CN105061786A - Bubble dispersion method for preparing graphene/epoxy resin composite materials - Google Patents
Bubble dispersion method for preparing graphene/epoxy resin composite materials Download PDFInfo
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Abstract
The invention belongs to the technical field of nanocomposite, and particularly relates to a bubble dispersion method for preparing graphene/epoxy resin composite materials. The method includes the steps that gas of proper pressure and flow is guided to a premixed material of graphene/epoxy resin, clustering of graphene is scattered through graphene particles, generated in the bubble generation and floating processes, in a volume expansion tensioning resin base body, and stretching of the graphene particles is promoted. Under the situation that dispersing agents are not used, the graphene is evenly dispersed in epoxy resin through relative motion of bubble wall films in the bubble generation, growing and breaking processes by means of a physical method, the dispersion process is simple in technology and convenient to control, the dispersion effect is good, popularization of the technology is achieved easily, and the graphene/epoxy resin composite materials excellent in performance can be obtained. The method is less in energy consumption, low in cost and free of pollution, factory mass production is achieved easily, and chemical properties of the obtained composite materials is obviously promoted.
Description
Technical field
The invention belongs to nano composite material technical field, particularly a kind of air bubbles dispersion method prepared for Graphene/epoxy resin composite material.
Background technology
Epoxy resin is one of most popular macromolecular material, has the physics of many excellences, chemistry and mechanical property, and such as: good stability of the dimension, hardness is high, good insulation preformance, and cohesiveness is strong, and stable chemical nature, has certain thermotolerance, etc.In recent years, output and the demand of epoxy resin constantly increase, especially in the high-end technical field development such as aerospace, electronic apparatus, machinofacture and military project fast.But on the other hand, the fragility of epoxy resin is large, impact resistance is weak, limit the further application of epoxy resin, the enhancing of epoxy resin, Research on Toughening also one of hot subject therefore becoming epoxy resin and field of compound material thereof.
As the low-dimensional carbon nanomaterial of latest find in 2004, Graphene has very excellent mechanical property, and its tensile strength can reach 130GPa, and Young's modulus is about 1100GPa, be measured and monitored the growth of standing timber material in the highest; Meanwhile, Graphene also has very high electronic mobility (20000cm
2/ (Vs)) and unique physical property such as thermal conductivity (3000W/ (mK)).From structure, Graphene is in the plane according to the two-dimension nano materials that phenyl ring hexagonal structure periodic regular arranges by carbon atom, be expected to form firmly interface cohesion with epoxy resin-base, improve toughness and the intensity of epoxy resin, the excellent electroconductibility of Graphene also can be utilized to prepare electroconductibility Graphene/epoxy resin composite material etc.
In the triturating of Graphene/epoxy resin composite material, a technical bottleneck being difficult to avoid is exactly the scattering problem of Graphene.Because the specific surface area of Graphene is large, surface energy is high, add its lateral dimension considerably beyond thickness, under the shearing dissemination that conventional mechanical stirs, Graphene is easy to curling agglomerating, and be difficult between macromolecule matrix form good interface cohesion, seriously undermined the activeness and quietness effect of Graphene.At present, promote technological method mainly dispersion agent method and the ultrasonic dispersion of graphene dispersion, more research is that both are combined acting in conjunction.Dispersion agent method utilizes the dispersion agents such as tensio-active agent to be formed at graphenic surface to align, and reduces Graphene surface tension in the base, reduce the Texturized of Graphene, but may have a negative impact to the mechanical property of matrix material; Ultrasonic disperse rule utilizes mechanical effect to produce tiny bubble, when utilizing bubble to produce-break form the high temperature of cavatition, High Pressure impels Graphene in the base dispersed, action effect is remarkable, but the method is successful in the liquid phase with certain polarity such as water, ethanol, in high viscosity, low-pole or nonpolar matrix phase, its action effect is very limited, and ultrasonic wave is subject to absorption and the buffering of high viscosity matrix, affect hyperacoustic effective range, be difficult to adapt to industrialized production needs.
Summary of the invention
Main purpose of the present invention is to provide a kind of air bubbles dispersion method prepared for Graphene/epoxy resin composite material, when not using dispersion agent, pass through physical method, utilize the generation of bubble, grow up and relative movement that in rupture process, walls film occurs, graphene uniform is disperseed in the epoxy; Dispersion process technique is simple, and manipulation is convenient, and dispersion effect is good, is easy to realize technique and amplifies, the Graphene/epoxy resin composite material of availability excellence.
