CN108299826A - Porous filamentous nanocarbon/special engineering plastics composite material and preparation method - Google Patents
Porous filamentous nanocarbon/special engineering plastics composite material and preparation method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
- D01F11/16—Chemical after-treatment of artificial filaments or the like during manufacture of carbon by physicochemical methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
- D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The present invention relates to porous filamentous nanocarbon/special engineering plastics composite material and preparation methods, include the following steps：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and N, N dimethylformamide, it is configured to spinning solution；Electrostatic spinning is carried out, carbonization, thermokalite are washed, dried, and porous filamentous nanocarbon is made；Surface acidification is carried out again, and the porous filamentous nanocarbon of surface acidification is made；It is immersed in resin matrix, porous filamentous nanocarbon preform is made；Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, direct fabrics are on porous filamentous nanocarbon preform, the porous filamentous nanocarbon preform containing multi-layer nano fibrofelt is made, laying, the porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform is prepared, is cured by moulding process, you can.Compared with prior art, preparation process of the present invention is simple, and composite material obtained has excellent tensile property and bending property.
Description
Technical field
The invention belongs to technical field of composite materials, are related to a kind of porous filamentous nanocarbon/special engineering plastics composite wood
Material and preparation method thereof.
Background technology
The resin matrix of current advanced composite material is just sent out towards the direction of high bending property, high intensity, high temperature resistant degree
Exhibition.Carbon fiber has been widely used in due to its unique structure and characteristic in composite material.Carbon fiber and its composite wood
Material is that have the chemistry of the good characteristics such as high intensity, high-modulus, high temperature resistant, corrosion-resistant, endurance, creep resistant, conductive heat transfer fine
Dimension, is the new material with structural material and functional material double duty, is widely used in aerospace, nuclear industry, building materials, body
Educate the every field such as articles for use.
Wherein, carbon nano-fiber（Carbon nanofibers, abbreviation CNF）It is one kind of chemical vapor-phase growing carbon fiber
Form is a kind of discontinuous class graphite fibre prepared by cracking gaseous hydrocarbon, is a kind of novel sub-micron enhancing
Material.It has the characteristics that high intensity, high resiliency, is to prepare the ideal lightweight reinforcing material of composite material, while also having height
Draw ratio and electric conductivity, heat conductivity are being parallel to axis and are showing prodigious difference on axis direction, can use
In anisotropic conductive material.The diameter of carbon nano-fiber is generally between tens nanometers ~ mono- micron, the specific surface with superelevation
Product（If the specific surface area of the carbon nano-fiber of diameter 100nm is 1000m2/ g or so）With big porosity.Electrostatic spinning is system
A kind of very easy and efficient method of standby carbon fiber, and due to of low cost, by everybody extensive concern.But by
It is the carbon fiber of non-porous structure in carbon fiber prepared by common method of electrostatic spinning, specific surface area is all relatively low, this is also limited significantly
The application of carbon fiber.For this defect, it is extensive then to cause people for high-ratio surface porous carbon fiber and its preparation in recent years
Research interest, become the hot spot of research and development.Currently, about the method containing mesoporous carbon fiber is prepared mainly with soft mode
The pore creating materials such as PMMA, ammonium chloride, diisopropyl azodiformate are either added in spinning solution by plate method, hard template method,
Based on calcining pore-creating.But generally by calcining performance of the micropore generated since material can not be improved by can not infiltrating.
Meanwhile it is at present that porous filamentous nanocarbon is compound excellent to prepare high intensity, high-modulus, mechanical property together with special engineering plastics
Different composite material is then rarely reported.
Invention content
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of porous nano carbon fibers
Dimension/special engineering plastics composite material.
Another object of the present invention is just to provide the system of the porous filamentous nanocarbon/special engineering plastics composite material
Preparation Method.
The purpose of the present invention can be achieved through the following technical solutions：
The preparation method of porous filamentous nanocarbon/special engineering plastics composite material, this method specifically include following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the obtained porous filamentous nanocarbon preform containing multi-layer nano fibrofelt, laying,
Prepare the porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains the porous filamentous nanocarbon/special engineering plastics composite material.
