CN105400141A - Preparation method of carbon nano tube doped TiO<2>/ epoxy hybridization fiberglass composite - Google Patents
Preparation method of carbon nano tube doped TiO<2>/ epoxy hybridization fiberglass composite Download PDFInfo
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- CN105400141A CN105400141A CN201510884096.7A CN201510884096A CN105400141A CN 105400141 A CN105400141 A CN 105400141A CN 201510884096 A CN201510884096 A CN 201510884096A CN 105400141 A CN105400141 A CN 105400141A
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Abstract
The invention discloses a preparation method of a carbon nano tube doped TiO<2>/ epoxy hybridization fiberglass composite. The preparation method includes the steps that tetrabutyl titanate serves as a precursor, acetylacetone serves as a complexing agent, absolute ethyl alcohol serves as solvent, carbonic acid n-butyl ester and distilled water are made to be subjected to hydrolysis, concentrated nitric acid serves as stabilizer, and TiO<2> sol is prepared; a processed carbon nano tube is doped into the sol, stirring is conducted, heating is conducted for removing most of the solvent, and stable gel is obtained; epoxy resin, a curing agent and an accelerant are added to the obtained gel, uniform stirring is conducted, a fiberglass resin base body is obtained, and fiberglass is prepared through a hand molding method; an obtained sample is heated for 1 hour at the temperature of 400 DEG C, and the carbon nano tube doped TiO<2>/ epoxy hybridization fiberglass composite is obtained. The fiberglass composite still has certain mechanical properties after treatment at the temperature of 400 DEG C, while ordinary fiberglass can only be used at the temperature lower than 60 DEG C. The carbon nano tube is introduced into the composite, and the mechanical and electrical performance of the composite is improved.
Description
Technical field
The present invention relates to hybrid composite material preparing technical field, particularly relate to a kind of carbon nano tube-doped TiO
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material.
Background technology
Simple glass steel heat resistance is poor, and use temperature is not generally higher than 60 DEG C, and poor electric conductivity, usually occur in electrostatic precipitator.Main purpose of the present invention is the heat resisting temperature improving glass reinforced plastic, improves its mechanics, electric property.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides carbon nano tube-doped TiO
2the preparation scheme of/epoxy hybrid glass fiber reinforced plastics composite material.By inorganic phase TiO
2add, improve the resistance to elevated temperatures of glass reinforced plastic, modified carbon nano-tube add the electricity and mechanical property of improving material.
The present invention adopts following technical scheme:
Carbon nano tube-doped TiO of the present invention
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material take tetrabutyl titanate as presoma, and methyl ethyl diketone is complexing agent, and obtain tetrabutyl titanate and the distilled water generation hydrolysis reaction of modification, dehydrated alcohol is solvent, and concentrated nitric acid is stablizer, preparation TiO
2colloidal sol.
The amount of substance of tetrabutyl titanate, methyl ethyl diketone, concentrated nitric acid, than being 1:1:0.3, works as metatitanic acid
When positive butyl ester is 17ml, dehydrated alcohol is 100ml.
To the carbon nanotube of direct facture process be adopted to mix wherein, tetrabutyl titanate be 1:0.005 with the ratio of the amount of substance of carbon nanotube.
The direct treatment step of carbon nanotube is:
1. the organo silane coupling agent for carbon nanotube (CNTs) 0.5wt%-1.0wt% is joined in 2-5 alcohol solution (water/alcohol=1/9) doubly, completely to be mixed after dispersion;
2. the CNTs of 5g is loaded in agitator;
3. at room temperature, limit uniform stirring CNTs, while add the alcohol solution of the organo silane coupling agent of aforementioned preparation in 10 minutes;
4. after treating that the alcohol solution of organo silane coupling agent all adds, then mechanical stirring mixes 12 hours;
5. again by the temperature of steel basin by 50 DEG C of gradient increased temperatures to 100 DEG C, each raise 10 DEG C, at 70 DEG C, the 80 DEG C each heating 1h in place, at all the other temperature, respectively heat 0.5h;
6. after being then down to room temperature, then drying is carried out.
