CN107698738B - Preparation method of oxidation modified CB/CFDSF/AG-80 epoxy resin composite material - Google Patents
Preparation method of oxidation modified CB/CFDSF/AG-80 epoxy resin composite material Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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- D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
- D06L1/02—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using organic solvents
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
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- D06M2101/40—Fibres of carbon
Abstract
The invention relates to a method for preparing oxidation modified CB/CFDSF/AG-80 epoxy resin composite material, which mainly comprises a first step of modifying Carbon Black (CB) by concentrated nitric acid, a second step of carrying out surface cleaning and surface modification treatment on carbon fiber double-layer spacer fabric (CFDSF) and a third step of pouring and thermosetting CFDSF by prepared modified CB/AG-80 epoxy resin system solution, wherein the preparation steps and specific process parameters thereof are adopted to prepare the concentrated nitric acid modified CB/CFDSF/AG-80 epoxy resin composite material which has good conductivity and thermodynamic property and small conductive material consumption, and the modified carbon black of the composite material is uniformly distributed in a matrix, has good conductivity stability, and can be widely applied to electronics, electrostatic protection and electrostatic protection, Electromagnetic shielding, microwave absorption, etc.
Description
Technical Field
The invention relates to the field of composite materials, in particular to an oxidation modified CB/CFDSF (carbon fiber double-layer spacer fabric)/AG-80 epoxy resin composite material and a preparation method thereof.
Background
With the increasing change of the electronic technology industry, the demand for functional composite materials with good electrical conductivity is also increasing. The conductive composite material has the characteristics of light weight, no corrosion, good dimensional stability and adjustable conductivity in a larger range, is easy to process into various complicated shapes and is easy for large-scale industrial production, so the conductive composite material is widely applied in the fields of electrostatic protection, electromagnetic shielding, microwave absorption and the like. At present, a common conductive composite material usually uses a polymer as a matrix, conductive substances such as carbon materials, metal fillers and the like are added at the same time, and the mixture is compounded by a physical or chemical method to obtain a multiphase composite material with certain conductive performance and good mechanical property.
The carbon-based material mainly comprises Carbon Black (CB), graphite, Carbon Fiber (CF), Carbon Nanotubes (CNTs), and the like, which are important components of conductive fillers in conductive composite materials. Carbon-based material filled polymer composites are gaining increasing attention in a number of areas because of their ease of molding, freedom from molding size limitations, and corrosion resistance, and their ability to be used in certain specific environments.
CB is the most widely used and used amount of conductive filler at present. It has low cost, high conductivity and low density. Therefore, a conductive composite material using CB particles as a conductive filler has excellent conductive properties and is widely used in various fields. Meanwhile, because of the high surface energy of the CB particles and the active groups distributed on the surfaces of the CB particles, the CB particles have large polymerization force, so that the particles are easy to polymerize with each other and are difficult to be dispersed. Therefore, in general, CB is required to be uniformly dispersed and filled in a matrix in a fine state. Otherwise, the material properties will be degraded, and thus, ensuring uniform dispersion of CB in the matrix is critical to the good properties of the conductive composite.
The modification of CB generally adopts a dispersant modification method, an oxidant modification method and a graft modification method. The researchers improve the uniformity of CB by utilizing a surfactant method, and the use of the dispersant is considered to be beneficial to uniformly dispersing CB in a solution such as benzene cyclohexane, n-heptane and the like, thereby effectively improving the uniformity of the system. The use of the salt of succinic acid diisooctyl-sulphonate enables stable dispersion of the CB in benzene solvents, and the use of ionic surfactants also enables uniform dispersion of the CB in certain systems, but if these systems are added to polymeric solutions, the uniformity of the CB is greatly impaired, resulting in sedimentation, and these dispersants have little potential for use in the coatings and inks industry; the oxidation modification method of CB is divided into a gas phase method, a liquid phase method and a plasma method, the gas phase method mainly utilizes gases such as oxygen to modify the surface of CB so as to improve active groups on the surface of particles, and the liquid phase method utilizes various different oxidants to fully react with CB respectively and introduce active groups such as hydroxyl, carboxyl and the like on the surface of particles so as to achieve the purpose of modification. Plasma physical oxidation; the graft modification is mainly to graft some polymer chains on the surface of the CB particles stably, and the polymer chains generate repulsion in water, so that the mutual distance among the particles is ensured, and the uniformity of the CB particles is ensured. The surface of the CB particles is grafted with a plurality of stable polymer chains, which are formed by the hydroxyl groups, the carboxyl groups, the hydrogen bonds and the like which are carried on the CB particles into various active functional groups, and the functional groups are easy to react with a substrate which also has active end groups, so that the CB particles are firmly combined with the substrate.
