CN116925423A - Chopped carbon fiber and preparation method and application thereof - Google Patents
Chopped carbon fiber and preparation method and application thereof Download PDFInfo
- Publication number
- CN116925423A CN116925423A CN202210364906.6A CN202210364906A CN116925423A CN 116925423 A CN116925423 A CN 116925423A CN 202210364906 A CN202210364906 A CN 202210364906A CN 116925423 A CN116925423 A CN 116925423A
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- Prior art keywords
- carbon fiber
- composite material
- chopped
- chopped carbon
- resin
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 425
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 425
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- 238000002360 preparation method Methods 0.000 title claims abstract description 47
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- 238000001237 Raman spectrum Methods 0.000 claims abstract description 48
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 37
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims description 24
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- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000002993 sponge (artificial) Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
-
- 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
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- 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
Abstract
The invention relates to the technical field of new material preparation, and particularly discloses a chopped carbon fiber, a preparation method and application thereof. Raman spectrum detection is adopted, and Raman spectrum I of the surface of the chopped carbon fiber D /I G The average value is less than or equal to 0.94; and detecting by adopting an X-ray photoelectron spectrum, wherein the integral area of a C1s peak in the X-ray photoelectron spectrum is taken as 100%, and the content of the pyridinium on the surface of the chopped carbon fiber is more than or equal to 2% by taking the integral area of a fitting peak corresponding to the pyridinium as the integral area. The chopped carbon fiber obtained by the invention has higher graphitization degree, high pyridinium content and better performance. The chopped carbon fiber of the invention has stronger reinforcement on polymer in application as modified fillerActing as a medicine. The preparation method of the invention has extremely high application value in the method for recovering the carbon fiber from the waste carbon fiber composite material.
Description
Technical Field
The invention relates to the technical field of new material preparation, in particular to a chopped carbon fiber, a preparation method and application thereof.
Background
Chopped carbon fibers are carbon fibers obtained by cutting continuous carbon fibers, and are an important application form of carbon fibers. In the past, chopped carbon fibers have been used primarily as an auxiliary filler for preparing continuous carbon fiber reinforced thermosetting polymer composites in small amounts. However, along with the global policy of energy saving and emission reduction, the traditional thermosetting polymer composite material is gradually replaced by the thermoplastic polymer composite material, and the chopped carbon fiber can be used for preparing the high-performance thermoplastic polymer composite material by injection molding, hot pressing, injection molding and other modes. This has led to an increasing demand for high performance chopped carbon fibers.
When the chopped carbon fibers are used as the reinforcing main body of the thermoplastic polymer composite material, the chopped carbon fibers do not have the stress conduction characteristics of continuous long fibers, so that higher requirements are put on the mechanical properties of the chopped carbon fibers. Meanwhile, the processing of thermoplastic polymers requires that the chopped carbon fibers have better dispersibility. In order to meet the two requirements, the preparation of the commercial chopped carbon fiber at present mainly comprises the steps of selecting continuous carbon fiber with high graphitization degree as a raw material, carrying out surface treatment on the carbon fiber by using methods of chemical grafting, physical impregnation and the like, and finally cutting to prepare the chopped carbon fiber. The preparation of the raw materials requires carbon fibers with high graphitization degree, which are expensive, and the surface of the raw materials needs to be modified, so that the preparation cost of the chopped carbon fibers is greatly increased. Therefore, reducing the raw material cost for preparing the chopped carbon fibers and reducing the carbon fiber surface treatment process are key to reducing the preparation cost of the chopped carbon fibers.
The waste carbon fiber composite material is different from carbon fiber precursor, and is a waste which is difficult to recycle. If the carbon fiber in the waste carbon fiber composite material can be recycled to prepare the chopped carbon fiber capable of replacing commercial chopped carbon fiber, the production cost of the chopped carbon fiber can be obviously reduced, and waste is changed into valuable. The present inventors have disclosed a method for rapidly high temperature cracking of carbon fiber composites using porous composites in the patent literature of CN 111100322A. The principle of the method is that a carbon skeleton micropore structure in the porous composite material is utilized to generate plasma by microwave irradiation under nitrogen atmosphere, so that the surface of the porous carbon material forms high temperature of more than 1000 ℃, and the polymer on the surface of the carbon fiber composite material can be cracked at high temperature, thereby recycling and reutilizing the carbon fiber. However, the carbon fiber obtained by CN 111100322A shows that the graphitization degree is not high, and the quality is inferior to that of the carbon fiber precursor, so that the recycling value of the carbon fiber precursor is affected.
