CN112848561A - Graphene modified multifunctional Glare laminate and preparation method thereof - Google Patents

Graphene modified multifunctional Glare laminate and preparation method thereof Download PDF

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Publication number
CN112848561A
CN112848561A CN202110087776.1A CN202110087776A CN112848561A CN 112848561 A CN112848561 A CN 112848561A CN 202110087776 A CN202110087776 A CN 202110087776A CN 112848561 A CN112848561 A CN 112848561A
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graphene
glare
multifunctional
epoxy resin
curing
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王朔
丛芳林
张业伟
孟庆实
崔旭
王治澍
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Shenyang Aerospace University
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Shenyang Aerospace University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/0076—Curing, vulcanising, cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/42—Alternating layers, e.g. ABAB(C), AABBAABB(C)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive

Abstract

The invention relates to the field of multifunctional composite materials, in particular to a graphene modified multifunctional Glare laminate and a preparation method thereof. The method comprises the following steps: (1) preparing a graphene suspension, adding the graphene suspension into an epoxy resin matrix, ultrasonically stirring, and volatilizing acetone to obtain a graphene modified adhesive; (2) the surface of the aluminum plate to be used is treated to form a rough surface which is beneficial to bonding; (3) after an epoxy resin curing agent is added into the graphene modified adhesive, the graphene modified adhesive and glass fibers are mixed to form a prepreg, the prepreg and an aluminum plate are layered through a wet method to form an alternate layering structure, and then the graphene modified multifunctional Glare laminate is formed through hot pressing and curing. The tensile property, the bending property and the electrochemical property of the multifunctional Glare laminate prepared by the method are better than those of the traditional Glare laminate, the multifunctional requirement of the Glare laminate in the using process can be met, the better application effect is achieved, and the multifunctional Glare laminate is expected to have wide application prospects in the fields of aerospace and transportation.

