CN112055528A - Preparation method of graphene-coated glass fiber reinforced plastic - Google Patents
Preparation method of graphene-coated glass fiber reinforced plastic Download PDFInfo
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- CN112055528A CN112055528A CN202010965244.9A CN202010965244A CN112055528A CN 112055528 A CN112055528 A CN 112055528A CN 202010965244 A CN202010965244 A CN 202010965244A CN 112055528 A CN112055528 A CN 112055528A
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Abstract
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of graphene-coated glass fiber reinforced plastic. The method comprises the following steps: and (5) surface treatment of the glass fiber reinforced plastic. The preparation of the graphene-coated glass fiber reinforced plastic is mainly divided into three steps for surface treatment of a glass material: hydroxylating the surface of the glass fiber, modifying a silane coupling agent and self-assembling bovine serum albumin, finishing pretreatment of the glass fiber through the three steps, further enhancing the binding performance of the glass fiber and graphene oxide, and enabling the graphene oxide to be self-assembled on the surface of the modified glass fiber to form a graphene oxide film. According to the invention, the graphene-wound modified glass fiber is used to form a carbon conductive network in the composite material, so that the composite material has an electric energy shielding function, and the modified glass fiber reinforced plastic-wound graphene composite material has good mechanical properties such as compression resistance and tensile resistance.
Description
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a preparation method of graphene-coated glass fiber reinforced plastic.
Background
Graphene is a carbon atom sp2The hybrid tracks form a hexagonal honeycomb lattice two-dimensional carbon nanomaterial. Graphene has excellent optical, electrical and mechanical properties, and many materials are prepared from graphene-based composite materials at present, and the conductive materials with excellent performance are expected to be obtained by utilizing high conductivity of the graphene. The glass fiber reinforced plastic has good mechanical property, heat resistance and corrosion resistance, and can be widely applied to the fields of traffic, buildings, electronic technology and the like, but the glass fiber reinforced plastic is difficult to realize the application in the field of electromagnetic shielding due to poor electric conductivity. In order to enhance the conductivity of the glass fiber reinforced plastic and expand the application of the glass fiber reinforced plastic in the aspect of electromagnetic shielding, the high conductivity of the graphene is combined with the high strength performance of the glass fiber reinforced plastic to prepare the modified glass fiber reinforced plastic graphene-wound composite conductive material.
Disclosure of Invention
The invention aims to provide a preparation method of graphene coated glass fiber reinforced plastic. According to the invention, the graphene-wound modified glass fiber is used to form a carbon conductive network in the composite material, so that the composite material has an electric energy shielding function, and the modified glass fiber reinforced plastic-wound graphene composite material has good mechanical properties.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of graphene-coated glass fiber reinforced plastic comprises the following steps: hydroxylating the surface of the glass fiber, modifying a silane coupling agent and self-assembling bovine serum albumin, and finishing pretreatment of the glass fiber through the three steps so as to enhance the bonding performance of the glass fiber and graphene oxide; then, the COOH groups on the surface of graphene oxide-modified glass fiber reinforced plastic graphene oxide show electronegativity in water, the silane coupling agent (KH 550) shows electropositivity, and positive and negative charges in the solution attract each other, so that the graphene oxide is self-assembled on the surface of the modified glass fiber to form a graphene oxide film, and finally the graphene-coated glass fiber reinforced plastic is obtained.
