quadrol.
Step (1) described carbon fiber is PAN-based carbon fiber or asphalt base carbon fiber; Step (1) described carbon fiber is the chopped carbon fiber of length 1 ~ 12mm, the carbon fiber filament bundle of 3K, 6K, 12K or the unidirectional or two-way twill carbon cloth of 200g, 300g specification.
In the preparation method of above-mentioned Liquid crystal epoxy resin-carbon fiber composite material, when step (1) described carbon fiber is the chopped carbon fiber of length 1 ~ 12mm, the consumption of the carbon fiber after step (3) described process is 0.5 ~ 5% of the carbon fiber total mass after accounting for branched epoxy resin by using liquid crystal, solidifying agent and process; When step (1) described carbon fiber is the carbon fiber filament bundle of 3K, 6K, 12K, the consumption of the carbon fiber after step (3) described process is 10 ~ 40% of the carbon fiber total mass after accounting for branched epoxy resin by using liquid crystal, solidifying agent and process; When the unidirectional or two-way twill carbon cloth that step (1) described carbon fiber is 200g, 300g specification, the consumption of the carbon fiber after step (3) described process is 20 ~ 40% of the carbon fiber total mass after accounting for branched epoxy resin by using liquid crystal, solidifying agent and process.
Branched epoxy resin by using liquid crystal described in step (2) is epoxy resin by using liquid crystal monomer 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-n, n=1 ~ 12), described branched epoxy resin by using liquid crystal structural formula as shown in Equation 1:
Formula 1
Wherein, n is the integer of 1 ~ 12.
Described branched epoxy resin by using liquid crystal is compound disclosed in the Chinese invention patent " a kind of branched epoxy resin by using liquid crystal and preparation method thereof, composition and purposes " of application number 200410052408.X, can obtain according to disclosed preparation method.
Solidifying agent described in step (2) is 4,4-diaminodiphenyl-methane (DDM), 4-aminophenyiamino sulfone (SAA), 4, more than one of 4-diaminodiphenyl oxide (DDE), 4,4-diamino thionyl benzenes (DDS), methylresorcinol diamines (DAT) and quadrol.
The described stage curing concrete operations of step (3) for: first under the condition higher than the branched epoxy resin by using liquid crystal second-order transition temperature 5 ~ 10 DEG C described in step (2), solidify 12 ~ 16h, at 150 ~ 170 DEG C, solidify 5 ~ 7h again, then at 200 DEG C, solidify 1h.
A kind of Liquid crystal epoxy resin-carbon fiber composite material prepared by above-mentioned preparation method.
Principle of the present invention:
The present invention adopts and adds carbon fiber to strengthen the method for epoxy resin by using liquid crystal thermomechanical property, and the surface treatment of carbon fiber, the interface cohesive force of carbon fiber and epoxy resin by using liquid crystal can be improved, make matrix material have better thermomechanical property and shape-memory properties.
The present invention has following advantage and effect relative to prior art:
(1) the present invention carries out surface treatment to carbon fiber, is beneficial to the dispersion of carbon fiber in composite material mixture, and make matrices of composite material have very strong interface cohesive force, the composite property obtained is excellent.
(2) the present invention uses the branched epoxy resin by using liquid crystal of carbon fiber modifying, can reduce costs, and improves the thermomechanical property of material.