Therefore, how to provide a method for recycling carbon fibers from a carbon fiber composite material and obtaining a high-quality carbon fiber material fundamentally solves the recycling problem of the carbon fibers in the carbon fiber composite material is always a research direction in the field.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the invention aims to provide a chopped carbon fiber, a preparation method and application thereof, and the method can not only recover the carbon fiber from the carbon fiber composite materialFurther, a high-quality carbon fiber material can be obtained, and the surface I of the obtained carbon fiber material D /I G The average value, the pyridinium content and other comprehensive properties are superior to those of the original carbon fiber added into the carbon fiber composite material and the existing commercial carbon fiber, and the chopped carbon fiber obtained by the invention has higher graphitization degree, high pyridinium content and better performance. The chopped carbon fiber has stronger reinforcing effect on the polymer in the application of serving as a modified filler. The preparation method of the invention has extremely high application value in the method for recovering the carbon fiber from the waste carbon fiber composite material.
The first aspect of the invention is to provide a chopped carbon fiber, the Raman spectrum I of the surface of the chopped carbon fiber is detected by Raman spectrum D /I G The average value is less than or equal to 0.94; and detecting by adopting an X-ray photoelectron spectrum, wherein the integral area of a C1s peak in the X-ray photoelectron spectrum is taken as 100%, and the content of the pyridinium on the surface of the chopped carbon fiber is more than or equal to 2% by taking the integral area of a fitting peak corresponding to the pyridinium as the integral area.
In a preferred embodiment of the invention, raman spectroscopy detection is used, raman spectroscopy I of the surface of the chopped carbon fiber D /I G The average value is 0.93 or less, preferably 0.92 or less, more preferably 0.88 to 0.92, and may be, for example, 0.88, 0.89, 0.90, 0.91, 0.92, and any value or any interval of any two values.
The graphitization degree of the chopped carbon fiber is higher than that of the original carbon fiber and the commercial chopped carbon fiber, preferably the Raman spectrum I of the surface of the chopped carbon fiber D /I G The average value is 0.94 or less, preferably 0.93 or less, more preferably 0.92 or less, still more preferably 0.88 to 0.92, and less than the original carbon fiber (0.95).
In a preferred embodiment of the present invention, the content of the pyridinium on the surface of the chopped carbon fiber is 2.5% or more, preferably 3% or more, more preferably 3% to 3.5%, for example, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, and any value or any interval of any two values, based on the integrated area of the C1s peak in the X-ray photoelectron spectrum as 100% and the integrated area of the fitted peak corresponding to the pyridinium, by using the X-ray photoelectron spectrum.
The surface pyridinium content of the chopped carbon fiber is higher than that of the carbon fiber in the raw material and the commercial chopped carbon fiber, preferably, the surface X-ray photoelectron spectroscopy of the chopped carbon fiber shows that the pyridinium content is 2-5%, preferably 2.5-4%, more preferably 3-3.5%, higher than that of the raw material (0.5%) and the commercial chopped carbon fiber (0.6%).
In a preferred embodiment of the invention, raman spectrum detection is used, raman spectrum I of the interior of the chopped carbon fiber D /I G The standard deviation is 0.045 or less, preferably 0.035 or less, more preferably 0.03 or less, still more preferably 0.02 to 0.03, and may be, for example, 0.02, 0.022, 0.024, 0.026, 0.028, 0.03, and any value or any interval of any two values.
The uniformity of the internal graphitization structure of the chopped carbon fiber is higher than that of the original carbon fiber and the commercial chopped carbon fiber, preferably the Raman spectrum I of the inside of the chopped carbon fiber D /I G The standard deviation is 0.01-0.045, preferably 0.015-0.035, more preferably 0.02-0.03, smaller than the original carbon fiber (0.068) and the commercial chopped carbon fiber (0.054).