The method specifically comprises the following steps:
(1) acid treatment: hydroxylating the surface of glass by adopting an acid treatment process, firstly calcining the glass fiber at 450 ℃ for 1h, removing impurities in the glass fiber, and soaking the glass fiber in 3mol/L hydrochloric acid solution for 70 min; the glass material has the highest hydroxylation level at this time;
(2) modification treatment of a silane coupling agent: soaking the glass fiber obtained after acid treatment in an alcohol-water solution with the concentration of a modifier silane coupling agent (KH 550) being 1.0wt.% for 30 min;
(3) self-assembly treatment of bovine serum albumin: immersing the glass fiber obtained by the treatment of the step (2) in 1.5wt% BSA solution for 60min to complete self-assembly treatment;
(4) modifying graphene oxide: preparing graphene oxide dispersion liquid with the concentration of 1.5mg/mL, placing 10-30 g of the glass fiber obtained in the step (3) in the graphite oxide dispersion liquid for 70min, pulling for 5-10 times, taking out, washing with distilled water, and drying; obtaining a graphene-coated glass fiber material;
(5) preparing a mixed solution of acetic acid and hydroiodic acid in a volume ratio of =2.5:1 in a beaker, placing the graphene-coated glass fiber material obtained in the step (4) on a support above the beaker, and carrying out water bath at 40 ℃ to ensure that the steam of the mixed solution passes through glass fiber reinforced plastic to reduce graphene oxide;
(6) and (3) weighing the graphene coated glass fiber material obtained in the step (5) (the dosage is 10wt% -40wt% of the unsaturated resin), adding the graphene coated glass fiber material into a mold, and dropwise adding the unsaturated resin to fill the mold, thereby finally obtaining the graphene coated glass fiber reinforced plastic material.
The invention has the following remarkable advantages:
(1) the glass fiber reinforced plastic has the advantages of corrosion resistance, light weight, high strength, good insulating and heat-insulating properties, easy design and easy processing, is widely applied to the aspects of buildings, chemical engineering, transportation and electrical engineering, and has the function of shielding electric energy by winding the modified glass fiber with the graphene to form a carbon conductive network in the composite material.
(2) The modified glass fiber reinforced plastic wound graphene composite material prepared by the invention has good mechanical properties. The modification of the graphene improves the compression resistance of the composite material to a certain extent, is favorable for enhancing the tensile property of the composite material, and improves the limit of tensile strength.
Drawings
FIG. 1 the effect of fiber loading on the compressive properties of a composite;
FIG. 2 the effect of fiber loading on the tensile properties of a composite;
fig. 3 shows the electromagnetic shielding effectiveness of the composite material. (wherein the mass of the graphene coated glass fiber material is 10wt.% to 40wt.% of the mass of the unsaturated resin).
Detailed Description
For further disclosure, but not limitation, the present invention is described in further detail below with reference to examples.
Example 1
The method specifically comprises the following steps:
(1) preparing 3mol/L hydrochloric acid solution, calcining the glass fiber at 450 ℃ for 1h, soaking the glass fiber by using the hydrochloric acid solution to hydroxylate the surface of the glass fiber, reducing the contact angle between the glass and water, and finishing the modification of the glass. The optimal process is that the treatment is carried out for 70min by using 3mol/L acid solution, and the contact angle is 21 degrees.
(2) Preparing 1 percent of gamma-aminopropyl trimethoxy silane (KH 550) by mass fraction. Soaking the glass fiber in 1.0wt.% aqueous alcohol solution of a modifier, namely a silane coupling agent (KH 550), for 30min for acid treatment. The modification results show that: the contact angle with water is increased after modification, and the hydrophilicity of the glass material is reduced; when the mass fraction of the coupling agent is less than 1.0%, the contact angle increases with the increase of the concentration to 68%, and when the mass fraction of the coupling agent is more than 1.0%, the increase of the concentration has little influence on the contact angle change. When the modification time is less than 30min, the modification effect increases with time, and when it exceeds 30min, the contact angle does not change significantly with time. The loss on ignition is adopted to represent the result of the coupling agent modifying the glass fiber, the concentration of the coupling agent is higher than 1wt.%, the treatment time is 30min, the treatment effect is optimal, and the result is consistent with the contact angle representation result.