(3) composite material of shape memory that prepared by the present invention has the high speed of response, high recovery stress, can be applied to the science and technology field such as bio-medical, aerospace.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
1) by length be chopped carbon fiber soaking and washing 100h in methylene dichloride of 1mm, then take out chopped carbon fiber and be placed in distilled water and soak 36h, then take out chopped carbon fiber in 80 DEG C of vacuum-drying 36h; Dried chopped carbon fiber is placed in concentrated nitric acid stirring and refluxing 2h at 100 DEG C, the chopped carbon fiber filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the chopped carbon fiber washing that obtains at 100 DEG C vacuum-drying 24h; Then the chopped carbon fiber after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide (DMF) reflux 3h, filter and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the chopped carbon fiber that solid trapped substance is chloride; Again the chopped carbon fiber of chloride is put into containing the DMAP (DMAP) of massfraction 0.5%, the triethylamine of massfraction 20% and 5% 4,24h is reacted in the tetrahydrofuran solution of 4-diaminodiphenyl-methane (DDM), then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, 100 DEG C of vacuum-drying 24h, obtain the chopped carbon fiber after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the chopped carbon fiber accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 0.5% after step (1) process, ultrasonic vibration 30min makes chopped carbon fiber be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 150 DEG C of solidification 7h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 2
1) by length be chopped carbon fiber soaking and washing 120h in methylene dichloride of 6mm, then take out chopped carbon fiber and be placed in distilled water and soak 40h, then take out chopped carbon fiber in 90 DEG C of vacuum-drying 30h; Dried chopped carbon fiber is placed in concentrated nitric acid stirring and refluxing 1.5h at 105 DEG C, the chopped carbon fiber filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the chopped carbon fiber washing that obtains at 100 DEG C vacuum-drying 24h; Then the chopped carbon fiber after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide (DMF) reflux 3h, filter and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the chopped carbon fiber that solid trapped substance is chloride; Again the chopped carbon fiber of chloride is put into containing the DMAP (DMAP) of massfraction 0.8%, the triethylamine of massfraction 25% and 8% 4,24h is reacted in the tetrahydrofuran solution of 4-diaminodiphenyl-methane (DDM), then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, 100 DEG C of vacuum-drying 24h, obtain the chopped carbon fiber after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the chopped carbon fiber accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 2% after step (1) process, ultrasonic vibration 30min makes chopped carbon fiber be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 78 DEG C of solidification 14h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 3
1) by length be chopped carbon fiber soaking and washing 140h in methylene dichloride of 12mm, then take out chopped carbon fiber and be placed in distilled water and soak 48h, then take out chopped carbon fiber in 100 DEG C of vacuum-drying 24h; Dried chopped carbon fiber is placed in concentrated nitric acid stirring and refluxing 1h at 110 DEG C, the chopped carbon fiber filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the chopped carbon fiber washing that obtains at 100 DEG C vacuum-drying 24h; Then the chopped carbon fiber after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide (DMF) reflux 3h, filter and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the chopped carbon fiber that solid trapped substance is chloride; Again the chopped carbon fiber of chloride is put into containing the DMAP (DMAP) of massfraction 1%, the triethylamine of massfraction 30% and 10% 4,24h is reacted in the tetrahydrofuran solution of 4-diaminodiphenyl-methane (DDM), then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, 100 DEG C of vacuum-drying 24h, obtain the chopped carbon fiber after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the chopped carbon fiber accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 5% after step (1) process, ultrasonic vibration 30min makes chopped carbon fiber be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 80 DEG C of solidification 12h, 170 DEG C of solidification 5h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 4
1) by length be chopped carbon fiber soaking and washing 120h in methylene dichloride of 1mm, then take out chopped carbon fiber and be placed in distilled water and soak 48h, then take out chopped carbon fiber in 100 DEG C of vacuum-drying 24h; The chopped carbon fiber taken out after vacuum-drying is placed in containing 1% massfraction amine epoxy resin solidifying agent 4, dispersion treatment in the acetone soln of 4-diamino thionyl benzene (DDS), again chopped carbon fiber is taken out the retort furnace putting into 600 DEG C and stop 30s, take out chopped carbon fiber acetone soln to wash, drying, obtains the chopped carbon fiber after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-1) and solidifying agent DDS, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the chopped carbon fiber accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 0.5% after step (1) process, ultrasonic vibration 30min makes chopped carbon fiber be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-1) molecular formula is:
Wherein, n=1.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 135 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 5
1) by length be chopped carbon fiber soaking and washing 120h in methylene dichloride of 6mm, then take out chopped carbon fiber and be placed in distilled water and soak 48h, then take out chopped carbon fiber in 100 DEG C of vacuum-drying 24h; The chopped carbon fiber taken out after vacuum-drying is placed in the acetone soln dispersion treatment containing 5% massfraction amine epoxy resin solidifying agent 4-aminophenyiamino sulfone, again chopped carbon fiber is taken out the retort furnace putting into 550 DEG C and stop 35s, take out chopped carbon fiber acetone soln to wash, drying, obtains the chopped carbon fiber after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-2) and solidifying agent 4-aminophenyiamino sulfone, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the chopped carbon fiber accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 5% after step (1) process, ultrasonic vibration 30min makes chopped carbon fiber be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-2) molecular formula is:
Wherein, n=2.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 115 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 6
1) by length be chopped carbon fiber soaking and washing 120h in methylene dichloride of 12mm, then take out chopped carbon fiber and be placed in distilled water and soak 48h, then take out chopped carbon fiber in 100 DEG C of vacuum-drying 24h; The chopped carbon fiber taken out after vacuum-drying is placed in containing 10% massfraction amine epoxy resin solidifying agent 4, dispersion treatment in the acetone soln of 4-diaminodiphenyl oxide, again chopped carbon fiber is taken out the retort furnace putting into 500 DEG C and stop 40s, take out chopped carbon fiber acetone soln to wash, drying, obtains the chopped carbon fiber after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-12) and solidifying agent 4,4-diaminodiphenyl oxide, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the chopped carbon fiber accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 10% after step (1) process, ultrasonic vibration 30min makes chopped carbon fiber be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-12) molecular formula is:
Wherein, n=12.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 45 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 7
1) by length be chopped carbon fiber soaking and washing 120h in methylene dichloride of 2mm, then take out chopped carbon fiber and be placed in distilled water and soak 48h, then take out chopped carbon fiber in 100 DEG C of vacuum-drying 24h, obtain the chopped carbon fiber after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-10) and solidifying agent methylresorcinol diamines, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the chopped carbon fiber accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 3% after step (1) process, ultrasonic vibration 30min makes chopped carbon fiber be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-10) molecular formula is:
Wherein, n=10.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 50 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 8
1) by 3K carbon fiber filament bundle soaking and washing 120h in methylene dichloride, then take out carbon fiber filament bundle and be placed in distilled water and soak 48h, then take out carbon fiber filament bundle in 100 DEG C of vacuum-drying 24h; The carbon fiber filament bundle taken out after vacuum-drying is placed in containing 3% massfraction amine epoxy resin solidifying agent 4, dispersion treatment in the acetone soln of 4-diaminodiphenyl-methane (DDM), again carbon fiber filament bundle is taken out the retort furnace putting into 600 DEG C and stop 30s, take out carbon fiber filament bundle acetone soln to wash, drying, obtains the carbon fiber filament bundle after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the carbon fiber filament bundle accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 40% after step (1) process again, soak 1h, ultrasonic vibration 30min makes carbon fiber filament bundle be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 9
1) by 6K carbon fiber filament bundle soaking and washing 120h in methylene dichloride, then take out carbon fiber filament bundle and be placed in distilled water and soak 48h, then take out carbon fiber filament bundle in 100 DEG C of vacuum-drying 24h; The carbon fiber filament bundle taken out after vacuum-drying is placed in the acetone soln dispersion treatment containing 3% massfraction amine epoxy resin curing agent ethylene diamine, again carbon fiber filament bundle is taken out the retort furnace putting into 600 DEG C and stop 30s, take out carbon fiber filament bundle acetone soln to wash, drying, obtains the carbon fiber filament bundle after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and curing agent ethylene diamine, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the carbon fiber filament bundle accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 20% after step (1) process again, soak 1h, ultrasonic vibration 30min makes carbon fiber filament bundle be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 10