Step（1）In the spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:
0.08-0.12:12-15。
The number-average molecular weight of the polyacrylonitrile is 80w-260w, and the pore creating material is the nano-silica that size is 3-8nm
The outer tube of SiClx, the tubular nanometer galapectite is 10-50nm, internal diameter 5-20nm, length 0.5-3um, and crystal layer number is 15-
40。
Step（2）The condition of the electrostatic spinning is：Control spinning voltage be 20-25kv, flow velocity 1.2-1.6ml/h,
Spinning distance is 20-25cm.
Step（2）The carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The pre-oxidation
Temperature be 200-220 DEG C, the time be 2-3 hours；The temperature of the high temperature cabonization is 820-900 DEG C, and carbonization time is that 1-3 is small
When, the whole process of subsequent cooled to room temperature, the high temperature cabonization carries out in an inert atmosphere.
Step（2）The condition that the thermokalite is washed is：A concentration of 1-1.5M of alkali, alkali cleaning temperature is 90-100 DEG C, when alkali cleaning
Between be 6-8 hours；The alkali includes at least one of sodium hydroxide, potassium hydroxide.
Step（3）Described in porous filamentous nanocarbon with the concentration of 0.8-3mg/ml be dispersed in 75-80 DEG C the concentrated sulfuric acid/it is dense
2-4 hours in nitric acid, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2-3:1.
Step（4）Described in porous filamentous nanocarbon preform the volume content of porous filamentous nanocarbon be 60-
72%, the resin matrix includes epoxy resin, unsaturated-resin, bimaleimide resin, phenolic resin or vinyl esters tree
One or more of fat.
Step（5）Described in the weight part ratios of nanofiber mats and resin matrix in porous filamentous nanocarbon preform be
2-6:100, a diameter of 200-800nm of nanofiber in the nanofiber mats, the special engineering plastics include polyether sulfone,
One or more of polysulfones, polyimides or polyether-ether-ketone, the organic solvent include dimethylformamide, dimethylacetamide
The one or more of amine, acetone, dichloromethane, trichloroethanes, dimethyl sulfoxide (DMSO), tetrahydrofuran.
Step（5）Described in the condition of electrostatic spinning be：Control spinning voltage is 20-25kv, flow velocity 1.2-1.6ml/
H, spinning distance are 16-18cm.
Step（7）Described in the cured condition of moulding process be：According to consolidating for 120 DEG C/2h+180 DEG C/2h+200 DEG C/1h
Chemical industry skill cure under pressure on vulcanizing press, pressure 20-35MPa.
The porous filamentous nanocarbon being prepared using the above method/special engineering plastics composite material.
The present invention introduces nano silicon dioxide as pore creating material, and use during preparing porous filamentous nanocarbon
Thermokalite removes the silica in fiber, while the tubular nanometer galapectite used（HNTs) it is a kind of natural many walls nanotube
Shape inorganic material belongs to aluminum silicate clay mineral, chemical formula Al4[Si4O10](OH)8·nH2The sheet of O, HNTs by
Oxygen-octahedron is formed with sial octahedron, due to SiO2In outer layer, Al2O3In internal layer, so its outer wall contains certain hydroxyl
Base has polarity, but different from common silicate, and the structural unit of HNTs is with the shape of the secondary bonds such as hydrogen bond and Van der Waals force
Formula combines, but mutually intermolecular forces are not strong, is easier to realize the dissociation and dispersion of structural unit, porous nano carbon fiber obtained
Dimension has high-specific surface area, and has micropore and meso-hole structure simultaneously, then handles porous filamentous nanocarbon by being acidified, can be
Its surface introduces a large amount of active groups, is immersed in such as epoxy resin, unsaturated-resin, bimaleimide resin, phenolic aldehyde
In the resin matrixes such as resin, the wellability of itself and resin matrix can be effectively improved, and good compatibility is formed with resin matrix,
Simultaneously because the presence of porosity characteristic, nano level interface increases the effect of the mechanical engagement between carbon fiber and resin matrix, changes
Interfacial structure has been apt to it, followed by the good electric conductivity of carbon fiber, using porous filamentous nanocarbon preform as electrostatic spinning
Receiver, directly nanofiber can be easily layed in porous by nanofiber spinning on preform by laying
The interlayer of carbon nano-fiber preform, the bigger serface and high porosity of nanofiber, improves resin matrix compound
The permeability of material interlayer and wellability to reinforcing fiber are easy that thermoplastic special engineering plastic is made to realize reaction induced phase point
From the fracture bending property of carbon fiber resin matrix composite significantly improves under less toughening element content, and can realize
High-strength tensile property.
