CN104356598A - Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene - Google Patents
Modified graphene, preparation method thereof and composite material comprising epoxy resin enhanced by modified graphene Download PDFInfo
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- CN104356598A CN104356598A CN201410611914.1A CN201410611914A CN104356598A CN 104356598 A CN104356598 A CN 104356598A CN 201410611914 A CN201410611914 A CN 201410611914A CN 104356598 A CN104356598 A CN 104356598A
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Abstract
The invention aims to provide an alkali modified graphene and a method for preparing a composite epoxy resin material with the graphene. The method comprises the following steps: the graphene is processed by using a mixed solution of a hydrogen peroxide solution and an ammonia solution, and the surface grafting modification of the graphene is realized, so that the modified graphene is homogeneously dispersed in an epoxy resin matrix, and the composite epoxy resin material enhanced by the graphene, with excellent mechanical property, can be prepared.
Description
Technical field
The present invention relates to Graphene modification field, particularly relate to a kind of method of basic cpd modified graphene, and the epoxy resin composite material strengthened.
Background technology
Since Graphene (graphene) this material in 2004 is found, about research and news were not just interrupted.Graphene is a kind of carbonaceous novel material of carbon atom tightly packed one-tenth individual layer bi-dimensional cellular shape crystalline network, the thickness of this Graphene crystal film only has 0.335nm, be only hair diameter 200,000/, it is the material that on current the known world, intensity is the highest, be the elementary cell building other dimension carbonaceous material (as zero dimension soccerballene, one dimension carbon nanotube, three-dimensional graphite), there is fabulous crystallinity and electric property.This material not only can be used for developing and produce ultra light aircraft material thin as the scraps of paper, manufactures the tough and tensile flak jackets of excess of export, and 2.3 ten thousand miles that scientist even can be allowed to dream of long space elevators become a reality.Similar with Single Walled Carbon Nanotube (SWCNT), Graphene has the excellent performance such as heat, power, electricity.
The key point preparing high performance Graphene/epoxy resin composite material with how when filling Graphene, it to be dispersed in epoxy resin-base uniformly.The method that present raising obturator disperses in the base mainly improves the interface binding power between obturator and matrix.Have much about the report improving interface binding power with acid modification Graphene at present, but seldom have about the report with alkali modification Graphene.
Summary of the invention
Technical problem to be solved by this invention there is provided a kind of alkali modification Graphene and prepares the method for Graphene epoxy resin composite material, achieve the homogeneous dispersion of modified graphene in epoxy resin-base, thus the Graphene epoxy resin composite material with excellent mechanical performance can be prepared.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
Step one, joins in the mixing solutions of hydrogen peroxide and ammoniacal liquor, supersound process at a certain temperature by Graphene, dilute with appropriate deionized water, then filter with sand core funnel and wash to neutral, product being placed in vacuum drying oven and drying, obtained surface-treated Graphene.
Step 2, in the process preparing matrix material, epoxy resin, solidifying agent and promotor mix according to certain mass ratio.First, take 49.0g solidifying agent, 70g epoxy resin (E-51), then modified graphene is taken according to epoxy resin, solidifying agent and promotor total mass certain proportion, Graphene is joined in the mixing solutions of solidifying agent and the epoxy resin taken, then the permanent stirred in water bath putting into 60 DEG C is even, and then is that 600W ultrasonic wave separating apparatus carries out supersound process 3h with power.
After supersound process terminates, 0.7g promotor is joined in mixed solution, to stir after 10min ultrasonic half hour again with glass stick.Put it in vacuum drying oven 60 DEG C, get rid of bubble 0.5h under-0.1MPa.After getting rid of bubble, taken out to be poured into and coated releasing agent and in the mould of preheating, stretch consistent with GB2568-811 and GB2570-81 standard respectively with the size of bend specimen mould, put into baking oven to be heating and curing, the condition of solidification is 90 DEG C of insulation 1h, 130 DEG C of constant temperature 2h, 160 DEG C of constant temperature 2h, then naturally cooling in an oven.
The further preferred version of the present invention is: the ratio of described ammoniacal liquor and hydrogen peroxide is 1 ~ 4: 1.
