CN110938304A - Hybrid fiber composite material and preparation method thereof - Google Patents
Hybrid fiber composite material and preparation method thereof Download PDFInfo
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- CN110938304A CN110938304A CN201911303561.8A CN201911303561A CN110938304A CN 110938304 A CN110938304 A CN 110938304A CN 201911303561 A CN201911303561 A CN 201911303561A CN 110938304 A CN110938304 A CN 110938304A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/10—Polyamides derived from aromatically bound amino and carboxyl groups of amino-carboxylic acids or of polyamines and polycarboxylic acids
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- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The invention discloses a hybrid fiber composite material and a preparation method thereof, belonging to the technical field of composite materials, wherein the hybrid fiber composite material comprises the following raw materials in parts by mass: 12-18 parts of glass fiber, 15-30 parts of carbon fiber, 6-12 parts of plant fiber, 20-25 parts of aramid fiber, 2-5 parts of carbon nano tube, 7-15 parts of cellulose nano fiber, 12-25 parts of epoxy resin, 5-10 parts of aromatic hydrocarbon resin and 3-6 parts of binder; the hybrid fiber composite material prepared by the invention has good mechanical property, and solves the problem that the composite material in the prior art has poor tensile strength and toughness.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a hybrid fiber composite material and a preparation method thereof.
Background
The hybrid composite material is a composite material obtained by reinforcing the same substrate or a plurality of substrates with two or more kinds of reinforcements. Hybrid composites can be viewed as the intermingling of two or more fiber or particle reinforced composites. According to the matrix composition, the hybrid composite material can be classified into a metal matrix hybrid composite material, a ceramic matrix hybrid composite material, a resin matrix hybrid composite material and a hybrid composite material compounded by various matrixes. According to the reinforcement, they can be classified into hybrid fiber composites, hybrid particle composites and fiber and particle hybrid composites. Hybrid composites are referred to as super-hybrid composites when there is more than one type of both the reinforcement and the matrix.
The hybrid composite material has the characteristics of high specific strength and high specific modulus, so that the hybrid composite material is an ideal material for aviation and aerospace product structures. The application of the hybrid composite material not only promotes the updating of structural products in the aerospace field, but also plays a positive role in relieving the problem of insufficient international energy at present.
Composite materials for aviation are classified into resin matrix composite (PMC), Metal Matrix Composite (MMC), Ceramic Matrix Composite (CMC), carbon-carbon composite (C/C), and the like. Resin-based composite materials have important properties required by modern aircraft, such as high specific strength, specific modulus, dimensional stability, excellent corrosion resistance, wear resistance, dielectric properties, electrical insulation properties, comprehensive mechanical properties, designable and formable process diversity of properties, and the like, and thus are widely used in the aviation industry. Resin-based composites are also known as fiber-reinforced plastics. Resin-based composite materials are classified into thermosetting resin-based composite materials and thermoplastic resin-based composite materials according to the type of resin. Thermosetting resin-based composites were the first applications in the aerospace industry, the largest number of composites currently in use in the aerospace industry. The outstanding characteristics of high specific strength and specific modulus make the material one of the most important airplane materials at present. The thermosetting resin-based composite material includes epoxy resin, phenolic resin, bismaleimide resin and the like according to different resin systems. Currently, epoxy resin occupies the dominance in composite materials for aviation. Epoxy resin-based composite materials are a class of composite materials which are mature in technology and wide in application. The reinforced fiber is mainly classified into carbon fiber Composites (CFRP), aramid fiber composites (AFRP), glass fiber composites (GFRP) and the like according to the difference of the reinforced fiber.
If two or more than two kinds of fibers are used together, the respective characteristics can be better played by making up for the deficiencies, even the synergistic effect is achieved, and the comprehensive performance of the composite material is improved. The hybrid composite material is obtained by reinforcing the same kind of resin matrix with various fibers in a hybrid manner. The hybrid composite material is a new composite mode composite material developed in the 70 s of the 20 th century. The method is divided into a plurality of modes such as in-layer mixing, interlayer mixing and composite mixing according to different fiber paving modes, wherein the interlayer mixing is the most common and easily realized composite mode.