For realizing above technical purpose, technical scheme of the present invention is:
A kind of air bubbles dispersion method prepared for Graphene/epoxy resin composite material, the air bubbles dispersion device adopted is made up of pressure generator, reducing valve, under meter, valve, sample pool and temperature control unit, pressure generator is communicated with bottom sample pool by valve, set temperature function unit around sample pool, the pipeline between pressure generator and valve is arranged reducing valve, under meter; The method specifically comprises the following steps:
(1) take epoxy resin and Graphene respectively in proportion, adopt mechanical stirring pre-mixing;
(2) be added to by Graphene/epoxy resin composition in the sample pool of air bubbles dispersion device, open temp function unit, design temperature also treats that it is stablized;
(3) start pressure generator, regulate reducing valve and under meter, gas is bloated from the valve of sample pool bottom, and bubble is formed gradually and slowly floats, and breaks after rising to liquid level; Bloat the size and number of bubble by gas flow adjustment, lasting air-blowing is operated to air-blowing and terminates front 10min, adds the triethylene tetramine that measures in advance as solidifying agent, continues air-blowing to setting-up time;
(4) Graphene/epoxy resin composition is taken out, be placed in vacuum drying oven and carry out casting after vacuum defoaming treatment, continue vacuum stripping process, until there is not obvious bubble in sample; Gained sample normal temperature leaves standstill 24h to complete curing molding, obtains Graphene/epoxy resin composite material.
The described air bubbles dispersion method prepared for Graphene/epoxy resin composite material, in step (2), the ratio of Graphene and epoxy resin is counted in mass ratio between 0.15% ~ 1.50%.
The described air bubbles dispersion method prepared for Graphene/epoxy resin composite material, in step (3), adopt gas to be pressurized air, nitrogen, helium, argon gas, CO
2in one or more mixtures, gas flow is at 200 ~ 1000mL/ (min valve).
The described air bubbles dispersion method prepared for Graphene/epoxy resin composite material, in step (3), the air-blowing time length is 2 ~ 12 hours.
The described air bubbles dispersion method prepared for Graphene/epoxy resin composite material, in step (3), the add-on of triethylene tetramine accounts for 5% ~ 15% of epoxy resin quality.
As compared to conventional disperse method (as: mechanical dispersion method, dispersion agent method and ultrasonic dispersion), advantage of the present invention and beneficial effect are:
(1) compared with mechanical dispersion method, the mechanical function mode of air bubbles dispersion method is more reasonable, is more suitable for the dispersion process of the two-dimension flexible materials such as Graphene.Mechanical dispersion, also claim to shear dispersion, mechanical movement particular by parts such as agitating vanes makes the different piece generation relative displacement of mixture, form shear surface, thus play the effect of dispersion (mixing), but Graphene one class is easy to two dimension or the one-dimensional material of deflection deformation, may occurs to be wound around or particle self curling between particle in mechanical agitation process, affect dispersion effect.Contrastingly air bubbles dispersion method provided by the present invention utilizes the stretching process of membranous wall in bubble generation and expansion process to produce stretching effect to Graphene particle pre-buried in matrix.As shown in Figure 1, adopt the present invention not only can the Graphene separate particles of agglomerated, curling Graphene particle more can be made to extend, improve the interfacial adhesion of Graphene and resin matrix, therefore show more significant dispersion and enhancement.
(2) compared with dispersion agent method, air bubbles dispersion method does not need to use any dispersion agent, not only reduces preparation cost, and eliminates the existence of dispersion agent at Graphene-resin boundary surface, and the mechanical property for matrix material has certain improvement result.
(3) compared with ultrasonic dispersion, the scope of application of air bubbles dispersion method is wider, is also more suitable for industrialization scale operation.The high temperature that ultrasonic disperse mainly utilizes cavatition to produce, high pressure and jet action, strengthen the dispersion effect of mixture, but the method is subject to the impact of the factor such as system volume, matrix phase viscosity.Contrastingly air bubbles dispersion method technique provided by the present invention is simple, and production energy consumption is little, cost is low, pollution-free, is easy to industry and amplifies, be more suitable for the large-scale production of black alkene/epoxy resin composite material.