At present, the current research situation at home and abroad of carbon black/epoxy resin composite materials is as follows:
the physical properties of conductive composites having CB as the conductive filler are related to many factors. The difference of the types and the content of the CB and the difference of the matrix can influence the distribution state of the CB and the structural state of the matrix to a great extent, and then influence the conductivity, the mechanical property, the thermal property and the like of the composite material.
Chensu et al studied the conductivity of polystyrene/CB composites in the paper "PS/carbon black composites conductivity. Experimental analysis shows that the volume resistivity of the polystyrene/CB system shows a nonlinear reduction phenomenon when the content of the CB is gradually increased, and the volume resistivity of the composite material system is obviously reduced when the content of the CB is between 20% and 30%.
Mohan raj g.t. et al studied composites with styrene butadiene rubber as the matrix and CB as the Conductive filler in "AC Impedance Analysis and EMI shielding efficiency of Conductive SBR composites. When the frequency range is between 7.8GHz and 12.4GHz, if the filling amount of the CB reaches 60 percent, the shielding performance of the composite material can reach 67dB at most.
Das N.C. et al prepared CB/CF/ethylene-Vinyl Acetate copolymer Composites having cost, mechanical properties and Shielding properties in consideration of "electronic Interference Shielding effect Based on Conductive Composites connections" research, and the Shielding properties of the composite could be as high as 40dB when the CB and CF contents are 30% and 20%, respectively.
The effect of "CB content and mixing time on the performance of CB/PP composites" of Hao Haishen et al, the mechanical properties of CB/polypropylene composites systems are studied in the plastics industry. The research result shows that the tensile strength curve of the CB/polypropylene system is increased and then decreased along with the gradual increase of the content of the CB, and the maximum tensile strength of the system is 23.71 MPa. At the same time, the elongation at break of the CB/PP system shows a tendency to decrease with increasing CB content.
The influence of the change of the content of CB on the mechanical property of a high-density polyethylene/CB composite material system is researched in a research paper of conducting and toughening of a polymer/carbon black composite material. Research and analysis show that the impact strength curve of the composite material shows a descending trend along with the increase of the content of the CB, and the impact strength is only 8.5KJ/m when the content of the CB is 18 percent2。
The electrical and mechanical properties of the fiber-reinforced modified epoxy system are researched by Zhang Qiu Ju in a paper of 'research on the electrical and mechanical properties of the fiber-reinforced modified epoxy system', wherein the preparation of a carbon fiber/epoxy resin composite material is related, carbon fibers are woven into a space fabric to be treated and then are used as a reinforcement to be added into an AG-80 epoxy resin matrix to form the composite material, although the thermodynamic properties of the composite material are improved, the electrical conductivity and the stability of the composite material are still not satisfied.
Chinese patent application (201310413596.3) discloses a modified carbon fiber/epoxy resin composite material and a preparation method thereof, wherein the preparation method comprises the steps of mixing graphene and liquid epoxy resin to obtain a first mixture, adding a curing agent capable of crosslinking and curing the liquid epoxy resin into the first mixture to obtain a second mixture, and adopting a composite material molding process to crosslink and cure the liquid epoxy resin by using the carbon fiber and the second mixture as raw materials to form the modified carbon fiber/epoxy resin composite material integrated with the carbon fiber.
As is apparent from the above documents, the difference in the type, content, etc. of CB greatly affects the properties of the matrix of the composite material, and in turn, greatly affects the physical properties of the composite material system. In order to make the composite material system have good conductive performance, the filling amount of the CB is generally large, and the mechanical property and the like of the system are greatly influenced after a large amount of the CB is filled. Therefore, in order to fully ensure good conductivity, thermodynamic property and the like of the composite material under the condition of keeping a low filling amount, modification treatment needs to be carried out on the conductive filler or the synergistic effect of the multi-component conductive filler on the composite material needs to be researched, and the bottleneck problem in the current development of the composite conductive material is solved.