Description

Graphene modified multifunctional Glare laminate and preparation method thereof
Technical Field
The invention relates to the field of multifunctional composite materials, in particular to a graphene modified multifunctional Glare laminate and a preparation method thereof.
Background
The Glare laminate is a second-generation fiber metal laminate, is formed by alternately laying glass fiber-epoxy resin prepreg and aluminum alloy, combines the characteristics of high specific strength and specific rigidity of metal, and also continues the characteristics of excellent fatigue performance, high damage tolerance and the like of a fiber composite material. The light-weight structural member is widely applied to the manufacturing of space shuttles. Repairing damaged Glare laminates is one of the indispensable technologies for the aerospace industry. The preparation process of the Glare laminate is simple, complex process equipment is not needed, and mass production can be carried out. In practical application, the composite material is generally used as an aviation bearing structure such as an aircraft wing skin. Safety and economy requirements require that the Glare laminate not only have sufficient load bearing capacity, but also facilitate Structural Health Monitoring (SHM) during use. SHMs seek to integrate sensors into a structure in a manner that continuously performs non-destructive testing. At present, in addition to common sensors such as strain resistance sheets and optical fiber sensors, piezoelectric sensors are increasingly used in the SHM technology. The in-situ monitoring can be realized by a structure health monitoring technology based on the electric signals of the structure. This places new demands on the versatility of Glare laminates.
In order to meet the multifunctional requirements of the Glare (R) laminate under the structural health detection requirements, the existing Glare (R) laminate must be improved. Graphene is a hexagonal honeycomb lattice two-dimensional nanomaterial composed of carbon atoms in an sp2 hybridization manner. Graphene has high conductivity, high strength, and ultra-light and thin properties, and has been used for modification of resin materials to adjust mechanical properties and conductivity of the materials. There are various methods for preparing graphene, and generally, the thermal expansion method is a low-cost and low-consumption method, and does not need expensive equipment or complex operation. The thermal expansion method is an effective method for rapidly and continuously producing graphene by subjecting a graphite layer compound to high-temperature expansion and ultrasonic oscillation.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention aims to provide a multifunctional Glare laminate and a preparation method thereof, wherein the addition amount and the like of the key multifunctional filler graphene in the Glare laminate are improved, and a corresponding preparation method is adopted, so that the problem of single function and the like of the Glare laminate can be effectively solved compared with the prior art. And then forming a Glare laminate by hot press curing. The addition amount of graphene in the multifunctional Glare laminate in the adhesive is 0.2-1% by mass (the mass ratio of graphene in the cured adhesive is referred to, namely the ratio of graphene to the total mass of graphene, epoxy resin and epoxy resin curing agent).
The specific scheme of the invention is as follows:
a graphene modified multifunctional Glare laminate comprises glass fibers, an aluminum plate and a graphene modified adhesive; the graphene modified adhesive is epoxy resin dispersed with graphene. Wherein the mass ratio of the modifier graphene is 0.2-1 wt%, and the optimal mass ratio is 1 wt% (the mass ratio of the graphene refers to the ratio of the graphene in the total mass of the epoxy resin, the epoxy resin curing agent and the graphene); the mechanical property of the adhesive tends to increase first and then decrease along with the increase of the mass ratio of the modifier graphene.
The graphene modified multifunctional Glare laminate can be prepared by the following method: after an epoxy resin curing agent is added into the graphene modified adhesive, the graphene modified adhesive is mixed with glass fibers to form a prepreg, the prepreg and an aluminum plate are paved by a wet method to form an alternate paving structure, and then the graphene modified multifunctional Glare laminated plate is formed by thermal pressure curing.
The preparation method of the graphene modified multifunctional Glare laminate specifically comprises the following steps:
step 1, preparing a graphene modified adhesive:
(1) the graphene suspension was prepared using the following method:
placing the graphite intercalation compound into a muffle furnace for heating and expansion, and then adding a certain amount of acetone for ultrasonic oscillation for a certain time to obtain a uniform graphene suspension;
the heating temperature of the muffle furnace can be 700-710 ℃, and the heating expansion time is 2 min; the mass ratio of the acetone to the graphite intercalation compound after heating expansion is more than 20:1, and the ultrasonic oscillation time is 5-6 h.
(2) Adding the obtained graphene suspension into epoxy resin, ultrasonically stirring for 1-2 hours to uniformly mix graphene and epoxy resin, and volatilizing acetone to obtain the graphene modified adhesive.
The mass of the graphite intercalation compound after heating expansion added into acetone in the step (1) is the mass of graphene in the obtained graphene suspension, and the proportion of the epoxy resin and the epoxy resin curing agent can be determined in advance according to corresponding process requirements. Therefore, the specific ratio of the graphene suspension to the epoxy resin can be determined according to the designed graphene mass ratio (the ratio of the graphene to the total mass of the epoxy resin, the epoxy resin curing agent and the graphene).
And 2, carrying out mechanical treatment and electrochemical treatment on the surface of the aluminum plate for the multifunctional Glare laminate to form a rough surface favorable for bonding on the surface.
And 3, mixing the graphene modified adhesive added with the epoxy resin curing agent with glass fibers to form a prepreg, carrying out wet laying on an aluminum plate and the prepreg alternately layer by layer, and then putting the aluminum plate and the prepreg into an autoclave for curing at a preset temperature to obtain the graphene modified multifunctional Glare laminate.
The preparation method of the graphene modified multifunctional Glare laminate comprises the following steps:
in the step 1, the acetone is volatilized by adopting a method of heating in an oil bath and magnetically stirring; the heating temperature of the oil bath is 70 ℃, and the stirring time is 7-8 h.