(4) the inventive method technique is simple, and energy consumption is little, cost is low, pollution-free, and be easy to realize plant sizeization and produce, the mechanical property of gained matrix material has obvious lifting.
Accompanying drawing explanation
Fig. 1 is Graphene particle strained condition schematic diagram in air bubbles dispersion process.In figure, 4 valves.
Fig. 2 is air bubbles dispersion device composition structural representation.In figure, 1 pressure generator; 2 reducing valve; 3 under meters; 4 valves; 5 sample pools; 6 temperature control units.
Fig. 3 a-Fig. 3 b is the Tensile fracture scanning electron microscope microscopic appearance of pure epoxy resin and Graphene/epoxy resin composite material.Wherein, Fig. 3 a pure epoxy resin; Fig. 3 b Graphene/epoxy resin composite material, Graphene volume is 0.15wt% (mass ratio of Graphene and epoxy resin), air flow quantity 400mL/min/ valve, air-blowing time 6h.
Fig. 4 a-Fig. 4 b is that the air bubbles dispersion time of preparation technology is to the affecting laws of sample mechanical property.Wherein, Fig. 4 a tensile strength; Fig. 4 b tensile modulus.Other important parameter: Graphene volume 0.45wt% (mass ratio of Graphene and epoxy resin), air flow quantity 1000mL/min/ valve.
Embodiment
In a specific embodiment, as shown in Figure 1, the present invention blasts gas from bottom by valve 4 in warm Graphene-mixed with resin system, the bottom-up motion of the bubble generated, and volume constantly expands and finally breaks, enters air; In bubble formation and expansion process, the liquid phase generation transversal displacement that bubble parietal layer adheres to, under matrix-Graphene interfacial adhesion effect, inner pre-buried Graphene agglomerated particles is spread out, or form stretching effect by the curling particle periphery of Graphene and Graphene stratiform construction stretch is opened, increase effective bond area of Graphene-resin, realize dispersed in resin matrix of Graphene reinforcement.
As shown in Figure 2, the air bubbles dispersion device chief component that the present invention is prepared for Graphene/epoxy resin composite material comprises: pressure generator 1 (as: gas cylinder), reducing valve 2, under meter 3, valve 4, sample pool 5, temperature control unit 6 (as: thermostatical water bath), concrete structure is as follows: pressure generator 1 is communicated with bottom sample pool 5 by valve 4, sample pool 5 surrounding set temperature function unit 6, the pipeline between pressure generator 1 and valve 4 is arranged reducing valve 2, under meter 3.
The present invention is used for the air bubbles dispersion method of Graphene/epoxy resin composite material, mainly comprises the following steps:
(1) take epoxy resin and Graphene respectively in proportion, adopt mechanical stirring pre-mixing;
(2) be added in the sample pool 5 of air bubbles dispersion device by Graphene/epoxy resin composition, open temperature control unit 6, design temperature also treats that it is stablized;
(3) open the valve of pressure generator 1, regulate reducing valve 2 and under meter 3; Gas bloats from the valve 4 of sample pool bottom, and bubble is formed gradually and slowly floats, and breaks after rising to liquid level.Bloated the size and number of bubble by gas flow adjustment, treat that gas flow reaches stable, record bubble size, speed, terminate front 10min to air-blowing, adds load weighted triethylene tetramine in advance and, as solidifying agent, continue air-blowing to setting-up time;
(4) Graphene/epoxy resin composition is taken out, be placed in rapidly vacuum drying oven and carry out vacuum-treat, object eliminates the bubble in mixture, then casting, continue vacuum stripping process, until there is not obvious bubble in sample, gained sample normal temperature leaves standstill 24h to complete curing molding, obtains Graphene/epoxy resin composite material.