Compared with prior art, the invention has the characteristics that：
1）For the present invention during preparing porous filamentous nanocarbon, the tubular nanometer galapectite of use has great specific surface
Long-pending, excellent mechanical performance, excellent absorption property and good chemical stability, unique cavity structure have
High plasticity, good high temperature resistant；
2）Preparation process of the present invention using the porous filamentous nanocarbon of acidification as matrix reinforcing material, by porosity characteristic,
Its surface can introduce a large amount of active groups on its surface, improve its wellability with resin matrix, and formed very with resin matrix
Good compatibility improves interfacial structure, realizes high-strength tensile property；
3）Due to using nanofiber, due to characteristics such as its diameter is small, bigger serface and high porosities, resin matrix is improved
Permeability in composite material interlayer and the wellability to reinforcing fiber can be easy that thermoplastic special engineering plastic is made to realize reaction
Induction phase separation, the fracture bending property of carbon fiber resin matrix composite significantly improves under less toughening element content；
4）Porous filamentous nanocarbon produced by the present invention/special engineering plastics composite material has excellent tensile property, for example,
High-strength：Tensile strength >=4900MPa, CV≤5%, 230 ~ 250GPa of stretch modulus, CV≤2%；High-strength middle model：Tensile strength
>=5500MPa, CV≤5%, 280 ~ 300GPa of stretch modulus, CV≤2%；Meanwhile also there is excellent bending strength and bending die
Amount, bending strength may be up to 1719MPa, and bending modulus may be up to 128Gpa, can be applied to Aeronautics and Astronautics, rail traffic, sea
The industry fields such as work, wind-powered electricity generation equipment, pressure vessel have good application prospect.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1：
The method that the present embodiment prepares porous filamentous nanocarbon/special engineering plastics composite material, specifically includes following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the porous filamentous nanocarbon preform containing 8 layers of nanofiber mats, laying, system is made
The standby porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains porous filamentous nanocarbon/special engineering plastics composite material.
Wherein, step（1）In spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:
0.1:12.The number-average molecular weight of polyacrylonitrile is 150w, and pore creating material is the nano silicon dioxide that size is 6nm, tubular nanometer angstrom
The outer tube of Lip river stone is 30nm, internal diameter 15nm, length 1um, and crystal layer number is 30.
Step（2）The condition of electrostatic spinning is：Control spinning voltage is 24kv, flow velocity 1.5ml/h, and spinning distance is
22cm。
Step（2）Carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The temperature of pre-oxidation is
220 DEG C, the time is 2 hours；The temperature of high temperature cabonization is 900 DEG C, and carbonization time is 2 hours, and subsequent cooled to room temperature is high
The whole process of temperature carbonization carries out in an inert atmosphere.
Step（2）The condition that thermokalite is washed is：A concentration of 1.2M of alkali, alkali cleaning temperature are 95 DEG C, and the alkali cleaning time is 6 hours；
Alkali is sodium hydroxide.
Step（3）It is small that middle porous filamentous nanocarbon is dispersed in 78 DEG C of the concentrated sulfuric acid/concentrated nitric acid 3 with the concentration of 1.2mg/ml
When, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2:1.
Step（4）The volume content of porous filamentous nanocarbon is 65% in middle porous filamentous nanocarbon preform, resin base
Body is epoxy resin.
Step（5）The weight part ratio of middle nanofiber mats and resin matrix in porous filamentous nanocarbon preform is 3:
100, a diameter of 600nm of nanofiber in nanofiber mats, special engineering plastics are polyether sulfone, and organic solvent is dimethyl second
The mixed solvent of amide and acetone；The condition of electrostatic spinning is：Control spinning voltage be 24kv, flow velocity 1.5ml/h, spinning away from
From for 16cm.