Stirred through 24 hours, 70 DEG C add heat abstraction solvent, obtain stable gel;
Epoxy resin, curing agent ethyl methyl ketone, promotor cobalt naphthenate are added respectively in gained gel, stir, epoxy resin, solidifying agent, promotor are 1:0.01:0.01:1 with the ratio of the amount of substance of tetrabutyl titanate.Obtain fiber glass resin matrix, hand sticks with paste legal system for glass reinforced plastic;
Gained sample, in 400 DEG C of heating 1 hour, obtains nanotube doped Ti O
2/ epoxy hybrid glass fiber reinforced plastics composite material.
Carbon nano tube-doped TiO of the present invention
2the concrete steps of the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material are as follows:
First by presoma tetrabutyl titanate and the mixing of complexing agent methyl ethyl diketone, stir 1h, obtain tetrabutyl titanate and the distilled water generation hydrolysis reaction of modification, then add solvent dehydrated alcohol, the ethanolic soln slowly dripping distilled water and stablizer concentrated nitric acid, stir 6h, obtain TiO
2colloidal sol;
TiO is mixed by adopting the carbon nanotube of direct facture process
2in colloidal sol, stirring at room temperature 24 hours, obtains carbon nano tube-doped TiO
2colloidal sol, then dry 4h at 70 DEG C, obtain stable gel;
Epoxy resin, solidifying agent, promotor are added respectively in gained gel, stir, obtain fiber glass resin matrix, hand sticks with paste legal system for glass reinforced plastic;
By gained glass reinforced plastic in 400 DEG C of heating 1 hour, obtain nanotube doped Ti O
2/ epoxy hybrid glass fiber reinforced plastics composite material.
The amount of substance of distilled water and tetrabutyl titanate is than being 2:1, and the ethanolic soln of distilled water is that 1:2 is formulated by volume by distilled water and dehydrated alcohol.
Compared with prior art, the invention has the beneficial effects as follows: gained glass fiber reinforced plastics composite material still has certain mechanical property after 400 DEG C of process, and common glass reinforced plastic can only lower than 60 DEG C of uses.Introduce carbon nanotube in this material, improve the mechanics of material, electric property.
Accompanying drawing explanation
Fig. 1 is the carbon nano tube-doped TiO of Sol-gel technique
2the technical process of/epoxy hybrid glass fiber reinforced plastics composite material;
Fig. 2 is the different Ti O obtained after 400 DEG C of process
2the carbon nano tube-doped TiO of content
2/ epoxy hybrid glass fiber reinforced plastics composite material.
Embodiment
The following examples describe in further detail of the present invention.
Embodiment 1
As shown in Figure 1, carbon nano tube-doped TiO of the present invention
2the concrete steps of the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material are as follows:
First by presoma tetrabutyl titanate and the mixing of complexing agent methyl ethyl diketone, stir 1h, obtain tetrabutyl titanate and the distilled water generation hydrolysis reaction of modification, then add solvent dehydrated alcohol and stablizer concentrated nitric acid, stir 6h, obtain TiO
2colloidal sol;
TiO is mixed by adopting the carbon nanotube of direct facture process
2in colloidal sol, stirring at room temperature 24 hours, obtains carbon nano tube-doped TiO
2colloidal sol, then dry 4h at 70 DEG C, obtain stable gel;
Epoxy resin, solidifying agent, promotor are added respectively in gained gel, stir, obtain fiber glass resin matrix, hand sticks with paste legal system for glass reinforced plastic;
By gained glass reinforced plastic in 400 DEG C of heating 1 hour, obtain nanotube doped Ti O
2/ epoxy hybrid glass fiber reinforced plastics composite material.
Distilled water is 2:1 with the amount of substance ratio of tetrabutyl titanate.
The amount of substance of tetrabutyl titanate, methyl ethyl diketone, concentrated nitric acid, than being 1:1:0.3, works as metatitanic acid
When positive butyl ester is 17ml, dehydrated alcohol is 100ml.
To the carbon nanotube of direct facture process be adopted to mix wherein, tetrabutyl titanate be 1:0.005 with the ratio of the amount of substance of carbon nanotube.