Raman Spectroscopy I D Is at a Raman shift of 1360cm -1 The peak intensity of the D peak at the left and right positions reflects the stretching vibration peak intensity of carbon atoms at the edge of the graphite sheet; raman Spectroscopy I G Is characterized by 1580cm in Raman shift -1 The peak intensity of the G peak at the left and right positions reflects the stretching vibration peak intensity of the carbon atoms in the plane of the graphite sheet. In the art, raman Spectroscopy I D /I G Average, internal raman spectrum I D /I G The standard deviation is related to the graphitization degree and graphitization uniformity of the chopped carbon fiber, and is described in, for example, raman spectroscopy study on the degree of homogenization of the T800-grade carbon fiber and PAN-based carbon fiber in surface treatment. General carbon fiber surface Raman Spectroscopy I D /I G The smaller the average value, the shorter the term carbonThe higher the graphitization degree of the fiber surface is, the Raman spectrum I of the inside of the carbon fiber is D /I G The smaller the standard deviation is, the higher the graphitization uniformity inside the chopped carbon fiber is, the higher the graphitization degree and graphitization uniformity of the chopped carbon fiber are, and the performance of the chopped carbon fiber is better.
The raman spectrum detection method and the subsequent data processing can adopt detection methods common in the field, and the invention can be realized. For example, the method described in the present invention can be used: the physical diameter of the light spot is 1 μm, the step size is 0.5 μm, and the length is 400-3000cm by using an inViaQontor microscopic confocal Raman spectrometer manufactured by Renisshaw company and using a 532nm wavelength laser light source -1 Raman shift, 50X 50 μm under optical microscope field of view 2 The surface of the chopped carbon fiber obtained in the example was subjected to Raman surface scanning within a range of 25X 25. Mu.m, under the field of view of an optical microscope 2 The inside of the chopped carbon fiber obtained in the example was subjected to raman surface scanning within the range. Carrying out batch processing on spectrum data obtained by Raman surface scanning by utilizing Matlab software to obtain I of the chopped carbon fiber obtained in the embodiment D /I G Distributing images and calculating I D /I G Mean and standard deviation of the values.
The pyridinium structure is a strong polar chemical structure, and is commonly used for improving the compatibility of inorganic materials and polymers, such as Epoxy Nanocomposites Based on High Temperature Pyridinium-Modified classes, and meanwhile, the pyridinium structure can also react with epoxy groups, such as Reaction of epoxy compounds with pyridine and pyridinium salts, so that the higher the pyridinium content on the surface of the chopped carbon fiber, the more favorable the combination of the carbon fiber and the polymers is when preparing the carbon fiber composite material.
The pyridine salt content of the chopped carbon fiber surface may be detected using methods common in the art such as, but not limited to, X-ray photoelectron spectroscopy.
When the X-ray photoelectron spectroscopy detection is adopted, the specific X-ray photoelectron spectroscopy detection method can be a detection method common in the field, and the invention can be realized. For example, the method described in the present invention can be used: x-ray photoelectron spectroscopy was measured using ESCA-LAB 250X-ray spectrometer manufactured by Thermo Fisher company.
Specific data processing methods after detection of the X-ray photoelectron spectroscopy may also employ data processing methods common in the art. For example, the method described in the present invention can be used: the integral area of the C1s peak in the X-ray photoelectron spectrum is calculated, and then the integral area of the fitting peak corresponding to the pyridinium is calculated, wherein the carbon element in the structural composition of the chopped carbon fiber occupies the main component, and the ratio of the integral area of the fitting peak corresponding to the pyridinium to the integral area of the C1s peak is multiplied by 100%, so that the content of the pyridinium can be calculated.
Specifically, the integrated area of the C1s peak in the X-ray photoelectron spectrum may be determined by a method conventional in the art, for example, a method of the present invention may be also used: the integrated area of the C1s peak in the 293-276eV range was calculated after background subtraction using XPS peak 4.1 software on a Shirley+Linear model with slope 0 for the C1s peak in the 293-276eV range.
The pyridine salt on the surface of the chopped carbon fiber generally has a peak corresponding to 401.5 + -0.5 eV, e.g. "N ] 2 –H 2 plasma functionalization of carbon fiber fabric for polyaniline grafting) is obtained by peak-by-peak fitting of an N1s peak in the range of 405-390eV in an X-ray photoelectron spectrum.