Step（7）The middle cured condition of moulding process is：According to the solidification work of 120 DEG C/2h+180 DEG C/2h+200 DEG C/1h
Skill cure under pressure on vulcanizing press, pressure 20MPa.
The tensile property and bending property of porous filamentous nanocarbon made from the present embodiment/special engineering plastics composite material
Test result it is as shown in table 1.
Comparative example 1：
Using carbon fiber（Toray T700SC）It is immersed in epoxy resin-base（The volume content of carbon fiber is 65%）In, system
Obtain carbon fibre preform；By polyether sulfone it is vacuum dried after, be dissolved in be made into dichloromethane a concentration of 10% polyether sulfone it is molten
Solution is poured on glass plate by liquid, and wet film maker is used in combination to strike off, and is placed 6 hours at room temperature, and solvent method preparation is obtained
Poly (ether sulfone) film places into vacuum drying oven and is warming up to 150 DEG C of removal residual solvents, is laid on carbon fibre preform successively,
It is laid with 8 layers altogether, the carbon fiber containing sandwich structure/special engineering plastics preform is prepared, according to the molding work of composite material
Skill cures, you can.
The tensile property of carbon fiber made from comparative example 1/special engineering plastics composite material and the test knot of bending property
Fruit is as shown in table 1.
Embodiment 2：
The method that the present embodiment prepares porous filamentous nanocarbon/special engineering plastics composite material, specifically includes following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the porous filamentous nanocarbon preform containing 8 layers of nanofiber mats, laying, system is made
The standby porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains porous filamentous nanocarbon/special engineering plastics composite material.
Wherein, step（1）In spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:
0.08:12.The number-average molecular weight of polyacrylonitrile is 120w, and pore creating material is the nano silicon dioxide that size is 3nm, tubular nanometer angstrom
The outer tube of Lip river stone is 35nm, internal diameter 12nm, length 1.2um, and crystal layer number is 35.
Step（2）The condition of electrostatic spinning is：Control spinning voltage is 20kv, flow velocity 1.2ml/h, and spinning distance is
20cm。
Step（2）Carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The temperature of pre-oxidation is
200 DEG C, the time is 3 hours；The temperature of high temperature cabonization is 820 DEG C, and carbonization time is 3 hours, and subsequent cooled to room temperature is high
The whole process of temperature carbonization carries out in an inert atmosphere.
Step（2）The condition that thermokalite is washed is：A concentration of 1M of alkali, alkali cleaning temperature are 95 DEG C, and the alkali cleaning time is 8 hours；Alkali
For potassium hydroxide.
Step（3）It is small that middle porous filamentous nanocarbon is dispersed in 75 DEG C of the concentrated sulfuric acid/concentrated nitric acid 4 with the concentration of 0.8mg/ml
When, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
Step（4）The volume content of porous filamentous nanocarbon is 60% in middle porous filamentous nanocarbon preform, resin base
Body is unsaturated-resin.
Step（5）The weight part ratio of middle nanofiber mats and resin matrix in porous filamentous nanocarbon preform is 2:
100, a diameter of 400nm of nanofiber in nanofiber mats, special engineering plastics are polysulfones, and organic solvent is dimethylacetamide
The mixed solvent of amine and tetrahydrofuran；The condition of electrostatic spinning is：Control spinning voltage is 20kv, flow velocity 1.2ml/h, spinning
Distance is 20cm.
Step（7）The middle cured condition of moulding process is：According to the solidification work of 120 DEG C/2h+180 DEG C/2h+200 DEG C/1h
Skill cure under pressure on vulcanizing press, pressure 24MPa.
The tensile property and bending property of porous filamentous nanocarbon made from the present embodiment/special engineering plastics composite material
Test result it is as shown in table 1.