1) by 12K carbon fiber filament bundle soaking and washing 120h in methylene dichloride, then take out carbon fiber filament bundle and be placed in distilled water and soak 48h, then take out carbon fiber filament bundle in 100 DEG C of vacuum-drying 24h; The carbon fiber filament bundle taken out after vacuum-drying is placed in the acetone soln dispersion treatment containing 3% massfraction amine epoxy resin solidifying agent methylresorcinol diamines, again carbon fiber filament bundle is taken out the retort furnace putting into 600 DEG C and stop 30s, take out carbon fiber filament bundle acetone soln to wash, drying, obtains the carbon fiber filament bundle after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent methylresorcinol diamines, dissolve in appropriate methylene dichloride, obtain mixed solution; Add the carbon fiber filament bundle accounting for branched epoxy resin by using liquid crystal, solidifying agent and carbon fiber total mass 10% after step (1) process again, soak 1h, ultrasonic vibration 30min makes carbon fiber filament bundle be uniformly dispersed in mixed solution, obtains composite material mixture;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) composite material mixture is slowly poured in the mould being sprayed with appropriate releasing agent, vacuumize 30 minutes under normal temperature to constant weight, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 11
1) by 300g specification carbon cloth soaking and washing 120h in methylene dichloride, then take out carbon cloth and be placed in distilled water and soak 48h, then take out carbon cloth in 100 DEG C of vacuum-drying 24h, obtain after processing carbon cloth.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM dissolves in appropriate methylene dichloride, obtain mixed solution; 30% carbon cloth accounting for branched epoxy resin by using liquid crystal, solidifying agent and the carbon fiber total mass after processing after step (1) being processed soaks 1h in mixed solution, and ultrasonic vibration 30min makes to mix;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) the carbon cloth uniform spreading after immersion is entered to be sprayed with in the mould of appropriate releasing agent, again mixed solution is slowly poured in mould, 30 minutes are vacuumized to constant weight under normal temperature, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 12
1) by 300g specification carbon cloth soaking and washing 120h in methylene dichloride, then take out carbon cloth and be placed in distilled water and soak 48h, then take out carbon cloth in 100 DEG C of vacuum-drying 24h; The carbon cloth taken out after vacuum-drying is placed in the acetone soln dispersion treatment containing 3% massfraction amine epoxy resin solidifying agent DDM, again carbon cloth is taken out the retort furnace putting into 600 DEG C and stop 30s, take out carbon cloth acetone soln to wash, dry, obtain the carbon cloth after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM dissolves in appropriate methylene dichloride, obtain mixed solution.30% carbon cloth accounting for branched epoxy resin by using liquid crystal, solidifying agent and the carbon fiber total mass after processing after step (1) being processed soaks 1h in mixed solution, and ultrasonic vibration 30min makes to mix;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) the carbon cloth uniform spreading after immersion is entered to be sprayed with in the mould of appropriate releasing agent, again mixed solution is slowly poured in mould, 30 minutes are vacuumized to constant weight under normal temperature, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 13
1) by 300g specification carbon cloth soaking and washing 120h in methylene dichloride, then take out carbon cloth and be placed in distilled water and soak 48h, then take out carbon cloth in 100 DEG C of vacuum-drying 24h; Dried carbon cloth is placed in concentrated nitric acid stirring and refluxing 2h at 105 DEG C, the carbon cloth filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the carbon cloth washing that obtains at 100 DEG C vacuum-drying 24h; Then the carbon cloth after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide (DMF) reflux 3h, filters and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the carbon cloth that solid trapped substance is chloride; Again the carbon cloth of chloride is put into containing the DMAP (DMAP) of massfraction 0.5%, the triethylamine of massfraction 20% and 5% 4, reaction 24h in the tetrahydrofuran solution of 4-diaminodiphenyl-methane (DDM), then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, 100 DEG C of vacuum-drying 24h, obtain the carbon cloth after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM dissolves in appropriate methylene dichloride, obtain mixed solution.30% carbon cloth accounting for branched epoxy resin by using liquid crystal, solidifying agent and the carbon fiber total mass after processing after step (1) being processed soaks 1h in mixed solution, and ultrasonic vibration 30min makes to mix;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) the carbon cloth uniform spreading after immersion is entered to be sprayed with in the mould of appropriate releasing agent, again mixed solution is slowly poured in mould, 30 minutes are vacuumized to constant weight under normal temperature, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 14