The further preferred version of the present invention is: the ratio of described Graphene and alkali mixing solutions is 0.001 ~ 0.01g/ml.
The further preferred version of the present invention is: described ultrasonic time is 2 ~ 8 hours.
The further preferred version of the present invention is: described ultrasonic temperature is 30 ~ 60 DEG C.
The further preferred version of the present invention is: described epoxy resin, solidifying agent and promotor are the mass mixing of the proportioning of 100: 50 ~ 80: 1 according to mass ratio
The further preferred version of the present invention is: the ratio that the quality that described Graphene adds accounts for total mass is 005% ~ 1%.
The method that the present invention adopts only just need can obtain modified graphene through mixing, ultrasonic, washing process, has the features such as technique is simple, material preparation cost is low, free from environmental pollution, easily realizes preparing on a large scale.
The present invention, owing to adopting modified graphene as the standby matrix material of filling system, has higher tensile strength and flexural strength.By Mechanics Performance Testing, when Graphene addition is 1%, the tensile strength of matrix material reaches 67.28Mpa, and flexural strength reaches 135.58Mpa.
Accompanying drawing explanation
Infrared spectrogram (FTIR) figure of accompanying drawing 1 modified graphene.
The matrix material tensile strength figure of the different modified graphene addition of accompanying drawing 2.
The matrix material flexural strength figure of the different modified graphene addition of accompanying drawing 3.
Accompanying drawing 4 fracture of composite materials Surface scan Electronic Speculum (SEM) photo.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be described in more detail
Embodiment 1
Step one, joins in the mixing solutions that 400ml hydrogen peroxide and ammoniacal liquor 1: 1 forms, supersound process 2h at 30 DEG C by 0.4g Graphene, dilute with appropriate deionized water, then filter with sand core funnel and wash to neutral, product being placed in vacuum drying oven and drying, obtained surface-treated Graphene.
Step 2, in the process preparing matrix material, epoxy resin, solidifying agent and promotor are the mass mixing of the proportioning of 100: 50: 1 according to mass ratio.First, take 49.0g solidifying agent, 70g epoxy resin (E-51), then modified graphene is taken according to 0.05% of epoxy resin, solidifying agent and promotor total mass, Graphene is joined in the mixing solutions of solidifying agent and the epoxy resin taken, then the permanent stirred in water bath putting into 600C is even, and then is that 600W ultrasonic wave separating apparatus carries out supersound process 3h with power.
After supersound process terminates, 0.7g promotor is joined in mixed solution, to stir after 10min ultrasonic half hour again with glass stick.Put it in vacuum drying oven 60 DEG C, get rid of bubble 0.5h under-0.1MPa.After getting rid of bubble, taken out to be poured into and coated releasing agent and in the mould of preheating, stretch consistent with GB2568-811 and GB2570-81 standard respectively with the size of bend specimen mould, put into baking oven to be heating and curing, the condition of solidification is 90 DEG C of insulation 1h, 130 DEG C of constant temperature 2h, 160 DEG C of constant temperature 2h, then naturally cooling in an oven.
Embodiment 2
Step one, joins in the mixing solutions that 400ml hydrogen peroxide and ammoniacal liquor 2: 1 forms, supersound process 4h at 40 DEG C by 0.6g Graphene, dilute with appropriate deionized water, then filter with sand core funnel and wash to neutral, product being placed in vacuum drying oven and drying, obtained surface-treated Graphene.
Step 2, in the process preparing matrix material, epoxy resin, solidifying agent and promotor are the mass mixing of the proportioning of 100: 60: 1 according to mass ratio.First, take 49.0g solidifying agent, 70g epoxy resin (E-51), then modified graphene is taken according to 0.1% of epoxy resin, solidifying agent and promotor total mass, Graphene is joined in the mixing solutions of solidifying agent and the epoxy resin taken, then the permanent stirred in water bath putting into 60 DEG C is even, and then is that 600W ultrasonic wave separating apparatus carries out supersound process 3h with power.