Disclosure of Invention
In order to overcome the technical problems, the invention researches a method for improving the electrical property, the mechanical property, the thermal property and the like of a composite material system by modifying a conductive filler and mixing a multi-component filler, and further provides an oxidation modified CB/CFDSF/AG-80 epoxy resin composite material which has good conductive property and thermodynamic property and uses a small amount of conductive material and a preparation method thereof. Therefore, the invention provides the following technical scheme:
the preparation method of the oxidation modified CB/CFDSF/AG-80 epoxy resin composite material is characterized by comprising the following steps:
(1) carrying out modification treatment on Carbon Black (CB) by using concentrated nitric acid, pouring 4-12 g of carbon black and 50-100 ml of concentrated nitric acid with the concentration of 65-70 wt% into a beaker respectively, heating to 100-110 ℃, fully stirring for 2-3 h, diluting with distilled water, carrying out suction filtration, carefully scraping the filtered CB, putting the filtered CB into the beaker, pouring a large amount of distilled water for continuously diluting, standing for a proper time, pouring out supernatant liquid, continuously carrying out suction filtration, repeating the operation for a plurality of times until the pH value of the supernatant liquid is about 7, then placing the filtered CB in an oven for drying, and grinding for 0.5-1 h after drying to obtain the oxidation modified carbon black O-CB;
(2) the method comprises the following steps of treating carbon fiber double-layer spacer fabric (CFDSF), and carrying out surface cleaning and surface modification treatment on the carbon fiber double-layer spacer fabric which is woven and cut in advance, wherein the specific process comprises the following steps: placing the cut double-layer carbon fiber spacer fabric in an ultrasonic cleaning solution at room temperature, soaking for 1-2 hours, washing for 30-50 minutes, taking out, drying at 95-110 ℃, coating a certain amount of silane coupling agent KH550 solution which is dissolved in water and contains 1.5-3 wt% of absolute ethyl alcohol on the double-layer spacer fabric, placing for 24-36 hours at room temperature so as to completely volatilize the ethyl alcohol, and sealing for later use;
(3) preparing a modified CB/AG-80 epoxy resin system solution to pour and thermally cure the CFDSF, respectively putting AG-80 epoxy resin, a hexahydrophthalic anhydride curing agent, a 2,4, 6-diaminomethylphenol accelerator, acetone and an absolute ethyl alcohol diluent in an oven at 38-45 ℃ for preheating for 1-2 hours, weighing 1.8-9.0 g of the modified carbon black which accounts for 3-15 wt% of the epoxy resin and is fully ground after being treated in the step (1), placing the modified carbon black in a proper amount of acetone solution for ultrasonic treatment for 0.5-1 h, pouring the modified carbon black into the epoxy resin according to the proportion, stirring for 3-5 h at 35-45 ℃, uniformly stirring, pouring the curing agent, the accelerator and the diluent in sequence, fully stirring uniformly again, performing ultrasonic treatment for 1-2 h, and vacuumizing for 1.5-2.5 h to obtain a modified CB/AG-80 epoxy resin system solution; and (3) placing the carbon fiber double-layer spacer fabric treated in the step (2) in a mold, coating a proper amount of methyl silicone oil, pouring the modified CB/AG-80 epoxy resin system solution, vacuumizing the whole mold for 1-2 h, standing for 36-48 h, performing thermosetting at a certain temperature for a certain time, treating at 180-190 ℃ for 1.5-3 h, and cooling to obtain the oxidation modified CB/CFDSF/AG-80 epoxy resin composite material.
Preferably, the concentration of the concentrated nitric acid in the step (1) is 68 wt%, and the heating and stirring are performed for 2.5h after heating to 100 ℃.
Preferably, the ultrasonic cleaning solution in the step (2) is a mixture of 10-30 wt% of an absolute ethyl alcohol solution and 20-40 wt% of an acetone solution according to a volume ratio of 1: 1-1: 1.5.
Preferably, in the step (3), the ratio of the AG-80 epoxy resin, the curing agent and the diluent is 45-50 wt%: 40-45 wt% and 5-15 wt%, and the volume ratio of the absolute ethyl alcohol to the acetone in the diluent is 1: 1-1: 1.5.
Preferably, the thermal curing in the step (3) is performed according to a curing process of the pure CB/CFDSF/AG-80 epoxy resin composite material of 80 ℃/1h → 120 ℃/4h → 160 ℃/4 h.
Preferably, in the step (2), the carbon fiber double-layer spacing fabric is a plain weave fabric with both upper and lower surface layers.
Preferably, the modified carbon black in the step (3) accounts for 12-15 wt% of the epoxy resin.
The beneficial technical effects obtained by the invention are as follows:
1. the invention adopts concentrated nitric acid to modify carbon black, adopts the specific modification process and parameter design and selects the carbon fiber double-layer spacer fabric as a matrix, leads the modified carbon black to be mixed with AG-80 epoxy resin under certain process and parameter conditions to form modified CB/AG-80 epoxy resin system solution, finally pours the oxidized modified CB/AG-80 epoxy resin system solution into a die which is placed with the carbon fiber double-layer spacer fabric in advance, obtains the carbon fiber double-layer spacer fabric with good conductivity through the heat curing process, the modified CB process is adopted, the carbon fiber double-layer spacer fabric is used as a matrix, and carbon black can be uniformly distributed in the matrix, so that the stability of the conductivity of the carbon fiber double-layer spacer fabric is ensured;
2. according to the invention, an ultrasonic cleaning process is adopted when the carbon fiber double-layer spacer fabric is cleaned, and the cleaning solution is a mixed solution of 10-30 wt% of absolute ethyl alcohol solution and 20-40 wt% of acetone solution according to the volume of 1: 1-1: 1.5, so that oil stains, impurities and the like adhered to the surface of the carbon fiber in the weaving or touch process can be quickly removed, and the surface modification treatment is facilitated;
3. in the process of determining the thermosetting process, the invention obtains the following results by performing linear regression analysis on the initial temperature, the peak top temperature and the peak valley temperature of a pure CB/CFDSF/AG-80 system and performing linear regression analysis according to different temperatures: finally, the curing process of the system is determined as follows: 80 ℃/1h → 120 ℃/4h → 160 ℃/4h, and finally processing for 1.5-3 h at 180-190 ℃, thereby improving the thermosetting efficiency without influencing the characteristics of the composite material.