In the step 2, the surface treatment method of the aluminum plate for the multifunctional Glare laminate is specifically to perform mechanical polishing and then perform anodic oxidation treatment to form a high-energy surface favorable for bonding.
In the step 3, a two-stage curing mode is adopted for curing and forming; wherein the first stage is a mild curing stage of the modified epoxy resin matrix, the curing temperature is 80-85 ℃, and the curing time is 25-30 min; the curing temperature of the second stage is 120-125 ℃, the curing time is 4-5 h, and the pressure is controlled to be 500-510 Ka in the two-stage curing process; the curing method is simple to operate and can obtain better curing results.
The reinforcing mechanism of graphene to Glare laminates mainly comprises three aspects:
1. the performance of the epoxy resin matrix in the graphene modified adhesive is improved: when cracks are generated and propagated in the resin matrix, the graphene can inhibit the propagation of the cracks through drawing and breaking, and the strength of the epoxy resin is improved.
2. The graphene can improve the interface performance of glass fiber and resin: graphene in the epoxy resin can be attached to the surface of the fiber, when the fiber and the graphene are debonded, namely the fiber is pulled out, the graphene participates in the debonding, more energy is absorbed in a pulling and breaking mode, and the interface performance of the fiber and the resin is enhanced.
3. The graphene can improve the interlayer performance of the aluminum plate surface and the epoxy resin matrix after treatment: the aluminum plate can form an uneven surface which is beneficial to bonding after surface treatment. Graphene can be attached to the surface of the aluminum plate, so that the adhesion force is enhanced, and the interlayer performance of the aluminum plate and the resin matrix is improved.
Therefore, the graphene modified adhesive adopted by the invention can improve the strength of the epoxy resin, can form a good matching effect with both the glass fiber and the metal plate layer of the Glare plate, and improves the bonding performance between the epoxy resin and the glass fiber interface or between the Glare plate layers. The mechanical strength of the Glare plate is improved as a whole.
The graphene has excellent conductivity, and the graphene modified Glare laminate has good mechanical strength and conductivity, can meet the multifunctional requirement of the Glare laminate in the using process, and achieves a better application effect. The method is expected to have wide application prospect in the fields of aerospace, transportation and transportation.
The invention has the beneficial effects that:
1. the invention adopts the surface treatment mode of the aluminum plate to form a microstructure which is beneficial to bonding, and improves the adhesive strength of the modified epoxy resin matrix.
2. When the modified epoxy resin matrix adopting the graphene as the modifier is broken, a large amount of energy is consumed for stretching and pulling the graphene, so that the cohesive force of the modified epoxy resin matrix is increased. Meanwhile, the graphene can also act on the interface between the epoxy resin matrix and the glass fiber, the prepreg layer (namely the composite material layer formed by the epoxy resin, the graphene and the glass fiber) and the interlayer of the aluminum plate, so that the interface and the interlayer strength are improved. The graphene is uniformly mixed in the epoxy resin matrix by adopting ultrasonic oscillation and ultrasonic stirring methods, so that the defect of agglomeration can be avoided, and the strength of the multifunctional Glare laminate can be better increased.
3. According to the invention, the graphene is adopted as a modifier, so that the mechanical property of the multifunctional Glare laminate can be improved, and the conductivity of the multifunctional Glare laminate can be improved due to excellent conductivity, and the graphene can be used for monitoring the structural health in the using process.
Drawings
FIG. 1 is a scanning electron microscope image of a cross section of the graphene-modified multifunctional Glare laminate in example 1.
FIG. 2 is a detailed lay-up of Glare plies of the invention, in which: 1-an aluminum plate layer; 2-fiberglass-epoxy prepreg layer.
FIG. 3 is a graph showing the tensile properties of the multifunctional Glare laminate of example 1, where (a) is the tensile strength and (b) is the Young's modulus.
FIG. 4 is a graph showing the flexural properties of the multifunctional Glare laminate of example 1, where (a) is the interlaminar shear strength (ILSS) at a cross-thickness ratio of 8/1, and (b) is the flexural strength at a cross-thickness ratio of 32/1.
FIG. 5 is a schematic diagram showing the electrochemical performance of the multifunctional Glare laminate of example 2.
FIG. 6 is a surface scanning electron micrograph of graphene modified Glare laminates of example 1 after tensile property testing at 0.2% by mass (panel a) and 1% by mass (panel b).
FIG. 7 is a cross-sectional micrograph of the graphene-modified Glare laminate of example 1 without the graphene modification (panel a) and 0.5% by mass (panel b) after three-point bending testing.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The graphene in the embodiment of the invention is obtained by thermal expansion of a graphite intercalation compound provided by the aid of archive Carbons, and the diameter of the graphene is 40-60 nm. The epoxy resin was a D230 type epoxy resin curing agent produced by Ciba-Geigy, Australia, and the epoxy resin curing agent was produced by Huntsman. In the embodiment of the invention, the mass ratio of the graphene is the ratio of the mass of the graphene to the total mass of the epoxy resin, the epoxy resin curing agent and the graphene; when the graphene suspension is prepared, the mass of the graphite intercalation compound added into acetone after heating expansion is the mass of the graphene in the obtained graphene suspension.
The following are specific examples:
example 1
In the multifunctional Glare laminate in this embodiment, graphene fillers are dispersed in an epoxy resin matrix of the multifunctional Glare laminate in an amount of 0, 0.2%, 0.3%, 0.5%, and 1% by mass. According to the formula proportion, the preparation method comprises the following steps:
step 1:
(1) placing the graphite intercalation compound into a muffle furnace at 700 ℃ for expansion for 2min, and then adding the graphite intercalation compound and acetone according to the mass ratio of 1:20 into acetone for ultrasonic oscillation for 5h to obtain a uniform graphene suspension;