Comparative example 2：
Using carbon fiber（Toray T700SC）It is immersed in unsaturated-resin matrix（The volume content of carbon fiber is 60%）In,
Carbon fibre preform is made；By polysulfones it is vacuum dried after, be dissolved in be made into dichloromethane a concentration of 10% polysulfones solution,
Solution is poured on glass plate, wet film maker is used in combination to strike off, is placed 6 hours at room temperature, the poly- of solvent method preparation is obtained
Sulfone film places into vacuum drying oven and is warming up to 150 DEG C of removal residual solvents, is laid on carbon fibre preform, spreads altogether successively
It is solid according to the moulding process of composite material if 8 layers, preparing the carbon fiber containing sandwich structure/special engineering plastics preform
Change, you can.
The tensile property of carbon fiber made from comparative example 2/special engineering plastics composite material and the test knot of bending property
Fruit is as shown in table 1.
Embodiment 3：
The method that the present embodiment prepares porous filamentous nanocarbon/special engineering plastics composite material, specifically includes following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the porous filamentous nanocarbon preform containing 8 layers of nanofiber mats, laying, system is made
The standby porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains porous filamentous nanocarbon/special engineering plastics composite material.
Wherein, step（1）In spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:
0.12:15.The number-average molecular weight of polyacrylonitrile is 260w, and pore creating material is the nano silicon dioxide that size is 8nm, tubular nanometer angstrom
The outer tube of Lip river stone is 42nm, internal diameter 18nm, length 2.4um, and crystal layer number is 32.
Step（2）The condition of electrostatic spinning is：Control spinning voltage is 25kv, flow velocity 1.6ml/h, and spinning distance is
25cm。
Step（2）Carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The temperature of pre-oxidation is
220 DEG C, the time is 2.5 hours；The temperature of high temperature cabonization is 900 DEG C, and carbonization time is 1 hour, subsequent cooled to room temperature,
The whole process of high temperature cabonization carries out in an inert atmosphere.
Step（2）The condition that thermokalite is washed is：A concentration of 1.5M of alkali, alkali cleaning temperature are 100 DEG C, and the alkali cleaning time is 6 hours；
Alkali is potassium hydroxide and sodium hydroxide is 1 in molar ratio:1 mixed solution.
Step（3）It is small that middle porous filamentous nanocarbon is dispersed in 80 DEG C of the concentrated sulfuric acid/concentrated nitric acid 2 with the concentration of 3mg/ml
When, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2.5:1.
Step（4）The volume content of porous filamentous nanocarbon is 72% in middle porous filamentous nanocarbon preform, resin base
Body is bimaleimide resin.
Step（5）The weight part ratio of middle nanofiber mats and resin matrix in porous filamentous nanocarbon preform is 6:
100, a diameter of 800nm of nanofiber in nanofiber mats, special engineering plastics are polyimides, and organic solvent is dimethyl
The mixed solvent of formamide, dichloromethane and dimethyl sulfoxide (DMSO)；The condition of electrostatic spinning is：Control spinning voltage is 25kv, stream
Speed is 1.6ml/h, and spinning distance is 25cm.
Step（7）The middle cured condition of moulding process is：According to the solidification work of 120 DEG C/2h+180 DEG C/2h+200 DEG C/1h
Skill cure under pressure on vulcanizing press, pressure 32MPa.
The tensile property and bending property of porous filamentous nanocarbon made from the present embodiment/special engineering plastics composite material
Test result it is as shown in table 1.
Comparative example 3：
Using carbon fiber（Toray T700SC）It is immersed in bimaleimide resin base body（The volume content of carbon fiber is
72%）In, carbon fibre preform is made；By polyimides it is vacuum dried after, be dissolved in dichloromethane and be made into a concentration of 10%
Polyimide solution, solution is poured on glass plate, wet film maker is used in combination to strike off, at room temperature place 6 hours, obtain
Polyimide film prepared by solvent method places into vacuum drying oven and is warming up to 150 DEG C of removal residual solvents, is laid on carbon fiber successively
It ties up on preform, is laid with 8 layers altogether, the carbon fiber containing sandwich structure/special engineering plastics preform is prepared, according to compound
The moulding process of material cures, you can.
The tensile property of carbon fiber made from comparative example 3/special engineering plastics composite material and the test knot of bending property
Fruit is as shown in table 1.