Above-mentioned air bubbles dispersion method and technological process thereof, be suitable for the preparation of Graphene/epoxy resin composite material, wherein the ratio of Graphene and epoxy resin is counted in mass ratio between 0.15% ~ 1.50%, provide the envrionment temperature of air bubbles dispersion technique to be set to 40 ~ 80 DEG C.Adopt the relative Graphene of gas and epoxy resin to be inert condition, without chemical action occur, pressurized air, nitrogen, helium, argon gas, CO can be adopted
2in one or more mixtures, gas flow is generally at 200 ~ 1000mL/min/ valve (valve on sample pool bottom surface in honeycomb arrangement, spacing 3 ~ 5cm).Air-blowing answers certain time to improve the dispersion effect of Graphene, is generally 2 ~ 12 hours.In addition, the temperature suitably improving Graphene/epoxy resin composition can reduce the viscosity of mixture, and be conducive to sparging process, but temperature is too high, viscosity is too little, and the cohesive force between resin and Graphene can be caused to reduce, impact traction dispersion effect.Mechanics Performance Testing finds, the tensile strength of sample reaches 20 ~ 30MPa, and corresponding tensile modulus can reach 1.2 ~ 2.0GPa.
In order to better understand the present invention, below in conjunction with embodiment, the present invention is set forth further, but the present invention protects content to be not only confined to described embodiment.
Embodiment 1
Take epoxy resin 100 parts, Graphene 0.15 part, namely the mass ratio of Graphene and epoxy resin is 0.15%, and Graphene is mixed in epoxy resin in advance.Arranging water-bath temperature is 55 DEG C, after homo(io)thermism, open the valve of pressurized air gas cylinder, regulate reducing valve and under meter, (the valve quantity of the present embodiment is 15 to make stability of flow keep 400mL/min/ valve, each valve per minute flow 400mL, in honeycomb arrangement on sample pool bottom surface, spacing 3cm), ready Graphene/epoxy resin composition is poured in the sample pool of air bubbles dispersion device, avoid Topical Dispersion uneven, carry out bubbling 6h; To bubbling 5 hours 50 points, take 10 parts of triethylene tetramines (10% of epoxy resin quality) and be added to sample pool, continue air-blowing to 4h; After air bubbles dispersion after sample casting, be placed in 80 DEG C of vacuum drying ovens, carry out froth in vacuum process 1h, take out, normal temperature 24h curing molding, tests its microtexture and mechanical property.The bright Graphene good dispersion of scanning electronic microscope (SEM) analytical table (Fig. 3 b), Graphene no longer becomes to reunite shape, with the smooth section of pure epoxy resin tensile failure (Fig. 3 a), after mixing Graphene, obviously rising and falling appears in the stressed section of matrix material, show that interface cohesion is tight, favourable to the enhancing of its tensile property.Mechanics Performance Testing finds, the tensile strength of sample reaches 27.66MPa, and corresponding tensile modulus can reach 1.69GPa.
Embodiment 2
Take epoxy resin 100 parts, Graphene 0.45 part, namely the mass ratio of Graphene and epoxy resin is 0.45%, and Graphene is mixed in epoxy resin in advance.Arranging water-bath temperature is 80 DEG C, after homo(io)thermism, open the valve of pressurized air gas cylinder, regulate reducing valve and under meter, (the valve quantity of the present embodiment is 20, in honeycomb arrangement on sample pool bottom surface to make stability of flow keep 1000mL/min/ valve, spacing 5cm), ready Graphene/epoxy resin composition is poured in the sample pool of air bubbles dispersion device, avoids Topical Dispersion uneven, bubbling 2h; To bubbling 1 hour 50 points, take 10 parts of triethylene tetramines (10% of epoxy resin quality) and be added to sample pool, continue air-blowing to 2h; After air bubbles dispersion after sample casting, be placed in 80 DEG C of vacuum drying ovens, carry out froth in vacuum process 1h, take out, normal temperature 24h curing molding, tests its microtexture and mechanical property.Mechanics Performance Testing finds, the tensile strength of sample and tensile modulus all first improve rear reduction (Fig. 4 a, Fig. 4 b) with the continuity of air-blowing process, reach maximum at air-blowing time about 2h, tensile strength can reach 21.51MPa, and tensile modulus can reach 1.43GPa.