1) by 200g specification carbon cloth soaking and washing 120h in methylene dichloride, then take out carbon cloth and be placed in distilled water and soak 48h, then take out carbon cloth in 100 DEG C of vacuum-drying 24h; Dried carbon cloth is placed in concentrated nitric acid stirring and refluxing 2h at 105 DEG C, the carbon cloth filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the carbon cloth washing that obtains at 100 DEG C vacuum-drying 24h; Then the carbon cloth after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide (DMF) reflux 3h, filters and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the carbon cloth that solid trapped substance is chloride; Again the carbon cloth of chloride is put into containing the DMAP (DMAP) of massfraction 0.5%, the triethylamine of massfraction 20% and 5% 4, reaction 24h in the tetrahydrofuran solution of 4-diaminodiphenyl-methane (DDM), then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, 100 DEG C of vacuum-drying 24h, obtain the carbon cloth after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM dissolves in appropriate methylene dichloride, obtain mixed solution.20% carbon cloth accounting for branched epoxy resin by using liquid crystal, solidifying agent and the carbon fiber total mass after processing after step (1) being processed soaks 1h in mixed solution, and ultrasonic vibration 30min makes to mix;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) the carbon cloth uniform spreading after immersion is entered to be sprayed with in the mould of appropriate releasing agent, again mixed solution is slowly poured in mould, 30 minutes are vacuumized to constant weight under normal temperature, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 15
1) by 200g specification carbon cloth soaking and washing 120h in methylene dichloride, then take out carbon cloth and be placed in distilled water and soak 48h, then take out carbon cloth in 100 DEG C of vacuum-drying 24h; Dried carbon cloth is placed in concentrated nitric acid stirring and refluxing 2h at 105 DEG C, the carbon cloth filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the carbon cloth washing that obtains at 100 DEG C vacuum-drying 24h; Then the carbon cloth after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide (DMF) reflux 3h, filters and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the carbon cloth that solid trapped substance is chloride; Again the carbon cloth of chloride is put into containing the DMAP (DMAP) of massfraction 0.5%, the triethylamine of massfraction 20% and 5% 4, reaction 24h in the tetrahydrofuran solution of 4-diaminodiphenyl-methane (DDM), then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, 100 DEG C of vacuum-drying 24h, obtain the carbon cloth after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM dissolves in appropriate methylene dichloride, obtain mixed solution.30% carbon cloth accounting for branched epoxy resin by using liquid crystal, solidifying agent and the carbon fiber total mass after processing after step (1) being processed soaks 1h in mixed solution, and ultrasonic vibration 30min makes to mix;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) the carbon cloth uniform spreading after immersion is entered to be sprayed with in the mould of appropriate releasing agent, again mixed solution is slowly poured in mould, 30 minutes are vacuumized to constant weight under normal temperature, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Embodiment 16
1) by 200g specification carbon cloth soaking and washing 120h in methylene dichloride, then take out carbon cloth and be placed in distilled water and soak 48h, then take out carbon cloth in 100 DEG C of vacuum-drying 24h; Dried carbon cloth is placed in concentrated nitric acid stirring and refluxing 2h at 105 DEG C, the carbon cloth filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the carbon cloth washing that obtains at 100 DEG C vacuum-drying 24h; Then the carbon cloth after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide (DMF) reflux 3h, filters and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the carbon cloth that solid trapped substance is chloride; Again the carbon cloth of chloride is put into containing the DMAP (DMAP) of massfraction 0.5%, the triethylamine of massfraction 20% and 5% 4, reaction 24h in the tetrahydrofuran solution of 4-diaminodiphenyl-methane (DDM), then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, 100 DEG C of vacuum-drying 24h, obtain the carbon cloth after processing.