The integral area calculation method of the fitting peak corresponding to the specific pyridinium comprises the following steps: background subtraction was performed using XPS peak 4.1 software on the Sherley+Linear model with slope 0 for the N1s peak in the 405-390eV range; reference "N 2 –H 2 plasma functionalization of carbon fiber fabric for polyaniline grafting sets fitting peaks at 398.8eV, 399.6eV, 400.5eV and 401.5eV, and performs iterative fitting calculation under the conditions that the deviation of the positions of the fitting peaks is smaller than +/-0.5 eV and the half-width of the fitting peaks is smaller than 2.7eV according to a Gaussian (80%) -Lorentzian (20%) function until the sum of the chi-square values of all the fitting peaks (Σχ 2 ) Fitting is completed when the number of the fitting points is less than or equal to 1.5; the integral area of the fitted peak at 401.5 + -0.5 eV is taken as the integral area of the fitted peak corresponding to the pyridinium salt.
In a preferred embodiment of the inventionWherein the specific surface area of the chopped carbon fiber is more than or equal to 1.8m 2 Preferably 2m or more 2 Preferably 2.2m or more 2 Preferably still, it is 2.2-3m 2 /g。
The chopped carbon fiber of the invention has a specific surface area higher than that of the original carbon fiber, preferably, the BET specific surface area of the chopped carbon fiber is 1.8-4m 2 Preferably 2-3.5m 2 Preferably 2.2-3m 2 Per gram, higher than the original carbon fiber (1.6 m 2 /g) and commercial chopped carbon fibers (1.4 m 2 /g)。
According to the present invention, the specific surface area of the chopped carbon fibers may be measured by a conventional method in the art, such as, but not limited to, a BET specific surface area measurement method, which is used in the embodiment of the present invention. For example, the chopped carbon fibers obtained in the examples were tested using AutosorbIQ from Anton Paar, inc., and the sample was vacuum degassed at 180℃for 10 hours prior to testing.
In a preferred embodiment of the present invention, the length of the chopped carbon fibers is 50mm or less, preferably 25mm or less, more preferably 15mm or less.
In a preferred embodiment of the present invention, the chopped carbon fibers are prepared by the following method:
under flowing nitrogen atmosphere, irradiating the carbon fiber composite material contacted with the porous composite material by microwaves, and initiating self-heating of the carbon fiber composite material by using the porous composite material to crack and remove a polymer matrix in the carbon fiber composite material so as to obtain carbon fibers; wherein the carbon fiber composite material contains carbon fibers, and the mass content of the carbon fibers in the carbon fiber composite material is more than 65%.
In a second aspect, the present invention provides a method for preparing the chopped carbon fiber, which comprises the following steps: under flowing nitrogen atmosphere, irradiating the carbon fiber composite material contacted with the porous composite material by microwaves, and initiating self-heating of the carbon fiber composite material by using the porous composite material to crack and remove a polymer matrix in the carbon fiber composite material so as to obtain carbon fibers; wherein the carbon fiber composite material contains carbon fibers, and the mass content of the carbon fibers in the carbon fiber composite material is more than 65%.
The inventor of the invention discovers through researches that the mass content of carbon fibers in the carbon fiber composite material is more than 65%, and the recycled chopped carbon fibers with better performance can be obtained by carrying out microwave irradiation under the atmosphere of the porous composite material and flowing nitrogen.
According to the invention, the mass content of the carbon fiber in the carbon fiber composite material is more than 65%, for example more than or equal to 65% and less than 100%, and the carbon fiber composite material has better technical effects. In a preferred embodiment of the present invention, the carbon fiber composite material has a mass content of 65% -85%, for example, 65%, 70%, 75%, 80%, 85%, and any number or any interval of any two numbers.
According to the present invention, the carbon fiber composite material has a wide source range, and in a preferred embodiment of the present invention, the carbon fiber composite material is selected from at least one of the following composite materials each containing carbon fibers: thermoset carbon fiber composites, thermoplastic carbon fiber composites, and carbon fiber prepregs.
According to the present invention, the carbon fiber length in the carbon fiber composite material is selected within a wide range, and in a preferred embodiment of the present invention, the carbon fiber length in the carbon fiber composite material is 50mm or less, preferably 25mm or less, and more preferably 15mm or less.