Solidifying agent and promotor are methylethylketone and cobalt naphthenate respectively.
Epoxy resin, solidifying agent, promotor are 1:0.01:0.01:1 with the ratio of the amount of substance of tetrabutyl titanate.
The direct treatment step of carbon nanotube is:
1. the organo silane coupling agent for carbon nanotube (CNTs) 0.5wt%-1.0wt% is joined in 2-5 alcohol solution (water/alcohol=1/9) doubly, completely to be mixed after dispersion;
2. the CNTs of 5g is loaded in agitator;
3. at room temperature, limit uniform stirring CNTs, while add the alcohol solution of the organo silane coupling agent of aforementioned preparation in 10 minutes;
4. after treating that the alcohol solution of organo silane coupling agent all adds, then mechanical stirring mixes 12 hours;
5. again by the temperature of steel basin by 50 DEG C of gradient increased temperatures to 100 DEG C, each raise 10 DEG C, at 70 DEG C, the 80 DEG C each heating 1h in place, at all the other temperature, respectively heat 0.5h;
6. after being then down to room temperature, then drying is carried out.
For the matrix material obtained, its resistance toheat is confirmed in material preparation process, and sinter 1 hour through 400 DEG C, material is still complete.Gained matrix material is measured respectively on surface resistivity tester, universal testing machine electricity and the mechanical property of sample, acquired results is as shown in table 1:
Table 1
As can be seen from Table 1, CNTs adds, and improves mechanics and the electric property of material, inorganic component TiO
2compound, improve the thermotolerance of material.
Although illustrate and describe embodiments of the invention, for the ordinary skill in the art, be appreciated that and can carry out multiple change, amendment, replacement and modification to these embodiments without departing from the principles and spirit of the present invention, scope of the present invention is by claims and equivalents thereof.
Claims (8)
1. a carbon nano tube-doped TiO
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: described method take tetrabutyl titanate as presoma, and methyl ethyl diketone is complexing agent, and dehydrated alcohol is solvent, and concentrated nitric acid is stablizer, preparation TiO
2colloidal sol; To the carbon nanotube of direct facture process be adopted to mix wherein, stirred through 24 hours, 70 DEG C add heat abstraction solvent, obtain stable gel;
Epoxy resin, solidifying agent, promotor are added respectively in gained gel, stir, obtain fiber glass resin matrix, hand sticks with paste legal system for glass reinforced plastic;
Gained sample, in 400 DEG C of heating 1 hour, obtains nanotube doped Ti O
2/ epoxy hybrid glass fiber reinforced plastics composite material.
2. carbon nano tube-doped TiO as claimed in claim 1
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: the amount of substance of tetrabutyl titanate, methyl ethyl diketone, concentrated nitric acid is than being 1:1:0.3, and when the amount of tetrabutyl titanate is 17ml, corresponding dehydrated alcohol is 100ml.
3. carbon nano tube-doped TiO as claimed in claim 1
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: described direct facture operation steps is:
1. the organo silane coupling agent for carbon nanotube (CNTs) 0.5wt%-1.0wt% is joined in 2-5 alcohol solution (water/alcohol=1/9) doubly, completely to be mixed after dispersion;
2. 5gCNTs is loaded in agitator;
3. at room temperature, limit uniform stirring CNTs, while add the alcohol solution of the organo silane coupling agent of aforementioned preparation in 10 minutes;
4. after treating that the alcohol solution of organo silane coupling agent all adds, then mechanical stirring mixes 12 hours;
5. again by the temperature of steel basin by 50 DEG C of gradient increased temperatures to 100 DEG C, each raise 10 DEG C, at 70 DEG C, the 80 DEG C each heating 1h in place, at all the other temperature, respectively heat 0.5h;
6. after being then down to room temperature, then drying is carried out.
4. carbon nano tube-doped TiO as claimed in claim 1
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: described carbon nanotube is 0.005:1 with the ratio of the amount of substance of tetrabutyl titanate.
5. carbon nano tube-doped TiO as claimed in claim 1
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: described solidifying agent and promotor are methylethylketone and cobalt naphthenate respectively.