The fiber reinforced composite material has the advantages of light weight, high strength, corrosion resistance, designability and the like, and is widely applied to other fields, along with the continuous and deep research, many basic theories and methods tend to be perfect, novel FRP materials emerge continuously, new application technologies emerge endlessly, and the application in infrastructure construction shows a trend of high-speed development. In China, research and development of FRP materials and application of FRP materials in infrastructure construction are rapidly developed. The fiber reinforced material has the properties of elastic materials, and has high strength, but poor tensile strength and toughness.
Disclosure of Invention
The invention aims to provide a hybrid fiber composite material and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a hybrid fiber composite material which comprises the following raw materials in parts by mass:
12-18 parts of glass fiber, 15-30 parts of carbon fiber, 6-12 parts of plant fiber, 20-25 parts of aramid fiber, 2-5 parts of carbon nano tube, 7-15 parts of cellulose nano fiber, 12-25 parts of epoxy resin, 5-10 parts of aromatic hydrocarbon resin and 3-6 parts of binder.
Further, the glass fiber is continuous alkali-free glass fiber, and the diameter of the glass fiber is 15-25 mu m.
Further, the plant fiber is selected from the following materials: ramie, jute, sisal, kenaf or kenaf, with a diameter of 50-70 μm.
Further, the plant fiber is subjected to alkali treatment, alcohol treatment and heat treatment before use.
Further, the carbon nanotubes are single-walled carbon nanotubes.
Further, the diameter of the cellulose nano-fiber is 10-28nm, and the length-diameter ratio is larger than 110.
Further, the epoxy resin is toughened epoxy resin 3323 cured at medium temperature.
Further, the binder is a mixture of butyronitrile modified phenolic resin and rubber powder.
The invention also provides a preparation method of the hybrid fiber composite material, which comprises the following steps:
(1) soaking aramid fiber in 80g/L NaOH solution for 2-3h under the protection of argon, taking out, soaking in ethanol solution for 1-2h, washing, and performing heat treatment at 150 ℃ for 1 h;
(2) adding epoxy resin into a container, stirring for 3min at 500-900r/min, sequentially adding glass fiber and carbon fiber, and stirring uniformly;
(3) adding aromatic hydrocarbon resin, stirring for 2min at 1300r/min of 1000-.
The invention discloses the following technical effects:
the hybrid fiber composite material prepared by the invention has good mechanical property, and solves the problem that the composite material in the prior art has poor tensile strength and toughness. The glass fiber has higher tensile strength, and can play a role in transferring cracks and pulling out when stressed after the composite material is introduced, and a large amount of energy can be absorbed in the process, so that the reinforcing effect is realized; the cellulose nano-fiber with the ultra-high length-diameter ratio can play a role similar to a beam, so that various fibers are tightly connected with each other, and the cellulose nano-fiber with the ultra-high length-diameter ratio can support a base material to a great extent when stressed, so that the elastic modulus and the bending strength of the base material are enhanced.
Failure of the composite is most easily initiated at the interface, which is characterized by interlaminar shear strength. The intermingling of different fibers places certain requirements on the resin matrix, which has certain strength and toughness to be compatible with fibers having different elongations to break and interfaces. The invention adopts toughened epoxy resin which is cured at medium temperature (125 ℃) as a matrix, and the toughened epoxy resin has good compatibility with the surfaces of glass fiber, aramid fiber and carbon fiber, so that the shearing strength of the composite material is higher.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a graph comparing tensile strength and impact toughness for examples 1-6 and comparative examples 1-2;
FIG. 2 is a graph comparing the elastic modulus and the bending strength of examples 1 to 6 and comparative examples 1 to 2.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
Example 1
The hybrid fiber composite material comprises the following raw materials in parts by mass:
15 parts of glass fiber, 22 parts of carbon fiber, 9 parts of plant fiber, 22 parts of aramid fiber, 4 parts of carbon nanotube, 9 parts of cellulose nanofiber, 19 parts of epoxy resin, 8 parts of aromatic hydrocarbon resin and 4 parts of binder.
The plant fiber is selected from kenaf, and has a diameter of 50-70 μm.
The adhesive is a mixture of butyronitrile modified phenolic resin and rubber powder in equal mass.