(3) The glass fiber after hydroxylation treatment was immersed in a 1.5wt% BSA solution for 60min for modification. The results show that: when the BSA concentration is more than 1wt.%, the ignition mass loss rate is at most 3.5%, and the maximum ignition mass loss rate does not change much as the concentration increases. When the treatment time is 60min, the modification effect of the bovine serum albumin is not changed greatly along with the increase of the time when the weight loss rate reaches the maximum value.
(4) Preparing a graphene oxide dispersion liquid with the concentration of 1.5mg/mL, taking 10-30 g of BSA modified glass fiber, placing for 70min, pulling for 5-10 times, taking out, washing with distilled water, and drying to obtain the graphene coated glass fiber reinforced plastic composite material. A mixed solution of acetic acid and hydroiodic acid =2.5:1 by volume was prepared in a beaker. The prepared material is placed above a beaker support, water bath is carried out at 40 ℃, the mixed solution steam penetrates through glass fiber reinforced plastic, graphene oxide is reduced, and the conductivity of the reduced graphene oxide is far greater than that of the graphene oxide. And weighing the obtained graphene coated glass fiber material (the dosage is 10wt% -40wt% of the unsaturated resin) in a mold, and dropwise adding the unsaturated resin to fill the mold, thereby finally obtaining the graphene coated glass fiber reinforced plastic material.
When the concentration of the graphene oxide is 1.5wt.%, the glass fiber is covered and modified by the graphene oxide in a large area, and the modified surface has a wrinkle effect; when the concentration of the graphene oxide is continuously increased to 2.0wt.%, the surfaces of graphene oxide lamella on the surface of the glass fiber are agglomerated, and the uniform and stable effect cannot be achieved.
(5) With the increase of the treatment time, the number of the sheets of the graphene oxide is increased, the coverage area is increased, and the effect is gradually improved. When the treatment time reaches 70min, the surface of the glass fiber obtains good covering effect, and obvious sheet layer wrinkles and areas are formed on the surface. When the time is continuously increased, the graphene modification layer is continuously thickened, and the change of the coating area is small.
(6) The optimal conditions for coating the glass fiber with the graphene oxide dispersion liquid are as follows: concentration 1.5wt.%, treatment time 70 min.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (8)
1. A preparation method of graphene coated glass fiber reinforced plastic is characterized by comprising the following steps: the method comprises the following steps: hydroxylating the surface of the glass fiber, modifying a silane coupling agent and self-assembling bovine serum albumin, then placing the glass fiber into graphite oxide dispersion liquid for lifting, enabling graphene oxide to be self-assembled on the surface of the modified glass fiber to form a graphene oxide film, curing the glass fiber with resin, and finally obtaining the graphene-coated glass fiber reinforced plastic.
2. The preparation method of the graphene-coated glass fiber reinforced plastic according to claim 1, wherein the preparation method comprises the following steps:
the method specifically comprises the following steps:
(1) acid treatment: hydroxylating the surface of glass by adopting an acid treatment process, firstly calcining the glass fiber at 450 ℃ for 1h, removing impurities in the glass fiber, and putting the glass fiber in a hydrochloric acid solution;
(2) modification treatment of a silane coupling agent: soaking the glass fiber obtained after acid treatment in an alcohol-water solution containing a modifier silane coupling agent for 30 min;
(3) self-assembly treatment of bovine serum albumin: immersing the glass fiber obtained by the treatment of the step (2) in 1.5wt% of BSA solution to complete self-assembly treatment;
(4) modifying graphene oxide: preparing a graphene oxide dispersion liquid with the concentration of 1.5mg/mL, placing 10-30 g of the glass fiber obtained in the step (3) in the graphite oxide dispersion liquid for 70min, pulling for 5-10 times, taking out, washing with distilled water, and drying; obtaining a graphene-coated glass fiber material;
(5) preparing a mixed solution of acetic acid and hydroiodic acid in a beaker, placing the graphene-coated glass fiber material obtained in the step (4) above an upper bracket of the beaker, and reducing graphene oxide by allowing steam of the mixed solution to pass through glass fibers in a water bath at 40 ℃;
(6) and (4) weighing the graphene-coated glass fiber material obtained in the step (5), adding the graphene-coated glass fiber material into a mold, and dropwise adding unsaturated resin to fill the mold, thereby finally obtaining the graphene-coated glass fiber reinforced plastic material.