Drawings
FIG. 1 is a schematic diagram of the preparation of the O-CB/CFDSF/AG-80 composite material of the present invention;
FIG. 2a is a scanning electron microscope image of the river region of impact cross section of the O-CB/CFDSF/AG-80 composite material of the present invention;
FIG. 2b is a scanning electron microscope image of the tough-pit area of the impact section of the O-CB/CFDSF/AG-80 composite material of the present invention;
FIG. 3a is a graph showing the dynamic analysis of the storage modulus E' of the O-CB/CFDSF/AG-80 composite material of the present invention;
FIG. 3b is a graph showing the dynamic analysis of the loss modulus E' of the O-CB/CFDSF/AG-80 composite material of the present invention;
FIG. 4a is a graph of the thermogravimetric TG of the O-CB/CFDSF/AG-80 composite material of the present invention;
FIG. 4b is a DTG graph of the O-CB/CFDSF/AG-80 composite material of the present invention;
FIG. 5 shows the effect of modified CB content of the present invention on the electrical properties of a modified CB/CFDSF/AG-80 composite.
Detailed Description
The technical solutions of the present invention are described in detail below by specific embodiments, which are only specific embodiments or preferred embodiments of the present invention, and therefore do not limit the protection scope of the present invention.
Example 1
The invention relates to a method for modifying Carbon Black (CB), which comprises the following steps of carrying out modification treatment by using a silane coupling agent and carrying out modification treatment by using an oxidant, and protecting a preparation method of an oxidation modified CB/CFDSF/AG-80 epoxy resin composite material;
a preparation method for preparing an oxidation modified CB/CFDSF/AG-80 epoxy resin composite material mainly comprises the following steps:
1. the Carbon Black (CB) is modified by concentrated nitric acid
Carrying out modification treatment on Carbon Black (CB) by using concentrated nitric acid, firstly, respectively pouring 4g of carbon black and 50ml of concentrated nitric acid with the concentration of 65 wt% into a beaker, heating to 100 ℃, fully stirring for 2 hours, then diluting with distilled water and carrying out suction filtration, carefully scraping the filtered CB, putting the filtered CB into the beaker, pouring a large amount of distilled water for continuous dilution, standing for a proper time, taking the supernatant to pour, continuously carrying out suction filtration, repeating the operations for a plurality of times until the pH value of the supernatant is about 7, then, placing the filtered CB into an oven for drying, and grinding for 0.5 hour after drying to obtain the oxidized modified carbon black O-CB;
2. treatment of carbon fiber double layer spacer fabrics (CFDSF)
The woven spacer fabric is characterized in that a certain distance can be formed between two parallel plane fabrics, the woven double-layer spacer fabric is adopted, an upper surface layer 1 and a lower surface layer 2 of the woven double-layer spacer fabric are connected through binding yarns 3 as shown in figure 1, and a modified CB/AG-80 epoxy resin system solution is poured and cured into the spacer fabric to obtain the composite material of the invention, wherein the specification of a mould 4 adopted in the invention is 14cm × 14.5cm, so that the specification of cutting all CFDSF fabrics is required to be 14cm × 14.5.5 cm;
carrying out surface cleaning and surface modification treatment on a pre-woven and cut carbon fiber double-layer spacer fabric, namely, placing the cut carbon fiber double-layer spacer fabric in an ultrasonic cleaning solution at room temperature for soaking for 1h and then washing for 30min, then taking out and drying at 95 ℃, coating a certain amount of silane coupling agent KH550 solution which is dissolved in water and contains 1.5 wt% of absolute ethyl alcohol on the double-layer spacer fabric after drying, and standing for 24h at room temperature so as to completely volatilize the ethyl alcohol and seal for later use;
3. preparing modified CB/AG-80 epoxy resin system solution to pour and thermally cure CFDSF
Placing AG-80 epoxy resin, hexahydrophthalic anhydride curing agent, 2,4, 6-diaminomethylphenol accelerator, acetone and absolute ethyl alcohol diluent in an oven at 38 ℃ respectively for preheating for 1 hour, weighing 1.8g of modified carbon black which accounts for 3 wt% of the epoxy resin and is fully ground after being treated in the step 1, placing the modified carbon black in a proper amount of acetone solution for ultrasonic treatment for 0.5 hour, pouring the modified carbon black into the epoxy resin according to the proportion, stirring the mixture for 5 hours at 35 ℃, uniformly stirring the mixture, pouring the curing agent, the accelerator and the diluent in sequence, fully stirring the mixture again, performing ultrasonic treatment for 1 hour again, and vacuumizing for 1.5 hours to obtain a modified CB/AG-80 epoxy resin system solution; and then placing the carbon fiber double-layer spacer fabric processed in the step 2 in a mold 4, coating a proper amount of methyl silicone oil, pouring the modified CB/AG-80 epoxy resin system solution, vacuumizing the whole mold 4 for 1h, standing for 36h, performing thermocuring under a certain temperature and time condition, finally, processing at 180 ℃ for 1.5, and cooling to obtain the oxidation modified CB/CFDSF/AG-80 epoxy resin composite material.