Embodiment 4：
The method that the present embodiment prepares porous filamentous nanocarbon/special engineering plastics composite material, specifically includes following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the porous filamentous nanocarbon preform containing 8 layers of nanofiber mats, laying, system is made
The standby porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains porous filamentous nanocarbon/special engineering plastics composite material.
Wherein, step（1）In spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:
0.12:15.The number-average molecular weight of polyacrylonitrile is 260w, and pore creating material is the nano silicon dioxide that size is 8nm, tubular nanometer angstrom
The outer tube of Lip river stone is 50nm, internal diameter 20nm, length 3um, and crystal layer number is 40.
Step（2）The condition of electrostatic spinning is：Control spinning voltage is 25kv, flow velocity 1.6ml/h, and spinning distance is
25cm。
Step（2）Carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The temperature of pre-oxidation is
220 DEG C, the time is 2.5 hours；The temperature of high temperature cabonization is 900 DEG C, and carbonization time is 1 hour, subsequent cooled to room temperature,
The whole process of high temperature cabonization carries out in an inert atmosphere.
Step（2）The condition that thermokalite is washed is：A concentration of 1.5M of alkali, alkali cleaning temperature are 100 DEG C, and the alkali cleaning time is 6 hours；
Alkali is potassium hydroxide and sodium hydroxide is 1 in molar ratio:1 mixed solution.
Step（3）It is small that middle porous filamentous nanocarbon is dispersed in 80 DEG C of the concentrated sulfuric acid/concentrated nitric acid 2 with the concentration of 3mg/ml
When, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2.5:1.
Step（4）The volume content of porous filamentous nanocarbon is 72% in middle porous filamentous nanocarbon preform, resin base
Body is bimaleimide resin.
Step（5）The weight part ratio of middle nanofiber mats and resin matrix in porous filamentous nanocarbon preform is 6:
100, a diameter of 800nm of nanofiber in nanofiber mats, special engineering plastics are polyimides, and organic solvent is dimethyl
The mixed solvent of formamide, dichloromethane and dimethyl sulfoxide (DMSO)；The condition of electrostatic spinning is：Control spinning voltage is 25kv, stream
Speed is 1.6ml/h, and spinning distance is 25cm.
Step（7）The middle cured condition of moulding process is：According to the solidification work of 120 DEG C/2h+180 DEG C/2h+200 DEG C/1h
Skill cure under pressure on vulcanizing press, pressure 32MPa.
The tensile property and bending property of porous filamentous nanocarbon made from the present embodiment/special engineering plastics composite material
Test result it is as shown in table 1.
Embodiment 5：
The method that the present embodiment prepares porous filamentous nanocarbon/special engineering plastics composite material, specifically includes following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the porous filamentous nanocarbon preform containing 8 layers of nanofiber mats, laying, system is made
The standby porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains porous filamentous nanocarbon/special engineering plastics composite material.
Wherein, step（1）In spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:
0.1:14.The number-average molecular weight of polyacrylonitrile is 80w, and pore creating material is the nano silicon dioxide that size is 4nm, tubular nanometer angstrom Lip river
The outer tube of stone is 10nm, internal diameter 5nm, length 0.5um, and crystal layer number is 15.
Step（2）The condition of electrostatic spinning is：Control spinning voltage is 21kv, flow velocity 1.4ml/h, and spinning distance is
20cm。
Step（2）Carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The temperature of pre-oxidation is
205 DEG C, the time is 3 hours；The temperature of high temperature cabonization is 870 DEG C, and carbonization time is 1.5 hours, subsequent cooled to room temperature,
The whole process of high temperature cabonization carries out in an inert atmosphere.
Step（2）The condition that thermokalite is washed is：A concentration of 1.4M of alkali, alkali cleaning temperature are 98 DEG C, and the alkali cleaning time is 6.5 small
When；Alkali is sodium hydroxide.
Step（3）Middle porous filamentous nanocarbon is dispersed in the concentration of 2.4mg/ml 3.6 in 78 DEG C of the concentrated sulfuric acid/concentrated nitric acid
Hour, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2:1.