6. carbon nano tube-doped TiO as claimed in claim 1
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: described epoxy resin, solidifying agent, promotor are 1:0.01:0.01:1 with the ratio of the amount of substance of tetrabutyl titanate.
7. carbon nano tube-doped TiO as claimed in claim 1
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: the concrete steps of described method are as follows:
First by presoma tetrabutyl titanate and the mixing of complexing agent methyl ethyl diketone, stir 1h, complexing obtains modification presoma, then adds solvent dehydrated alcohol, the ethanolic soln slowly dripping distilled water and stablizer concentrated nitric acid, stirs 6h, obtain TiO
2colloidal sol;
TiO is mixed by adopting the carbon nanotube of direct facture process
2in colloidal sol, stirring at room temperature 24 hours, obtains carbon nano tube-doped TiO
2colloidal sol, then dry 4h at 70 DEG C, obtain stable gel;
Epoxy resin, solidifying agent, promotor are added respectively in gained gel, stir, obtain fiber glass resin matrix, hand sticks with paste legal system for glass reinforced plastic;
By gained glass reinforced plastic in 400 DEG C of heating 1 hour, obtain nanotube doped Ti O
2/ epoxy hybrid glass fiber reinforced plastics composite material.
8. carbon nano tube-doped TiO as claimed in claim 7
2the preparation method of/epoxy hybrid glass fiber reinforced plastics composite material, is characterized in that: the amount of substance of distilled water and tetrabutyl titanate is than being 2:1, and the ethanolic soln of distilled water is that 1:2 is formulated by volume by distilled water and dehydrated alcohol.
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| CN105885385A (en) * | 2016-04-25 | 2016-08-24 | 东莞市联洲知识产权运营管理有限公司 | Carbon nanotube-TiO2-polyfurfuryl alcohol ternary composite material and method for preparing same |
| RU2637227C1 (en) * | 2016-09-30 | 2017-12-01 | Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский государственный технологический университет "СТАНКИН" (ФГБОУ ВО "МГТУ "СТАНКИН") | Method of producing polymeric composite materials |
| CN107828188A (en) * | 2017-11-30 | 2018-03-23 | 万丰航空工业有限公司 | A kind of manufacture method of carbon fibre composite for airplane skin |
| CN108582350A (en) * | 2017-12-07 | 2018-09-28 | 常州思宇环保材料科技有限公司 | A kind of method of the drying of wood |
| CN108912608A (en) * | 2018-06-29 | 2018-11-30 | 江苏德溢利新材料科技有限公司 | A kind of the glass reinforced plastic photovoltaic bracket and its processing technology of modification |
| CN109554071A (en) * | 2018-11-20 | 2019-04-02 | 西安西电电气研究院有限责任公司 | A kind of compound static conductive heat radiation coating of nano titania carbon and preparation method thereof |
| CN114031950A (en) * | 2021-11-11 | 2022-02-11 | 浙江明辉电力设备有限公司 | Composite glass fiber reinforced plastic cable protection pipe sleeve |
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| CN105885385A (en) * | 2016-04-25 | 2016-08-24 | 东莞市联洲知识产权运营管理有限公司 | Carbon nanotube-TiO2-polyfurfuryl alcohol ternary composite material and method for preparing same |
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| CN108582350A (en) * | 2017-12-07 | 2018-09-28 | 常州思宇环保材料科技有限公司 | A kind of method of the drying of wood |
| CN108912608A (en) * | 2018-06-29 | 2018-11-30 | 江苏德溢利新材料科技有限公司 | A kind of the glass reinforced plastic photovoltaic bracket and its processing technology of modification |
| CN109554071A (en) * | 2018-11-20 | 2019-04-02 | 西安西电电气研究院有限责任公司 | A kind of compound static conductive heat radiation coating of nano titania carbon and preparation method thereof |
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| CN114031950A (en) * | 2021-11-11 | 2022-02-11 | 浙江明辉电力设备有限公司 | Composite glass fiber reinforced plastic cable protection pipe sleeve |
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