2) take branched epoxy resin by using liquid crystal 2,5-bis-that mol ratio is 2:1 [4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) and solidifying agent DDM dissolves in appropriate methylene dichloride, obtain mixed solution.40% carbon cloth accounting for branched epoxy resin by using liquid crystal, solidifying agent and the carbon fiber total mass after processing after step (1) being processed soaks 1h in mixed solution, and ultrasonic vibration 30min makes to mix;
Epoxy resin by using liquid crystal 2,5-bis-[4-(glycidyl ether) benzoyloxy] benzoic ether (EP-6) molecular formula is:
Wherein, n=6.
3) the carbon cloth uniform spreading after immersion is entered to be sprayed with in the mould of appropriate releasing agent, again mixed solution is slowly poured in mould, 30 minutes are vacuumized to constant weight under normal temperature, treat that solvent volatilizes, successively at 75 DEG C of solidification 16h, 160 DEG C of solidification 6h, 200 DEG C of solidification 1h, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material.
Carry out performance test to the product of embodiment and undressed epoxy resin by using liquid crystal, test result is as shown in table 1 and table 2:
Testing method
Dynamic thermo-mechanical property analyzes (NETZSCH5) two cantilever mode, temperature rise rate 5 DEG C/min ,-120 DEG C-250 DEG C, frequency 2Hz, amplitude 30 μm, dynamic force 5N, static force 0.5N.
Thermogravimetic analysis (TGA) (Pyris1TGAPE), nitrogen flow 20ml/min, temperature rise rate 10 DEG C/min, temperature range 40 ~ 800 DEG C.
Test result
The dynamic storage modulus of table 1 Liquid crystal epoxy resin-carbon fiber composite material
The resistance toheat of table 2 Liquid crystal epoxy resin-carbon fiber composite material
Can learn from test result, product Liquid crystal epoxy resin-carbon fiber composite material of the present invention all has obvious lifting than untreated epoxy resin by using liquid crystal in mechanical property and resistance toheat.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (7)
1. a preparation method for Liquid crystal epoxy resin-carbon fiber composite material, is characterized in that comprising the steps:
(1) surface treatment of carbon fibers, undertaken by the step of following a or b:
A, by carbon fiber soaking and washing 100 ~ 140h in methylene dichloride, then take out carbon fiber be placed in distilled water soak 36 ~ 48h, then take out carbon fiber in 80 ~ 100 DEG C of vacuum-drying 24 ~ 36h; The carbon fiber taken out after vacuum-drying is placed in the acetone soln dispersion treatment containing 1 ~ 10% massfraction amine epoxy resin solidifying agent, again carbon fiber is taken out the retort furnace putting into 500 ~ 600 DEG C and stop 30 ~ 40s, take out carbon fiber acetone soln to wash, drying, obtains the carbon fiber after processing;
B, by carbon fiber soaking and washing 100 ~ 140h in methylene dichloride, then take out carbon fiber be placed in distilled water soak 36 ~ 48h, then take out carbon fiber in 80 ~ 100 DEG C of vacuum-drying 24 ~ 36h; Dried carbon fiber is placed in concentrated nitric acid stirring and refluxing 1 ~ 2h at 100 ~ 110 DEG C, the carbon fiber filtered to reflux 24h with distilled water at 100 DEG C again, filters, by after the carbon fiber washing that obtains at 100 DEG C vacuum-drying 24h; Then the carbon fiber after vacuum-drying is placed in thionyl chloride, after adding catalyzer dimethyl formamide reflux 2 ~ 3h, filters and with tetrahydrofuran (THF) washing to remove excessive thionyl chloride, obtain the carbon fiber that solid trapped substance is chloride; The tetrahydrofuran solution put into by the carbon fiber of chloride containing the amine epoxy resin solidifying agent of the DMAP of massfraction 0.5 ~ 1%, the triethylamine of massfraction 20 ~ 30% and massfraction 5 ~ 10% reacts 24h again, then tetrahydrofuran (THF), acetone, methylene dichloride, distilled water wash is used successively, vacuum-drying 24h at 100 DEG C again, obtains the carbon fiber after processing;