Embodiment 3
Take epoxy resin 100 parts, Graphene 1.5 parts, namely the mass ratio of Graphene and epoxy resin is 1.50%, and Graphene is mixed in epoxy resin in advance.Arranging water-bath temperature is 55 DEG C, after homo(io)thermism, open the valve of pressurized air gas cylinder, regulate reducing valve and under meter, (the valve quantity of the present embodiment is 30, in honeycomb arrangement on sample pool bottom surface to make stability of flow keep 200mL/min/ valve, spacing 4cm), ready Graphene/epoxy resin composition is poured in the sample pool of air bubbles dispersion device, avoids Topical Dispersion uneven, bubbling 12h; To bubbling 11 hours 50 points, take 10 parts of triethylene tetramines (10% of epoxy resin quality) and be added to sample pool, continue air-blowing to 12h; After air bubbles dispersion after sample casting, be placed in 80 DEG C of vacuum drying ovens, carry out froth in vacuum process 2h, take out, normal temperature 24h curing molding, tests its microtexture and mechanical property.Better (Fig. 3 b), Graphene no longer becomes to reunite shape the bright graphene dispersion of scanning electronic microscope (SEM) analytical table, and the interface cohesion of stressed section is comparatively tight, favourable to the enhancing of its tensile property.Mechanics Performance Testing finds, the tension of sample can reach 29.42MPa by force, and corresponding tensile modulus can reach 1.75GPa.
Embodiment result shows, the gas of suitable pressure, flow is incorporated in Graphene/epoxy resin pre-composition by the present invention, bubble is utilized to produce and the Graphene particle in the volumetric expansion stretch-draw resin matrix in floating-upward process, break up the reunion of Graphene, promote the stretching, extension of Graphene particle, the tensile strength of matrix material obtained by air bubbles dispersion technique, tensile modulus and fracture toughness property are all improved to some extent.
Claims (5)
1. the air bubbles dispersion method prepared for Graphene/epoxy resin composite material, it is characterized in that, the air bubbles dispersion device adopted is made up of pressure generator, reducing valve, under meter, valve, sample pool and temperature control unit, pressure generator is communicated with bottom sample pool by valve, set temperature function unit around sample pool, the pipeline between pressure generator and valve is arranged reducing valve, under meter; The method specifically comprises the following steps:
(1) take epoxy resin and Graphene respectively in proportion, adopt mechanical stirring pre-mixing;
(2) be added to by Graphene/epoxy resin composition in the sample pool of air bubbles dispersion device, open temp function unit, design temperature also treats that it is stablized;
(3) start pressure generator, regulate reducing valve and under meter, gas is bloated from the valve of sample pool bottom, and bubble is formed gradually and slowly floats, and breaks after rising to liquid level; Bloat the size and number of bubble by gas flow adjustment, lasting air-blowing is operated to air-blowing and terminates front 10min, adds the triethylene tetramine that measures in advance as solidifying agent, continues air-blowing to setting-up time;
(4) Graphene/epoxy resin composition is taken out, be placed in vacuum drying oven and carry out casting after vacuum defoaming treatment, continue vacuum stripping process, until there is not obvious bubble in sample; Gained sample normal temperature leaves standstill 24h to complete curing molding, obtains Graphene/epoxy resin composite material.
2. the air bubbles dispersion method prepared for Graphene/epoxy resin composite material according to claim 1, it is characterized in that: in step (2), the ratio of Graphene and epoxy resin is counted in mass ratio between 0.15% ~ 1.50%.
3. the air bubbles dispersion method prepared for Graphene/epoxy resin composite material according to claim 1, is characterized in that: in step (3), adopt gas to be pressurized air, nitrogen, helium, argon gas, CO
2in one or more mixtures, gas flow is at 200 ~ 1000mL/ (min valve).
4. the air bubbles dispersion method prepared for Graphene/epoxy resin composite material according to claim 1, it is characterized in that: in step (3), the air-blowing time length is 2 ~ 12 hours.
5. the air bubbles dispersion method prepared for Graphene/epoxy resin composite material according to claim 1, it is characterized in that: in step (3), the add-on of triethylene tetramine accounts for 5% ~ 15% of epoxy resin quality.
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| CN105837790A (en) * | 2016-06-20 | 2016-08-10 | 山东欧铂新材料有限公司 | Preparation method of graphene modified epoxy resin |
| US10934407B2 (en) * | 2016-10-11 | 2021-03-02 | Palo Alto Research Center Incorporated | Process for making horizontally-aligned epoxy graphene material |
| CN117164838A (en) * | 2023-08-30 | 2023-12-05 | 浙江建兴科技有限公司 | Melt straight-pull semitransparent solar backboard base film and production process thereof |
| CN117164838B (en) * | 2023-08-30 | 2024-07-26 | 浙江建兴科技有限公司 | Melt straight-pull semitransparent solar backboard base film and production process thereof |
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