After supersound process terminates, 0.7g promotor is joined in mixed solution, to stir after 10min ultrasonic half hour again with glass stick.Put it in vacuum drying oven 60 DEG C, get rid of bubble 0.5h under-0.1MPa.After getting rid of bubble, taken out to be poured into and coated releasing agent and in the mould of preheating, stretch consistent with GB2568-811 and GB2570-81 standard respectively with the size of bend specimen mould, put into baking oven to be heating and curing, the condition of solidification is 90 DEG C of insulation 1h, 130 DEG C of constant temperature 2h, 160 DEG C of constant temperature 2h, then naturally cooling in an oven.
Embodiment 3
Step one, joins in the mixing solutions that 400ml hydrogen peroxide and ammoniacal liquor 3: 1 forms, supersound process 6h at 50 DEG C by 0.8g Graphene, dilute with appropriate deionized water, then filter with sand core funnel and wash to neutral, product being placed in vacuum drying oven and drying, obtained surface-treated Graphene.
Step 2, in the process preparing matrix material, epoxy resin, solidifying agent and promotor are the mass mixing of the proportioning of 100: 70: 1 according to mass ratio.First, take 49.0g solidifying agent, 70g epoxy resin (E-51), then modified graphene is taken according to 0.5% of epoxy resin, solidifying agent and promotor total mass, Graphene is joined in the mixing solutions of solidifying agent and the epoxy resin taken, then the permanent stirred in water bath putting into 60 DEG C is even, and then is that 600W ultrasonic wave separating apparatus carries out supersound process 3h with power.
After supersound process terminates, 0.7g promotor is joined in mixed solution, to stir after 10min ultrasonic half hour again with glass stick.Put it in vacuum drying oven 60 DEG C, get rid of bubble 0.5h under-0.1MPa.After getting rid of bubble, taken out to be poured into and coated releasing agent and in the mould of preheating, stretch consistent with GB2568-811 and GB2570-81 standard respectively with the size of bend specimen mould, put into baking oven to be heating and curing, the condition of solidification is 90 DEG C of insulation 1h, 130 DEG C of constant temperature 2h, 160 DEG C of constant temperature 2h, then naturally cooling in an oven.
Embodiment 4
Step one, joins in the mixing solutions that 400ml hydrogen peroxide and ammoniacal liquor 4: 1 forms, supersound process 8h at 60 DEG C by 1g Graphene, dilute with appropriate deionized water, then filter with sand core funnel and wash to neutral, product being placed in vacuum drying oven and drying, obtained surface-treated Graphene.
Step 2, in the process preparing matrix material, epoxy resin, solidifying agent and promotor are the mass mixing of the proportioning of 100: 80: 1 according to mass ratio.First, take 49.0g solidifying agent, 70g epoxy resin (E-51), then modified graphene is taken according to 1% of epoxy resin, solidifying agent and promotor total mass, Graphene is joined in the mixing solutions of solidifying agent and the epoxy resin taken, then the permanent stirred in water bath putting into 60 DEG C is even, and then is that 600W ultrasonic wave separating apparatus carries out supersound process 3h with power.
After supersound process terminates, 0.7g promotor is joined in mixed solution, to stir after 10min ultrasonic half hour again with glass stick.Put it in vacuum drying oven 60 DEG C, get rid of bubble 0.5h under-0.1MPa.After getting rid of bubble, taken out to be poured into and coated releasing agent and in the mould of preheating, stretch consistent with GB2568-811 and GB2570-81 standard respectively with the size of bend specimen mould, put into baking oven to be heating and curing, the condition of solidification is 90 DEG C of insulation 1h, 130 DEG C of constant temperature 2h, 160 DEG C of constant temperature 2h, then naturally cooling in an oven.
Below the preferred embodiments of the present invention are illustrated, but the present invention is not limited to described embodiment, those of ordinary skill in the art also can make all equivalent modification or replacement under the prerequisite without prejudice to spirit of the present invention, and these equivalent modification or replacement are all included in the application's claim limited range.
Claims (7)
1. prepare claim modified graphene and prepare the method for modified graphene epoxy resin composite material, it is characterized in that obtaining by following method:
Step one, joins in the mixing solutions of hydrogen peroxide and ammoniacal liquor, supersound process at a certain temperature by Graphene, dilute with appropriate deionized water, then filter with sand core funnel and wash to neutral, product being placed in vacuum drying oven and drying, obtained surface-treated Graphene.