Example 2
Modification treatment of Carbon Black (CB) the inventors of the present application studied modification treatment with a silane coupling agent and modification treatment with an oxidizing agent, and protected a preparation method of an oxidatively modified CB/CFDSF/AG-80 epoxy resin composite material;
a preparation method for preparing an oxidation modified CB/CFDSF/AG-80 epoxy resin composite material mainly comprises the following steps:
1. the Carbon Black (CB) is modified by concentrated nitric acid
Carrying out modification treatment on Carbon Black (CB) by using concentrated nitric acid, pouring 8g of carbon black and 75ml of concentrated nitric acid with the concentration of 68 wt% into a beaker respectively, heating to 100 ℃, then fully stirring for 2.5h, then diluting with distilled water and carrying out suction filtration, carefully scraping the filtered CB, putting the filtered CB into the beaker, pouring a large amount of distilled water for continuous dilution, standing for a proper time, taking the supernatant to pour, carrying out suction filtration continuously, repeating the operations for a plurality of times until the pH value of the supernatant is about 7, then placing the filtered CB into an oven for drying, and grinding for 1h after drying to obtain the oxidized modified carbon black O-CB;
2. processing a carbon fiber double-layer spacer fabric (CFDSF);
the woven spacer fabric is characterized in that a certain distance can be formed between two parallel plane fabrics, the woven double-layer spacer fabric is adopted, an upper surface layer 1 and a lower surface layer 2 of the woven double-layer spacer fabric are connected through binding yarns 3 as shown in figure 1, and a modified CB/AG-80 epoxy resin system solution is poured and cured into the spacer fabric to obtain the composite material of the invention, wherein the specification of a mould 4 adopted in the invention is 14cm × 14.5cm, so that the specification of cutting all CFDSF fabrics is required to be 14cm × 14.5.5 cm;
the method comprises the following steps of carrying out surface cleaning and surface modification treatment on a pre-woven and cut carbon fiber double-layer spacer fabric, namely, placing the cut carbon fiber double-layer spacer fabric in an ultrasonic cleaning solution at room temperature, soaking for 1.5h, and then washing for 40min, wherein the ultrasonic cleaning solution is a mixed solution of 10 wt% of absolute ethyl alcohol solution and 20 wt% of acetone solution according to the volume ratio of 1:1, then taking out the fabric to dry at 105 ℃, coating a certain amount of silane coupling agent KH550 solution which is dissolved in water and contains 2 wt% of absolute ethyl alcohol on the double-layer spacer fabric after drying, placing the fabric at room temperature for 30h so that the ethanol is completely volatilized, and sealing for later use;
3. preparing modified CB/AG-80 epoxy resin system solution to pour and thermally cure CFDSF
Placing AG-80 epoxy resin, hexahydrophthalic anhydride curing agent, 2,4, 6-diaminomethylphenol accelerator, acetone and absolute ethyl alcohol diluent in a 42 ℃ oven for preheating for 1.5 hours respectively, weighing 5.4g of modified carbon black which accounts for 9 wt% of the epoxy resin and is fully ground in the step 1, placing the modified carbon black in an appropriate amount of acetone solution for ultrasonic treatment for 1 hour, pouring the modified carbon black into the epoxy resin according to the proportion, stirring for 4 hours at 40 ℃, uniformly stirring, and pouring the curing agent, the accelerator and the diluent in sequence, wherein the proportion of the AG-80 epoxy resin, the curing agent and the diluent is 45 wt%: 40 wt% to 15 wt%, wherein the volume ratio of absolute ethyl alcohol to acetone in the diluent is 1:1, fully and uniformly stirring again, carrying out ultrasonic treatment for 1.5h, and vacuumizing for 2h to obtain a modified CB/AG-80 epoxy resin system solution; and then placing the carbon fiber double-layer spacer fabric processed in the step 2 in a mold 4, coating a proper amount of methyl silicone oil, pouring the modified CB/AG-80 epoxy resin system solution, vacuumizing the whole mold 4 for 1.5h, standing for 42h, performing thermosetting according to the curing process of the pure CB/CFDSF/AG-80 epoxy resin composite material, namely 80 ℃/1h → 120 ℃/4h → 160 ℃/4h, finally, processing for 2h at 185 ℃, and cooling to obtain the oxidized modified CB/CFDSF/AG-80 epoxy resin composite material.