According to the invention, the three dimensions of the carbon fiber composite material in the x, y and z spatial directions are selected in a wide range, and in a preferred embodiment of the invention, the dimensions of the carbon fiber composite material in the x, y and z spatial directions are all less than or equal to 50mm. The carbon fiber composite material of the above-mentioned dimensions may be obtained by, but not limited to, a treatment such as cutting.
According to the present invention, the mass ratio of the carbon fiber composite material to the porous composite material is selected to be wide in a range, and in a preferred embodiment of the present invention, the mass ratio of the carbon fiber composite material to the porous composite material is (0.1 to 10): 1, preferably (0.2-5): 1, more preferably (0.5-2): 1, for example, may be 0.5:1, 1:1, 1.5:1, 2:1, and any number between 0.5 and 2 or any interval of any two numbers to 1 ratio.
According to the present invention, the porous composite material has a wide selection range, and in a preferred embodiment of the present invention, the porous composite material includes an inorganic porous skeleton and a carbon material supported on the inorganic porous skeleton; preferably, the carbon material accounts for 0.001% -99% of the total mass of the porous composite material; and/or the inorganic porous skeleton is an inorganic material having a porous structure; preferably, the inorganic porous skeleton has an average pore diameter of 0.01 to 1000 μm; the porosity is 1% -99.99%.
The porous composite material in the present invention includes, but is not limited to, the porous composite material described in CN111100322a (a method of microwave pyrolysis of carbon fiber composite material disclosed in CN 201811264420.5), and preferably the porous composite material described in CN111100322a is used.
For example, the porous composite includes: an inorganic porous skeleton and a carbon material supported on the inorganic porous skeleton. The loading refers to the fixation of the carbon material on the surface or in the structure of the inorganic porous skeleton through a certain binding force.
The carbon material accounts for 0.001-99%, preferably 0.01-90%, more preferably 0.1-80% of the total mass of the porous composite material;
The inorganic porous skeleton is an inorganic material with a porous structure; the average pore diameter of the inorganic porous skeleton is 0.01 to 1000. Mu.m, preferably 0.05 to 500. Mu.m, more preferably 0.2 to 250. Mu.m; the porosity is 1% -99.99%; preferably 10% to 99.9%, more preferably 30% to 99%. The pore size of individual pores is derived from the shortest value in the SEM photograph of the intersection distance of the straight line passing through the center of the pore and the pore profile.
The carbon material is at least one of graphene, carbon nanotubes, carbon nanofibers, graphite, carbon black, carbon fibers, carbon dots, carbon nanowires, products obtained by carbonizing a carbonizable organic substance or products obtained by carbonizing a mixture of carbonizable organic substances, preferably at least one of graphene, carbon nanotubes, products obtained by carbonizing a carbonizable organic substance and products obtained by carbonizing a mixture of carbonizable organic substances.
The mixture of carbonizable organic compounds is a mixture of carbonizable organic compounds, inorganic compounds of non-metal and non-metal compounds, and other organic compounds of non-metal compounds.
The carbonization refers to: and (3) treating the organic matters at a certain temperature under the condition of atmosphere, wherein all or most of hydrogen, oxygen, nitrogen, sulfur and the like in the organic matters volatilize, so that a synthetic material with high carbon content is obtained.
The carbonizable organic matter is preferably an organic polymer compound, and the organic polymer compound comprises a synthetic polymer compound and a natural organic polymer compound; the synthetic polymer compound is preferably rubber or plastic; the plastic includes thermosetting plastic and thermoplastic plastic.
The natural organic polymer compound is preferably at least one of starch, viscose, lignin and cellulose.
The synthetic polymer compound is preferably at least one selected from the group consisting of epoxy resin, phenolic resin, furan resin, polystyrene, styrene-divinylbenzene copolymer, polyacrylonitrile, polyaniline, polypyrrole, polythiophene, styrene-butadiene rubber, and urethane rubber.
The mixture of carbonizable organics is preferably at least one of coal, natural pitch, petroleum pitch, or coal tar pitch.
The inorganic material of the inorganic porous skeleton is one or a combination of more of carbon, silicate, aluminate, borate, phosphate, germanate, titanate, oxide, nitride, carbide, boride, sulfide, silicide and halide; wherein the oxide is preferably at least one of alumina, silica, zirconia, magnesia, ceria and titania; the nitride is preferably at least one of silicon nitride, boron nitride, zirconium nitride, hafnium nitride, and tantalum nitride; the carbide is preferably at least one of silicon carbide, zirconium carbide, hafnium carbide and tantalum carbide; the boride is preferably at least one of zirconium boride, hafnium boride and tantalum boride.