(2) composite material mixture preparation: take branched epoxy resin by using liquid crystal and solidifying agent that mol ratio is 2:1, be dissolved in methylene dichloride, obtain mixed solution; Add the carbon fiber after step (1) process again, ultrasonic vibration makes carbon fiber dispersed in mixed solution, obtains composite material mixture;
(3) curing molding: composite material mixture poured in mould, is evacuated to constant weight under normal temperature, and treat that solvent evaporates is complete, stage curing, die sinking, obtains Liquid crystal epoxy resin-carbon fiber composite material;
Branched epoxy resin by using liquid crystal structural formula described in step (2) is as shown in Equation 1:
Wherein, n is the integer of 1 ~ 12;
Solidifying agent described in step (2) is more than one of 4,4-diaminodiphenyl-methane, 4-aminophenyiamino sulfone, 4,4-diaminodiphenyl oxides, 4,4-diamino thionyl benzenes, methylresorcinol diamines and quadrol.
2. the preparation method of Liquid crystal epoxy resin-carbon fiber composite material according to claim 1, it is characterized in that: described amine epoxy resin solidifying agent is 4,4-diaminodiphenyl-methane, 4-aminophenyiamino sulfone, 4, more than one of 4-diaminodiphenyl oxide, 4,4-diamino-phenyl sulfoxides, methylresorcinol diamines and quadrol.
3. the preparation method of Liquid crystal epoxy resin-carbon fiber composite material according to claim 1 and 2, is characterized in that: step (1) described carbon fiber is PAN-based carbon fiber or asphalt base carbon fiber.
4. the preparation method of Liquid crystal epoxy resin-carbon fiber composite material according to claim 1 and 2, it is characterized in that: step (1) described carbon fiber is the chopped carbon fiber of length 1 ~ 12mm, the carbon fiber filament bundle of 3K, 6K, 12K or the unidirectional or two-way twill carbon cloth of 200g, 300g specification.
5. the preparation method of Liquid crystal epoxy resin-carbon fiber composite material according to claim 4, it is characterized in that: when step (1) described carbon fiber is the chopped carbon fiber of length 1 ~ 12mm, the consumption of the carbon fiber after step (3) described process is 0.5 ~ 5% of the carbon fiber total mass after accounting for branched epoxy resin by using liquid crystal, solidifying agent and process;
When step (1) described carbon fiber is the carbon fiber filament bundle of 3K, 6K, 12K, the consumption of the carbon fiber after step (3) described process is 10 ~ 40% of the carbon fiber total mass after accounting for branched epoxy resin by using liquid crystal, solidifying agent and process;
When the unidirectional or two-way twill carbon cloth that step (1) described carbon fiber is 200g, 300g specification, the consumption of the carbon fiber after step (3) described process is 20 ~ 40% of the carbon fiber total mass after accounting for branched epoxy resin by using liquid crystal, solidifying agent and process.
6. the preparation method of Liquid crystal epoxy resin-carbon fiber composite material according to claim 1, it is characterized in that: the described stage curing concrete operations of step (3) for: first under the condition higher than the branched epoxy resin by using liquid crystal second-order transition temperature 5 ~ 10 DEG C described in step (2), solidify 12 ~ 16h, at 150 ~ 170 DEG C, solidify 5 ~ 7h again, then at 200 DEG C, solidify 1h.
7. the Liquid crystal epoxy resin-carbon fiber composite material prepared by the preparation method described in any one of claim 1 ~ 6.