(2) adding the obtained graphene suspension into epoxy resin according to the mass ratio of graphene (0, 0.2%, 0.3%, 0.5% and 1%), ultrasonically stirring for 2 hours to uniformly mix the graphene and the epoxy resin, and volatilizing acetone by adopting an oil bath heating magnetic stirring manner to obtain the graphene modified adhesive. The heating temperature of the oil bath is 70 ℃, and the magnetic stirring time is 8 hours;
step 2, carrying out mechanical polishing treatment and surface anodization treatment on the surface of the aluminum plate for the multifunctional Glare laminate to form a rough surface which is favorable for bonding on the surface and is convenient for being combined with a modified epoxy resin matrix;
and 3, mixing the graphene modified adhesive added with the epoxy resin curing agent and glass fibers to form a prepreg, carrying out wet laying on an aluminum plate and the prepreg alternately layer by layer, then placing the aluminum plate and the prepreg into an autoclave for curing at a preset temperature to obtain the graphene modified multifunctional Glare laminate, wherein the specific placement mode of the wet laying is shown in FIG. 2. And the curing adopts a two-stage curing mode, namely the first stage adopts a mode of curing at 80 ℃ for 25min, then the second stage adopts a mode of curing at 120 ℃ for 4h, the pressure is controlled to be 500-510 KPa in the two-stage curing process, and finally the graphene modified Glare laminate with different mass ratios is obtained.
The tensile properties of the graphene modified Glare laminate with different mass ratios are tested according to the test standard ASTM D3039, and the results are shown in FIG. 3, and as shown in FIG. 3, the tensile strength of the obtained Glare laminate is increased along with the increase of the mass ratio of the graphene, the maximum tensile strength (1%) is 245.45 +/-12.27 MPa, and is much higher than that of the Glare laminate without the added graphene (194.41 MPa); the Young modulus increases with the mass ratio of the graphene and then decreases, the maximum Young modulus (0.5%) is 58.33 +/-0.55 GPa, the difference of the Young modulus of the Glare plate modified by the graphene is not large in different mass ratios, but the Young modulus is increased obviously compared with that of the Glare plate without the graphene.
The flexural properties of graphene modified Glare laminates of different mass fractions were tested according to test standard ASTM D790, with the results shown in fig. 4. With the increase of the mass ratio of the graphene, the interlaminar shear strength (ILSS) under the condition of the span-thickness ratio 8/1 and the bending strength under the condition of the span-thickness ratio 32/1 tend to increase and then decrease, the maximum interlaminar shear strength under the condition of the span-thickness ratio 8/1 is 19.06 +/-0.95 MPa, and the maximum bending strength under the condition of the span-thickness ratio 32/1 is 260.22 +/-13.01 MPa. The bending strength of the graphene modified Glare (Glare) laminate is obviously higher than that of a Glare (Glare) laminate without graphene.
A scanning electron micrograph of a cross section of the graphene modified Glare (Glare) laminate with a mass fraction of 0.5 wt.% is shown in fig. 1.
Fig. 6 is a surface scanning electron microscope photograph of 0.2% and 1% graphene modified Glare laminate subjected to tensile property test, after the Glare laminate is subjected to tensile load fiber failure, fibers in the 0.2% graphene modified Glare laminate are in beard-shaped irregularity, which indicates that the interface property between the fibers and the resin matrix is relatively weak, and the fibers in the 1% graphene modified Glare laminate are relatively flat after breakage, which indicates that the interface property between the fibers and the resin matrix is relatively strong, and shows the reinforcing effect of the graphene on the interface of the epoxy resin and the glass fiber.
Fig. 7 is a cross-sectional micrograph of a graphene-unmodified Glare (Glare) laminate (graphene mass percentage is 0%) and a graphene-modified Glare laminate (graphene mass percentage is 1%) after a three-point bending test, and it can be seen from fig. 7 that the glass fiber-epoxy resin layer and the aluminum plate layer of the graphene-modified Glare (Glare) laminate (graphene mass percentage is 1%) are debonded, while the glass fiber-epoxy resin layer and the aluminum plate layer of the graphene-modified Glare (Glare) laminate (graphene mass percentage is 1%) have good bonding performance, and the interlayer reinforcing effect of graphene on metal and resin is reflected.
Example 2
In the multifunctional Glare laminate in this embodiment, 0.5% by mass of graphene filler is dispersed in an epoxy resin matrix of the multifunctional Glare laminate.
The multifunctional Glare laminate is prepared according to the formula proportion by the following method:
step 1:
(1) placing the graphite intercalation compound into a muffle furnace at 710 ℃ for expansion for 2min, and then adding the graphite intercalation compound and acetone according to the mass ratio of 1:25 to the acetone for ultrasonic oscillation for 6h to obtain a uniform graphene suspension;
(2) adding the obtained graphene suspension into epoxy resin according to the mass ratio of 0.5% of graphene, ultrasonically stirring for 1h to uniformly mix the graphene and the epoxy resin, and volatilizing acetone by adopting an oil bath heating magnetic stirring manner to obtain the graphene modified adhesive. The heating temperature of the oil bath is 70 ℃, and the magnetic stirring time is 7 h.
Step 2, carrying out mechanical polishing treatment and surface anodization treatment on the surface of the aluminum plate for the multifunctional Glare laminate to form a rough surface which is favorable for bonding on the surface and is convenient for being combined with a modified epoxy resin matrix;
and 3, mixing the graphene modified adhesive added with the epoxy resin curing agent with glass fibers to form a prepreg, carrying out wet laying on an aluminum plate and the prepreg alternately layer by layer, and then putting the aluminum plate and the prepreg into an autoclave for curing at a preset temperature to obtain the graphene modified multifunctional Glare laminate. The curing adopts a two-stage curing mode, namely the first stage adopts a mode of curing at 85 ℃ for 30min, then the second stage adopts a mode of curing at 125 ℃ for 5h, and the pressure is controlled to be 500-510 KPa in the two-stage curing process.
The electrochemical performance of the obtained 0.5% mass ratio graphene modified multifunctional Glare (Glare) laminate was measured by an electrochemical workstation, as shown in fig. 5. The specific capacitances at different scan speeds (40,80,100mV/s) were 1.76,2.47, and 2.88F/g.