3. The preparation method of the graphene-coated glass fiber reinforced plastic according to claim 2, wherein the preparation method comprises the following steps: the soaking in the step (1) is specifically soaking in 3mol/L hydrochloric acid solution for 70 min.
4. The preparation method of the graphene-coated glass fiber reinforced plastic according to claim 2, wherein the preparation method comprises the following steps: the silane coupling agent is specifically KH550, and the concentration of KH550 in the alcohol aqueous solution containing the modifier silane coupling agent is 1.0 wt.%.
5. The preparation method of the graphene-coated glass fiber reinforced plastic according to claim 2, wherein the preparation method comprises the following steps: and (4) the immersion time in the step (3) is 60 min.
6. The preparation method of the graphene-coated glass fiber reinforced plastic according to claim 2, wherein the preparation method comprises the following steps:
in the step (5), the volume ratio of the acetic acid to the hydroiodic acid is 2.5: 1.
7. The preparation method of the graphene-coated glass fiber reinforced plastic according to claim 2, wherein the preparation method comprises the following steps: and (3) the mass of the graphene coated glass fiber material in the step (6) is 10-40 wt% of that of the unsaturated resin.
8. Graphene-coated glass fiber reinforced plastic prepared according to the method of any one of claims 1 to 6.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670329A (en) * | 2016-04-05 | 2016-06-15 | 江苏宏远科技工程有限公司 | Preparation method of graphene-modified glass-fiber-reinforced composite material |
| CN107189495A (en) * | 2017-06-29 | 2017-09-22 | 铜陵市永创变压器电子有限公司 | A kind of dopamine coats nano-silicon dioxide modified conductive and heat-conductive glass fiber compound material and preparation method thereof |
| CN107265888A (en) * | 2017-07-13 | 2017-10-20 | 济南大学 | A kind of Fe3O4 of high magnetic permeability is grapheme modified/glass fiber compound material and preparation method thereof |
| CN107354500A (en) * | 2017-07-13 | 2017-11-17 | 济南大学 | A kind of glass fiber compound material of the grapheme modified claddings of nanoscale Fe3O4 and preparation method thereof |
| CN110746879A (en) * | 2019-09-26 | 2020-02-04 | 安徽鼎吉玻璃有限公司 | Modification method of electromagnetic shielding aging-resistant glass coating liquid |
-
2020
- 2020-09-15 CN CN202010965244.9A patent/CN112055528A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105670329A (en) * | 2016-04-05 | 2016-06-15 | 江苏宏远科技工程有限公司 | Preparation method of graphene-modified glass-fiber-reinforced composite material |
| CN107189495A (en) * | 2017-06-29 | 2017-09-22 | 铜陵市永创变压器电子有限公司 | A kind of dopamine coats nano-silicon dioxide modified conductive and heat-conductive glass fiber compound material and preparation method thereof |
| CN107265888A (en) * | 2017-07-13 | 2017-10-20 | 济南大学 | A kind of Fe3O4 of high magnetic permeability is grapheme modified/glass fiber compound material and preparation method thereof |
| CN107354500A (en) * | 2017-07-13 | 2017-11-17 | 济南大学 | A kind of glass fiber compound material of the grapheme modified claddings of nanoscale Fe3O4 and preparation method thereof |
| CN110746879A (en) * | 2019-09-26 | 2020-02-04 | 安徽鼎吉玻璃有限公司 | Modification method of electromagnetic shielding aging-resistant glass coating liquid |
Non-Patent Citations (1)
| Title |
|---|
| 陆豪: "石墨烯包覆玻璃纤维复合材料的制备", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
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