Step（4）The volume content of porous filamentous nanocarbon is 68% in middle porous filamentous nanocarbon preform, resin base
Body is phenolic resin.
Step（5）The weight part ratio of middle nanofiber mats and resin matrix in porous filamentous nanocarbon preform is 4:
100, a diameter of 200nm of nanofiber in nanofiber mats, special engineering plastics are polyether-ether-ketone, and organic solvent is dimethyl
The mixed solvent of formamide, trichloroethanes, tetrahydrofuran and acetone；The condition of electrostatic spinning is：Control spinning voltage is 21kv,
Flow velocity is 1.4ml/h, and spinning distance is 20cm.
Step（7）The middle cured condition of moulding process is：According to the solidification work of 120 DEG C/2h+180 DEG C/2h+200 DEG C/1h
Skill cure under pressure on vulcanizing press, pressure 34MPa.
The tensile property and bending property of porous filamentous nanocarbon made from the present embodiment/special engineering plastics composite material
Test result it is as shown in table 1.
Embodiment 6：
The method that the present embodiment prepares porous filamentous nanocarbon/special engineering plastics composite material, specifically includes following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the porous filamentous nanocarbon preform containing 8 layers of nanofiber mats, laying, system is made
The standby porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains porous filamentous nanocarbon/special engineering plastics composite material.
Wherein, step（1）In spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:
0.1:13.The number-average molecular weight of polyacrylonitrile is 210w, and pore creating material is the nano silicon dioxide that size is 6nm, tubular nanometer angstrom
The outer tube of Lip river stone is 15nm, internal diameter 8nm, length 1.2um, and crystal layer number is 20.
Step（2）The condition of electrostatic spinning is：Control spinning voltage is 20kv, flow velocity 1.3ml/h, and spinning distance is
23cm。
Step（2）Carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The temperature of pre-oxidation is
215 DEG C, the time is 2.5 hours；The temperature of high temperature cabonization is 860 DEG C, and carbonization time is 2.5 hours, then naturally cools to room
The whole process of temperature, high temperature cabonization carries out in an inert atmosphere.
Step（2）The condition that thermokalite is washed is：A concentration of 1.1M of alkali, alkali cleaning temperature are 94 DEG C, and the alkali cleaning time is 7 hours；
Alkali is sodium hydroxide.
Step（3）It is small that middle porous filamentous nanocarbon is dispersed in 76 DEG C of the concentrated sulfuric acid/concentrated nitric acid 4 with the concentration of 1.2mg/ml
When, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
Step（4）The volume content of porous filamentous nanocarbon is 70% in middle porous filamentous nanocarbon preform, resin base
Body is phenolic resin.
Step（5）The weight part ratio of middle nanofiber mats and resin matrix in porous filamentous nanocarbon preform is 3.5:
100, a diameter of 350nm of nanofiber in nanofiber mats, special engineering plastics are that polysulfones is in mass ratio with polyether-ether-ketone
3:1 mixes, and organic solvent is the mixed solvent of dimethylformamide, trichloroethanes, tetrahydrofuran and acetone；Electrostatic spinning
Condition be：Control spinning voltage is 20kv, and flow velocity 1.3ml/h, spinning distance is 23cm.
Step（7）The middle cured condition of moulding process is：According to the solidification work of 120 DEG C/2h+180 DEG C/2h+200 DEG C/1h
Skill cure under pressure on vulcanizing press, pressure 28MPa.
The tensile property and bending property of porous filamentous nanocarbon made from the present embodiment/special engineering plastics composite material
Test result it is as shown in table 1.
It is tested using universal tensile strength-testing machine, the thickness of pressed sheet is 2mm, and plate cutting is at 80*6mm's
Sample.