Claims (8)

1. The graphene modified multifunctional Glare laminate is characterized by comprising glass fibers, an aluminum plate and a graphene modified adhesive; the graphene modified adhesive is epoxy resin dispersed with graphene;
after an epoxy resin curing agent is added into the graphene modified adhesive, the graphene modified adhesive is mixed with glass fibers to form a prepreg, the prepreg and an aluminum plate are paved by a wet method to form an alternate paving structure, and then the graphene modified multifunctional Glare laminated plate is formed by thermal pressure curing.
2. The graphene-modified multifunctional Glare laminate according to claim 1, wherein in the graphene-modified adhesive, the mass ratio of graphene is 0.2-1% of the total mass of graphene, epoxy resin and epoxy resin curing agent.
3. The graphene-modified multifunctional Glare laminate according to claim 2, wherein in the graphene-modified adhesive, the mass ratio of graphene is 1% of the total mass of graphene, epoxy resin and epoxy resin curing agent.
4. The method for preparing graphene modified multifunctional Glare (Glare) laminate according to any one of claims 1 to 3, comprising the following steps:
step 1, preparing a graphene modified adhesive:
(1) the graphene suspension was prepared using the following method:
placing the graphite intercalation compound into a muffle furnace for heating and expansion, and then adding a certain amount of acetone for ultrasonic oscillation for a certain time to obtain a uniform graphene suspension;
(2) adding the obtained graphene suspension into epoxy resin, ultrasonically stirring for 1-2 hours to uniformly mix graphene and epoxy resin, and volatilizing acetone to obtain a graphene modified adhesive;
step 2, carrying out mechanical treatment and electrochemical treatment on the surface of the aluminum plate for the multifunctional Glare laminate to form a rough surface which is favorable for bonding on the surface;
and 3, mixing the graphene modified adhesive added with the epoxy resin curing agent with glass fibers to form a prepreg, carrying out wet laying on an aluminum plate and the prepreg alternately layer by layer, and then putting the aluminum plate and the prepreg into an autoclave for curing at a preset temperature to obtain the graphene modified multifunctional Glare laminate.
5. The preparation method of the graphene modified multifunctional Glare laminate according to claim 4, wherein in the step 1(1), the heating temperature of a muffle furnace is 700-710 ℃, the expansion time is 2min, the mass ratio of acetone to the graphite intercalation compound after heating expansion is more than 20:1, and the ultrasonic oscillation time is 5-6 h.
6. The preparation method of the graphene modified multifunctional Glare laminate according to claim 4, wherein in the step 1, the acetone is volatilized by heating in an oil bath and magnetic stirring, the heating temperature of the oil bath is 70 ℃, and the stirring time is 7-8 h.
7. The method for preparing the graphene-modified multifunctional Glare (Glare) laminate according to claim 4, wherein in the step 2, the method for mechanically and electrochemically treating the surface of the aluminum plate for the multifunctional Glare laminate comprises the following steps: firstly, mechanical polishing is carried out, and then anodic oxidation treatment is carried out.
8. The preparation method of the graphene modified multifunctional Glare (Glare) laminate according to claim 4, wherein in the step 3, the curing is performed in a two-stage curing manner: wherein the first stage is a gentle curing stage, the curing temperature is 80-85 ℃, and the curing time is 25-30 min; the curing temperature of the second stage is 120-125 ℃, and the curing time is 4-5 h; meanwhile, the pressure is controlled to be 500-510 KPa in the two-stage curing process.
CN202110087776.1A 2021-01-22 2021-01-22 Graphene modified multifunctional Glare laminate and preparation method thereof Pending CN112848561A (en)