Example 3
Modification treatment of Carbon Black (CB) the inventors of the present application studied modification treatment with a silane coupling agent and modification treatment with an oxidizing agent, and protected a preparation method of an oxidatively modified CB/CFDSF/AG-80 epoxy resin composite material;
a preparation method for preparing an oxidation modified CB/CFDSF/AG-80 epoxy resin composite material mainly comprises the following steps:
1. the Carbon Black (CB) is modified by concentrated nitric acid
Carrying out modification treatment on Carbon Black (CB) by using concentrated nitric acid, pouring 12g of carbon black and 100ml of concentrated nitric acid with the concentration of 70 wt% into a beaker respectively, heating to 110 ℃, fully stirring for 3h, diluting with distilled water and carrying out suction filtration, carefully scraping the filtered CB, putting the filtered CB into the beaker, pouring a large amount of distilled water for further dilution, standing for a proper time, taking the supernatant, pouring the supernatant, carrying out suction filtration continuously, repeating the operations for a plurality of times until the pH value of the supernatant is about 7, then placing the filtered CB into an oven for drying, and grinding for 1h after drying to obtain the oxidized modified carbon black O-CB;
2. processing a carbon fiber double-layer spacer fabric (CFDSF);
the woven spacer fabric is characterized in that a certain distance can be formed between two parallel plane fabrics, the woven double-layer spacer fabric is adopted, an upper surface layer 1 and a lower surface layer 2 of the woven double-layer spacer fabric are connected through binding yarns 3 as shown in figure 1, and a modified CB/AG-80 epoxy resin system solution is poured and cured into the spacer fabric to obtain the composite material of the invention, wherein the specification of a mould 4 adopted in the invention is 14cm × 14.5cm, so that the specification of cutting all CFDSF fabrics is required to be 14cm × 14.5.5 cm;
the method comprises the following steps of carrying out surface cleaning and surface modification treatment on a pre-woven and cut carbon fiber double-layer spacer fabric, namely, placing the cut carbon fiber double-layer spacer fabric in an ultrasonic cleaning solution at room temperature, soaking for 2 hours, and then washing for 50 minutes, wherein the ultrasonic cleaning solution is a mixed solution of 30 wt% of absolute ethyl alcohol solution and 40 wt% of acetone solution according to the volume ratio of 1:1.5, then taking out the fabric to dry at 110 ℃, coating a certain amount of silane coupling agent KH550 solution which is dissolved in water and contains 3 wt% of absolute ethyl alcohol on the double-layer spacer fabric after drying, placing the fabric at room temperature for 36 hours so that the ethyl alcohol is completely volatilized, and sealing for later use;
3. preparing modified CB/AG-80 epoxy resin system solution to pour and thermally cure CFDSF
Placing AG-80 epoxy resin, hexahydrophthalic anhydride curing agent, 2,4, 6-diaminomethylphenol accelerator, acetone and absolute ethyl alcohol diluent in a 45 ℃ oven respectively for preheating for 2 hours, weighing 9g of modified carbon black which accounts for 15 wt% of the epoxy resin and is fully ground after being treated in the step 1, placing the modified carbon black in a proper amount of acetone solution for ultrasonic treatment for 1 hour, pouring the modified carbon black into the epoxy resin according to the proportion, stirring the mixture for 3 hours at 45 ℃, uniformly stirring the mixture, and pouring the curing agent, the accelerator and the diluent in sequence, wherein the proportion of the AG-80 epoxy resin, the curing agent and the diluent is 50 wt%: 45 wt% to 5 wt%, wherein the volume ratio of absolute ethyl alcohol to acetone in the diluent is 1:1.5, fully and uniformly stirring again, carrying out ultrasonic treatment for 2 hours, and vacuumizing for 2.5 hours, so as to obtain a modified CB/AG-80 epoxy resin system solution; and then placing the carbon fiber double-layer spacer fabric processed in the step 2 in a mold 4, coating a proper amount of methyl silicone oil, pouring the modified CB/AG-80 epoxy resin system solution, vacuumizing the whole mold 4 for 2h, standing for 48h, performing thermosetting according to the curing process of the pure CB/CFDSF/AG-80 epoxy resin composite material, namely 80 ℃/1h → 120 ℃/4h → 160 ℃/4h, and finally, processing for 3h at 190 ℃ and cooling to obtain the oxidized modified CB/CFDSF/AG-80 epoxy resin composite material.
The carbon fiber double-layer spacer fabric used in step 2 in the above embodiments 1 to 3 is a plain weave fabric having both the upper and lower surface layers, and of course, a twill, satin or other fabric weave structure may be used as the weave of the carbon fiber double-layer spacer fabric.