The preparation method of the hybrid fiber composite material comprises the following steps:
(1) soaking aramid fiber in 80g/L NaOH solution for 2.5h under the protection of argon, taking out, soaking in ethanol solution for 1h, washing, and performing heat treatment at 150 ℃ for 1 h;
(2) adding epoxy resin into a container, stirring for 3min at 700r/min, sequentially adding glass fiber and carbon fiber, and stirring uniformly;
(3) adding aromatic hydrocarbon resin, stirring at 1150r/min for 2min, reducing the stirring speed to 400r/min, adding plant fiber, carbon nanotube and cellulose nanofiber, stirring for 2min, adding binder, stirring for 5min, adding aramid fiber, stirring for 5min, curing at 125 deg.C for 100min, and granulating.
Example 2
The hybrid fiber composite material comprises the following raw materials in parts by mass:
18 parts of glass fiber, 15 parts of carbon fiber, 12 parts of plant fiber, 20 parts of aramid fiber, 5 parts of carbon nanotube, 7 parts of cellulose nanofiber, 25 parts of epoxy resin, 5 parts of aromatic hydrocarbon resin and 6 parts of binder.
The plant fiber is selected from kenaf, and has a diameter of 50-70 μm.
The adhesive is a mixture of butyronitrile modified phenolic resin and rubber powder in equal mass.
The preparation method of the hybrid fiber composite material comprises the following steps:
(1) soaking aramid fiber in 80g/L NaOH solution for 2h under the protection of argon, taking out, soaking in ethanol solution for 2h, washing, and performing heat treatment at 150 ℃ for 1 h;
(2) adding epoxy resin into a container, stirring for 3min at a speed of 500r/min, sequentially adding glass fiber and carbon fiber, and stirring uniformly;
(3) adding aromatic hydrocarbon resin, stirring at 1300r/min for 2min, reducing the stirring speed to 300r/min, adding plant fiber, carbon nanotube and cellulose nanofiber, stirring for 2min, adding binder, stirring for 5min, adding aramid fiber, stirring for 5min, curing at 125 deg.C for 100min, and granulating.
Example 3
The hybrid fiber composite material comprises the following raw materials in parts by mass:
12 parts of glass fiber, 30 parts of carbon fiber, 6 parts of plant fiber, 25 parts of aramid fiber, 2 parts of carbon nanotube, 15 parts of cellulose nanofiber, 12 parts of epoxy resin, 10 parts of aromatic hydrocarbon resin and 3 parts of binder.
The plant fiber is selected from sisal, and has a diameter of 50-70 μm.
The adhesive is a mixture of butyronitrile modified phenolic resin and rubber powder in equal mass.
The preparation method of the hybrid fiber composite material comprises the following steps:
(1) soaking aramid fiber in 80g/L NaOH solution for 3h under the protection of argon, taking out, soaking in ethanol solution for 1h, washing, and performing heat treatment at 150 ℃ for 1 h;
(2) adding epoxy resin into a container, stirring for 3min at 900r/min, sequentially adding glass fiber and carbon fiber, and stirring uniformly;
(3) adding aromatic hydrocarbon resin, stirring at 1000r/min for 2min, reducing the stirring speed to 500r/min, adding plant fiber, carbon nanotube and cellulose nanofiber, stirring for 2min, adding binder, stirring for 5min, adding aramid fiber, stirring for 5min, curing at 125 deg.C for 100min, and granulating.
Example 4
The hybrid fiber composite material comprises the following raw materials in parts by mass:
13 parts of glass fiber, 28 parts of carbon fiber, 7 parts of plant fiber, 24 parts of aramid fiber, 3 parts of carbon nanotube, 13 parts of cellulose nanofiber, 15 parts of epoxy resin, 9 parts of aromatic hydrocarbon resin and 4 parts of binder.
The plant fiber is selected from jute, and has diameter of 50-70 μm.
The adhesive is a mixture of butyronitrile modified phenolic resin and rubber powder in equal mass.
The preparation method of the hybrid fiber composite material comprises the following steps:
(1) soaking aramid fiber in 80g/L NaOH solution for 3h under the protection of argon, taking out, soaking in ethanol solution for 1h, washing, and performing heat treatment at 150 ℃ for 1 h;
(2) adding epoxy resin into a container, stirring for 3min at 900r/min, sequentially adding glass fiber and carbon fiber, and stirring uniformly;
(3) adding aromatic hydrocarbon resin, stirring at 1100r/min for 2min, reducing the stirring speed to 350r/min, adding plant fiber, carbon nanotube and cellulose nanofiber, stirring for 2min, adding binder, stirring for 5min, adding aramid fiber, stirring for 5min, curing at 125 deg.C for 100min, and granulating.