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* Cited by examiner, † Cited by third party
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CN101289017A (en) * 2007-04-18 2008-10-22 上海磁浮交通工程技术研究中心 Composite material construction for high-speed train and its manufacturing method
CN103153896A (en) * 2010-09-14 2013-06-12 Ppg工业俄亥俄公司 Low density and high strength fiber glass for reinforcement applications
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CN103895315A (en) * 2014-02-19 2014-07-02 南京航空航天大学 Preparation molding method of Glare component
KR20160079326A (en) * 2014-12-26 2016-07-06 홍익대학교세종캠퍼스산학협력단 Method for manufacturing hybrid composite material comprising glass fiber reinforced plastic and aluminum and hybrid composite material
CN105968718A (en) * 2016-05-20 2016-09-28 北京化工大学 Preparation method of carbon fiber/graphene/epoxy resin prepreg and carbon fiber composite material
CN106003920A (en) * 2016-04-22 2016-10-12 苏州派欧技术咨询服务有限公司 Interlayer composite material for high-speed rail and bullet train floor
CN111849400A (en) * 2020-07-30 2020-10-30 沈阳航空航天大学 Method for repairing Glare laminate by modified adhesive through adhesive bonding

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289017A (en) * 2007-04-18 2008-10-22 上海磁浮交通工程技术研究中心 Composite material construction for high-speed train and its manufacturing method
CN103153896A (en) * 2010-09-14 2013-06-12 Ppg工业俄亥俄公司 Low density and high strength fiber glass for reinforcement applications
US20130316148A1 (en) * 2010-11-29 2013-11-28 Gtm-Advanced Products B.V. Metal sheet-fiber reinforced composite laminate
CN103895315A (en) * 2014-02-19 2014-07-02 南京航空航天大学 Preparation molding method of Glare component
KR20160079326A (en) * 2014-12-26 2016-07-06 홍익대학교세종캠퍼스산학협력단 Method for manufacturing hybrid composite material comprising glass fiber reinforced plastic and aluminum and hybrid composite material
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CN111849400A (en) * 2020-07-30 2020-10-30 沈阳航空航天大学 Method for repairing Glare laminate by modified adhesive through adhesive bonding

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