1 material tensile property of table and bending property test result
Claims (10)
1. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, which is characterized in that this method specifically includes
Following steps：
Step（1）：By the mixing of polyacrylonitrile, pore creating material, tubular nanometer galapectite and n,N-Dimethylformamide, it is configured to spin
Silk liquid；
Step（2）：Using step（1）Spinning solution obtained carries out electrostatic spinning, is then carbonized, then washed through thermokalite, dry, that is, makes
Obtain porous filamentous nanocarbon；
Step（3）：By step（2）Porous filamentous nanocarbon obtained is dispersed in concentrated acid solution, after cooling, be transferred to from
It in sub- water, stirs, centrifuges, remove supernatant, deionized water is used in combination constantly to clean up to supernatant pH is neutral, obtained table
The porous filamentous nanocarbon of face acidification；
Step（4）：By step（3）The porous filamentous nanocarbon of surface acidification obtained is immersed in resin matrix, is made porous
Carbon nano-fiber preform；
Step（5）：Special engineering plastics are dissolved in organic solvent, electrostatic spinning solution is made, it is pre- with porous filamentous nanocarbon
Receiver of the formed body as electrostatic spinning, direct fabrics form one layer of Nanowire on porous filamentous nanocarbon preform
Tie up felt；
Step（6）：Repeat step（5）, the obtained porous filamentous nanocarbon preform containing multi-layer nano fibrofelt, laying,
Prepare the porous filamentous nanocarbon containing nanofiber sandwich structure/special engineering plastics preform；
Step（7）：By step（6）Porous filamentous nanocarbon obtained/special engineering plastics preform is according to composite material
Moulding process cures, and obtains the porous filamentous nanocarbon/special engineering plastics composite material.
2. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 1
In step（1）In the spinning solution, the weight part ratio of polyacrylonitrile, pore creating material and n,N-Dimethylformamide is 2:0.08-
0.12:12-15。
3. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 2
In, the number-average molecular weight of the polyacrylonitrile is 80w-260w, and the pore creating material is the nano silicon dioxide that size is 3-8nm,
The outer tube of the tubular nanometer galapectite is 10-50nm, internal diameter 5-20nm, length 0.5-3um, and crystal layer number is 15-40.
4. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 1
In step（2）The condition of the electrostatic spinning is：Control spinning voltage be 20-25kv, flow velocity 1.2-1.6ml/h, spinning away from
From for 20-25cm.
5. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 1
In step（2）The carbonization includes the high temperature cabonization in aerial pre-oxidation and inert atmosphere；The temperature of the pre-oxidation
It it is 200-220 DEG C, the time is 2-3 hours；The temperature of the high temperature cabonization is 820-900 DEG C, and carbonization time is 1-3 hours, with
The whole process of cooled to room temperature afterwards, the high temperature cabonization carries out in an inert atmosphere.
6. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 1
In step（2）The condition that the thermokalite is washed is：A concentration of 1-1.5M of alkali, alkali cleaning temperature are 90-100 DEG C, and the alkali cleaning time is 6-
8 hours；The alkali includes at least one of sodium hydroxide, potassium hydroxide.
7. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 1
In step（3）Described in porous filamentous nanocarbon 75-80 DEG C of the concentrated sulfuric acid/concentrated nitric acid is dispersed in the concentration of 0.8-3mg/ml
2-4 hours middle, wherein the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 2-3:1.
8. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 1
In step（4）Described in porous filamentous nanocarbon preform the volume content of porous filamentous nanocarbon be 60-72%, it is described
Resin matrix includes one in epoxy resin, unsaturated-resin, bimaleimide resin, phenolic resin or vinyl ester resin
Kind is several.
9. the preparation method of porous filamentous nanocarbon/special engineering plastics composite material, feature exist according to claim 1
In step（5）Described in nanofiber mats and porous filamentous nanocarbon preform the weight part ratio of resin matrix be 2-6:
100, a diameter of 200-800nm of nanofiber in the nanofiber mats, the special engineering plastics include polyether sulfone, poly-
One or more of sulfone, polyimides or polyether-ether-ketone, the organic solvent include dimethylformamide, dimethylacetamide
The one or more of amine, acetone, dichloromethane, trichloroethanes, dimethyl sulfoxide (DMSO), tetrahydrofuran.
10. multiple using porous filamentous nanocarbon/special engineering plastics that any one of claim 1 to 9 the method is prepared
Condensation material.
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| CN110818306A (en) * | 2019-11-21 | 2020-02-21 | 四川大学 | Reinforcing and toughening agent for concrete and preparation method and application thereof |
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