Example 5
The hybrid fiber composite material comprises the following raw materials in parts by mass:
17 parts of glass fiber, 16 parts of carbon fiber, 11 parts of plant fiber, 22 parts of aramid fiber, 3 parts of carbon nanotube, 9 parts of cellulose nanofiber, 23 parts of epoxy resin, 7 parts of aromatic hydrocarbon resin and 5 parts of binder.
The plant fiber is selected from ramie, and has a diameter of 50-70 μm.
The adhesive is a mixture of butyronitrile modified phenolic resin and rubber powder in equal mass.
The preparation method of the hybrid fiber composite material comprises the following steps:
(1) soaking aramid fiber in 80g/L NaOH solution for 2h under the protection of argon, taking out, soaking in ethanol solution for 2h, washing, and performing heat treatment at 150 ℃ for 1 h;
(2) adding epoxy resin into a container, stirring at 800r/min for 3min, sequentially adding glass fiber and carbon fiber, and stirring uniformly;
(3) adding aromatic hydrocarbon resin, stirring at 1200r/min for 2min, reducing the stirring speed to 450r/min, adding plant fiber, carbon nanotube and cellulose nanofiber, stirring for 2min, adding binder, stirring for 5min, adding aramid fiber, stirring for 5min, curing at 125 deg.C for 100min, and granulating.
Comparative example 1
The difference from example 1 is that the aspect ratio of the cellulose nanofibers used in comparative example 1 is between 10 and 30.
Comparative example 2
The difference from example 1 is that comparative example 2 replaces carbon nanotubes with carbon fibers in equal amounts.
The hybrid fiber composite materials of examples 1-5 and comparative examples 1-2 were made into sample blocks of 20mm by 30mm by 5mm and tested for performance. The tensile strength and impact toughness are shown in FIG. 1, and it can be seen that the hybrid fiber composites prepared in examples 1-5 have both tensile strength and impact toughness significantly better than those of comparative examples 1-2; the elastic modulus and bending strength are shown in FIG. 2, and it can be seen that the hybrid fiber composites prepared in examples 1-5 have significantly better elastic modulus and bending strength than comparative examples 1-2.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. The hybrid fiber composite material is characterized by comprising the following raw materials in parts by mass:
12-18 parts of glass fiber, 15-30 parts of carbon fiber, 6-12 parts of plant fiber, 20-25 parts of aramid fiber, 2-5 parts of carbon nano tube, 7-15 parts of cellulose nano fiber, 12-25 parts of epoxy resin, 5-10 parts of aromatic hydrocarbon resin and 3-6 parts of binder.
2. A hybrid fiber composite according to claim 1, wherein said glass fibers are continuous alkali-free glass fibers having a diameter of 15-25 μm.
3. A hybrid fiber composite according to claim 1, wherein said plant fibers are selected from the group consisting of: ramie, jute, sisal, kenaf or kenaf, with a diameter of 50-70 μm.
4. A hybrid fiber composite according to claim 1, wherein said plant fibers are subjected to alkali treatment, alcohol treatment and heat treatment before use.
5. A hybrid fiber composite as claimed in claim 1, wherein said carbon nanotubes are single-walled carbon nanotubes.
6. A hybrid fiber composite according to claim 1, wherein said cellulose nanofibers have a diameter of 10-28nm and an aspect ratio of greater than 110.
7. A hybrid fiber composite according to claim 1, wherein said epoxy resin is a mid-temperature cured toughened epoxy resin 3323.
8. A hybrid fiber composite according to claim 1, wherein the binder is a mixture of butyronitrile modified phenolic resin and rubber powder.
9. A method for preparing a hybrid fiber composite according to any one of claims 1 to 8, comprising the steps of:
(1) soaking aramid fiber in 80g/L NaOH solution for 2-3h under the protection of argon, taking out, soaking in ethanol solution for 1-2h, washing, and performing heat treatment at 150 ℃ for 1 h;
(2) adding epoxy resin into a container, stirring for 3min at 500-900r/min, sequentially adding glass fiber and carbon fiber, and stirring uniformly;
(3) adding aromatic hydrocarbon resin, stirring for 2min at 1300r/min of 1000-.
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Application publication date: 20200331 |