Step 2, in the process preparing matrix material, epoxy resin, solidifying agent and promotor mix according to certain mass ratio.First, take solidifying agent, epoxy resin (E-51), then modified graphene is taken according to epoxy resin, solidifying agent and promotor total mass certain proportion, Graphene is joined in the mixing solutions of solidifying agent and the epoxy resin taken, then the permanent stirred in water bath putting into 60 DEG C is even, and then is that 600W ultrasonic wave separating apparatus carries out supersound process 3h with power.
After supersound process terminates, promotor is joined in mixed solution, to stir after 10min ultrasonic half hour again with glass stick.Put it in vacuum drying oven 60 DEG C, get rid of bubble 0.5h under-0.1MPa.After getting rid of bubble, taken out to be poured into and coated releasing agent and in the mould of preheating, stretch consistent with GB2568-811 and GB2570-81 standard respectively with the size of bend specimen mould, put into baking oven to be heating and curing, the condition of solidification is 90 DEG C of insulation 1h, 130 DEG C of constant temperature 2h, 160 DEG C of constant temperature 2h, then naturally cooling in an oven.
2. preparation method according to claim 1, it is characterized in that, the ratio of described ammoniacal liquor and hydrogen peroxide is 1 ~ 4: 1.
3. preparation method according to claim 1, it is characterized in that, described ultrasonic time is 2 ~ 8 hours.
4. preparation method according to claim 1, it is characterized in that, the ratio of described Graphene and alkali mixing solutions is 0.001 ~ 0.01g/ml.
5. preparation method according to claim 1, it is characterized in that, described ultrasonic time is 2 ~ 8 hours.
6. preparation method according to claim 1, it is characterized in that, described epoxy resin, solidifying agent and promotor are the mass mixing of the proportioning of 100: 50 ~ 80: 1 according to mass ratio.
7. preparation method according to claim 1, is characterized in that, the ratio that the quality that described Graphene adds accounts for total mass is 0.05% ~ 1%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104830027A (en) * | 2015-05-20 | 2015-08-12 | 叶芳 | Method for preparing novel epoxy resin laminated composite material for sports equipment |
| CN104861910A (en) * | 2015-05-20 | 2015-08-26 | 北京化工大学 | Graphene-coated inorganic filler and epoxy resin composite adhesive and preparation method thereof |
| US20180366624A1 (en) * | 2017-05-12 | 2018-12-20 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Led packaging material and manufacturing method of the same |
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| CN102153835A (en) * | 2011-03-15 | 2011-08-17 | 北京航空航天大学 | Modified graphene/epoxy resin composite material and preparation method thereof |
| CN102286189A (en) * | 2011-06-24 | 2011-12-21 | 中国科学院理化技术研究所 | Method for preparing graphene oxide/epoxide resin nano composite material |
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Patent Citations (2)
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| CN102153835A (en) * | 2011-03-15 | 2011-08-17 | 北京航空航天大学 | Modified graphene/epoxy resin composite material and preparation method thereof |
| CN102286189A (en) * | 2011-06-24 | 2011-12-21 | 中国科学院理化技术研究所 | Method for preparing graphene oxide/epoxide resin nano composite material |
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| MYKOLA SEREDYCH ET.AL: "Mechanism of ammonia retention on graphite oxides: role of surface chemistry and structure", 《J.PHYS.CHEM.C》 * |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104830027A (en) * | 2015-05-20 | 2015-08-12 | 叶芳 | Method for preparing novel epoxy resin laminated composite material for sports equipment |
| CN104861910A (en) * | 2015-05-20 | 2015-08-26 | 北京化工大学 | Graphene-coated inorganic filler and epoxy resin composite adhesive and preparation method thereof |
| US20180366624A1 (en) * | 2017-05-12 | 2018-12-20 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | Led packaging material and manufacturing method of the same |
| US10418531B2 (en) * | 2017-05-12 | 2019-09-17 | Shenzhen China Star Optoelectronics Technology Co., Ltd. | LED packaging material and manufacturing method of the same |
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