The thermodynamic performance and the conductivity of the oxidation modified CB/CFDSF/AG-80 epoxy resin composite material prepared by the invention are tested and researched.
1. Research on impact section of oxidation modified CB/CFDSF/AG-80 composite material
FIG. 2a and FIG. 2b are the scanning electron micrographs of the impact cross-section river zone and the dimple zone of the O-CB/CFDSF/AG-80 system with 15% O-CB content, respectively; as can be seen from FIG. 2a, the river area of the O-CB/CFDSF/AG-80 system also had many white extractives that prevented further crack propagation. As can be seen from figure 2b, the impact section of the system is in the shape of fish scale concave-convex, and a plurality of tough pits exist, so that the system shows good toughening characteristics.
2. Research on dynamic mechanical properties of oxidation-modified CB/CFDSF/AG-80 composite material
Dynamic mechanical analysis is a test means for testing the mechanical properties of high molecular polymers. The dynamic storage modulus E 'and the loss modulus E' of the composite material can be obtained through dynamic mechanical analysis. E 'and E' can be used for respectively characterizing the rigidity of the material and the viscous component of the material, and the mechanical internal consumption of the material is generally expressed by tan delta, namely the ratio of E 'to E'.
FIGS. 3a and 3b are respectively the dynamic analysis diagram E 'and the dynamic analysis diagram E' of the O-CB/CFDSF/AG-80 composite material. It can be seen that as the temperature increases, both E' and E "rise first and then fall. And the change of the E ' of the O-CB/CFDSF/AG-80 system is not large during the period of increasing the room temperature to 100 ℃, and the comparison of the two graphs shows that when the O-CB content is 3 percent, the storage modulus E ' of the O-CB/CFDSF/AG-80 system is small, and the loss modulus E ' is large, which indicates that the toughness of the system is good at the moment. When the content of the O-CB is 15 percent, the loss modulus E' of the composite material is the largest, which shows that the composite material has the best toughness and the toughening effect of the O-CB is obvious.
3. Thermodynamic test analysis of oxidatively modified CB/CFDSF/AG-80 composite
The thermal property of the composite material mainly means that the composite material responds to the ambient temperature in the using process so as to show different thermal properties, and the thermal property is one of important properties of the composite material, and the stability of the thermal property of the composite material is obtained by analyzing the initial and maximum thermal decomposition temperatures of a system. As shown in FIGS. 4a and 4b, the thermogravimetric curves TG and DTG of the O-CB/CFDSF/AG-80 composite system at different contents of O-CB are respectively shown. In summary, the initial thermal decomposition temperature of the O-CB/CFDSF/AG-80 system is gradually increased and the maximum thermal decomposition temperature thereof is slightly fluctuated when the content of O-CB is gradually increased, and the initial and maximum thermal decomposition temperatures of the system are 258.75 ℃ and 389.79 ℃ respectively when the content of O-CB is 15%, and the heat resistance is the best and the heat resistance of the whole composite material is good. Because inorganic substances are all relatively heat-resistant, the thermal properties of the O-CB system are improved after the O-CB is added.
4. Electrical property test analysis of oxidation modified CB/CFDSF/AG-80 composite material
FIG. 5 shows the volume resistivity of the oxidatively modified CB composite system O-CB/CFDSF/AG-80. As can be seen from the figure, the volume resistivity of the CB-filled epoxy resin-based composite material has been decreasing. When the content of the modified CB is small, the volume resistivity change is not obvious, along with the increase of the content of the CB, when a certain content interval is reached, the volume resistivity of the modified CB is reduced relatively to a large extent to form a section of steep curve, and when the content of the modified CB exceeds the interval, the volume resistivity curve of the system is gradually gentle. Meanwhile, the volume resistivity of the composite material is the largest and is about 39.7 omega cm when the content of the CB is smaller, because when the conductive electrode is arranged on the side surface, the conductive electrode can be directly contacted with the carbon fiber cloth, at the moment, the main conductive network is composed of CF, and the conductive network formed by the CB can play a synergistic effect, so that the volume resistivity of the composite material can be influenced by the change of the content of the CB.
The above embodiments of the present invention and the experimental results thereof are described in detail, and it will be apparent to those skilled in the art that the embodiments may be changed, modified, replaced, integrated and modified in the process parameters without departing from the spirit and the principle of the present invention.