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| CN103965583B (en) * | 2014-04-28 | 2016-04-13 | 中科院广州化学有限公司南雄材料生产基地 | A kind of shape memory epoxy resin by using liquid crystal-glass fibre-silicon dioxide composite material and preparation method thereof |
| CN104479296B (en) * | 2014-12-24 | 2017-01-11 | 芜湖市汽车产业技术研究院有限公司 | Method for improving impact strength of epoxy resin/carbon fiber composite material |
| CN106589809B (en) * | 2015-10-19 | 2019-02-15 | 张家港市舜辰机械有限公司 | A kind of preparation method of carbon fiber/epoxy resin composite material |
| CN107880490B (en) * | 2017-11-29 | 2019-09-13 | 哈尔滨工业大学 | A kind of thermosetting epoxy resin based composites preparation method suitable for 4D printing |
| CN111635617A (en) * | 2020-06-22 | 2020-09-08 | 合肥工业大学 | Preparation method for improving conductivity of composite material epoxy resin matrix |
| CN112537057A (en) * | 2020-11-26 | 2021-03-23 | 湖南碳谷新材料有限公司 | Carbon-carbon support ring preparation mold and preparation method |
| CN113278258A (en) * | 2021-06-30 | 2021-08-20 | 山东大学 | Bending-resistant mesophase pitch carbon fiber composite heat dissipation film and preparation method and application thereof |
| CN115703892A (en) * | 2021-08-09 | 2023-02-17 | 中南民族大学 | High-performance degradable epoxy resin-carbon fiber composite material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101186742A (en) * | 2007-11-14 | 2008-05-28 | 哈尔滨工业大学 | Shape memory composite material and preparation method thereof |
| CN101195701A (en) * | 2007-11-09 | 2008-06-11 | 中国科学院广州化学研究所 | Epoxy resin shape memory polymer material and method for producing the same |
| CN102153833A (en) * | 2010-09-20 | 2011-08-17 | 青岛科技大学 | Carbon fiber (powder)/epoxy resin composite material used for rapid prototyping die |
| WO2013051404A1 (en) * | 2011-10-04 | 2013-04-11 | 東レ株式会社 | Carbon fiber-reinforced thermoplastic resin composition, molding material, prepreg, and methods for producing same |
-
2013
- 2013-10-31 CN CN201310535143.8A patent/CN103602042B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195701A (en) * | 2007-11-09 | 2008-06-11 | 中国科学院广州化学研究所 | Epoxy resin shape memory polymer material and method for producing the same |
| CN101186742A (en) * | 2007-11-14 | 2008-05-28 | 哈尔滨工业大学 | Shape memory composite material and preparation method thereof |
| CN102153833A (en) * | 2010-09-20 | 2011-08-17 | 青岛科技大学 | Carbon fiber (powder)/epoxy resin composite material used for rapid prototyping die |
| WO2013051404A1 (en) * | 2011-10-04 | 2013-04-11 | 東レ株式会社 | Carbon fiber-reinforced thermoplastic resin composition, molding material, prepreg, and methods for producing same |
Non-Patent Citations (4)
| Title |
|---|
| Anisotropically ordered liquid crystalline epoxy network on carbon fiber surface;Jun Yeob lee et;《Polymer Bulletin》;20070330;第13页第2段，第14页1.2实验方法 * |
| Composites based on carbon fibers and liquid crystalline epoxy resin,2 Dynamic-mechanical analysis and fracture toughness behavior;Cosimo Carfagna.et;《Macromolecular Chemistry and Physics》;20001231;实验部分 * |
| Transverse Alignment of Liquid Crystalline Epoxy Resin on Carbon Fiber Surface;Jun Yeob Lee;《Journal of Applied Polymer Science》;20061231;第684页实验部分第1-5行，第685页的表面处理过程，第689页的结论部分 * |
| 碳纤维表面改性研究;殷永霞等;《航天返回与遥感》;20040331;第25卷(第2期);第52页第2列第8-14行 * |
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