Claims (7)
1. The preparation method of the oxidation modified CB/CFDSF/AG-80 epoxy resin composite material is characterized by comprising the following steps:
(1) carrying out modification treatment on Carbon Black (CB) by using concentrated nitric acid, pouring 4-12 g of carbon black and 50-100 ml of concentrated nitric acid with the concentration of 65-70 wt% into a beaker respectively, heating to 100-110 ℃, fully stirring for 2-3 h, diluting with distilled water, carrying out suction filtration, carefully scraping the filtered CB, putting the filtered CB into the beaker, pouring a large amount of distilled water for continuously diluting, standing for a proper time, pouring out supernatant liquid, continuously carrying out suction filtration, repeating the operation for a plurality of times until the pH value of the supernatant liquid is about 7, then placing the filtered CB in an oven for drying, and grinding for 0.5-1 h after drying to obtain the oxidation modified carbon black O-CB;
(2) the method comprises the following steps of treating carbon fiber double-layer spacer fabric (CFDSF), and carrying out surface cleaning and surface modification treatment on the carbon fiber double-layer spacer fabric which is woven and cut in advance, wherein the specific process comprises the following steps: placing the cut double-layer carbon fiber spacer fabric in an ultrasonic cleaning solution at room temperature, soaking for 1-2 hours, washing for 30-50 minutes, taking out, drying at 95-110 ℃, coating a certain amount of silane coupling agent KH550 solution which is dissolved in water and contains 1.5-3 wt% of absolute ethyl alcohol on the double-layer spacer fabric, placing for 24-36 hours at room temperature so as to completely volatilize the ethyl alcohol, and sealing for later use; the ultrasonic cleaning liquid is a mixed liquid of 10-30 wt% of absolute ethyl alcohol solution and 20-40 wt% of acetone solution according to the volume of 1: 1-1: 1.5;
(3) preparing a modified CB/AG-80 epoxy resin system solution to pour and thermally cure the CFDSF, respectively putting AG-80 epoxy resin, a hexahydrophthalic anhydride curing agent, a 2,4, 6-diaminomethylphenol accelerator, acetone and an absolute ethyl alcohol diluent in an oven at 38-45 ℃ for preheating for 1-2 hours, weighing 5.4-9.0 g of modified carbon black which accounts for 9-15 wt% of the epoxy resin and is fully ground after being treated in the step (1), placing the modified carbon black in a proper amount of acetone solution for ultrasonic treatment for 0.5-1 h, pouring the modified carbon black into the epoxy resin according to the proportion, stirring for 3-5 h at 35-45 ℃, uniformly stirring, pouring the curing agent, the accelerator and the diluent in sequence, fully stirring uniformly again, performing ultrasonic treatment for 1-2 h, and vacuumizing for 1.5-2.5 h to obtain a modified CB/AG-80 epoxy resin system solution; placing the carbon fiber double-layer spacer fabric treated in the step (2) in a mold, coating a proper amount of methyl silicone oil, pouring the modified CB/AG-80 epoxy resin system solution, vacuumizing the whole mold for 1-2 h, standing for 36-48 h, performing thermosetting at a certain temperature for a certain time, treating at 180-190 ℃ for 1.5-3 h, and cooling to obtain an oxidation modified CB/CFDSF/AG-80 epoxy resin composite material; the river flow area of the impact section of the oxidation modified CB/CFDSF/AG-80 epoxy resin composite material is provided with a white pull-out object capable of preventing crack propagation, and the impact section is in a fish scale concave-convex shape under a scanning electron microscope.
2. The method for preparing an oxidatively modified CB/CFDSF/AG-80 epoxy resin composite material as claimed in claim 1, wherein the concentration of said concentrated nitric acid in said step (1) is 68 wt%, and said heating and stirring are carried out for 2.5h after heating to 100 ℃.
3. The preparation method of the oxidation-modified CB/CFDSF/AG-80 epoxy resin composite material as claimed in claim 1 or 2, wherein in the step (3), the ratio of the AG-80 epoxy resin to the curing agent to the diluent is 45-50 wt%: 40-45 wt% and 5-15 wt%, and the volume ratio of the absolute ethyl alcohol to the acetone in the diluent is 1: 1-1: 1.5.
4. The method for preparing an oxidatively modified CB/CFDSF/AG-80 epoxy resin composite material according to claim 1 or 2, wherein the heat curing in the step (3) is performed according to the curing process of the pure CB/CFDSF/AG-80 epoxy resin composite material of 80 ℃/1h → 120 ℃/4h → 160 ℃/4 h.
5. The method for preparing an oxidation-modified CB/CFDSF/AG-80 epoxy resin composite material as claimed in claim 1 or 2, wherein in the step (2), the carbon fiber double-layer spacing fabric is plain weave fabric with upper and lower surface layers.
6. The preparation method of the oxidation-modified CB/CFDSF/AG-80 epoxy resin composite material, which is described in the claim 1 or 2, wherein the modified carbon black in the step (3) accounts for 12-15 wt% of the epoxy resin.
7. The method for preparing the oxidation-modified CB/CFDSF/AG-80 epoxy resin composite material as claimed in claim 1 or 2, wherein in the step (2), the carbon fiber double-layer spacing fabric adopts a twill and satin weave structure.
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