The inorganic material of the inorganic porous skeleton is more preferably at least one of carbon, silicate, alumina, magnesia, zirconia, silicon carbide, boron nitride, and potassium titanate.
The inorganic porous skeleton is preferably at least one of the following specific skeletons: a carbon skeleton obtained after carbonization of the polymer sponge, a porous skeleton formed by inorganic fibers, an inorganic sponge skeleton, a skeleton formed by stacking inorganic particles, a ceramic sponge skeleton obtained after roasting of a ceramic precursor sponge, and a ceramic fiber skeleton obtained after roasting of a ceramic precursor fiber; preferably, the porous skeleton is a skeleton obtained by carbonizing melamine sponge, a skeleton obtained by carbonizing phenolic resin sponge, a porous skeleton of aluminum silicate fiber (such as aluminum silicate rock wool), a porous skeleton of mullite fiber, a porous skeleton of alumina fiber (such as alumina fiber board), a porous skeleton of zirconia fiber, a porous skeleton of magnesia fiber, a porous skeleton of boron nitride fiber, a porous skeleton of boron carbide fiber, a porous skeleton of silicon carbide fiber, a porous skeleton of potassium titanate fiber, and a ceramic fiber skeleton obtained by calcining ceramic precursor fiber.
The porous structure of the inorganic porous skeleton may be derived from the pore structure of the skeleton material itself, for example in the form of a sponge-like structure; the porous structure can also be formed by stacking fiber materials, such as fiber cotton, fiber felt, fiber board and other structural forms; pore structures, such as sand pack structures, may also result from the accumulation of particulate material; but may also come from a combination of the above. Preferably from a pore structure of stacked fibrous material. In particular, the porous skeleton made of the inorganic fibers described above is a porous structure made up of a skeleton in which fibrous materials are stacked, and does not mean that the fibers themselves have a porous structure.
The porous composite material can generate high-temperature electric arcs in microwaves, such as electric arcs which can heat the porous composite material to more than 1000 ℃ in a 900w microwave field, and the porous composite material is resistant to high temperature, and can resist high temperature of 3000 ℃ at most. The porous composite material for generating electric arc in the microwave is a novel and efficient microwave heating material.
Specifically, the preparation method of the porous composite material preferably comprises the following steps:
a. preparing a carbon material for loading or a carbon material precursor solution or dispersion;
b. immersing the inorganic porous skeleton or the precursor of the inorganic porous skeleton into the solution or the dispersion liquid in the step a, so that the pores of the inorganic porous skeleton or the precursor of the inorganic porous skeleton are filled with the solution or the dispersion liquid; the carbon material and/or the carbon material precursor accounts for 0.001% -99.999%, preferably 0.01% -99.99%, more preferably 0.1% -99.9% of the total mass of the inorganic porous skeleton material or the inorganic porous skeleton material precursor and the carbon material and/or the carbon material precursor;
c. taking out the porous material obtained in the step b, heating, drying, and separating out or solidifying the carbon material or the precursor of the carbon material, and loading the carbon material or the precursor of the carbon material on an inorganic porous skeleton or the precursor of the inorganic porous skeleton; the heating and drying temperature is 50-250 ℃, preferably 60-200 ℃, more preferably 80-180 ℃;
If the raw materials adopt carbon materials and inorganic porous frameworks, obtaining the porous composite material generating electric arc in the microwaves after the step c; if the raw material adopts at least one of a carbon material precursor or an inorganic porous skeleton precursor, the following step d) is needed to be continued:
d. heating the porous material obtained in the step c in inert gas atmosphere, converting the precursor of the inorganic porous skeleton into the inorganic porous skeleton, and/or reducing or carbonizing the precursor of the carbon material to obtain the porous composite material generating electric arc in the microwaves; the heating temperature is 400-1800 ℃, preferably 600-1500 ℃, more preferably 800-1200 ℃.
Among them, preferred is:
the inorganic porous skeleton precursor is a porous material which can be converted into an inorganic porous skeleton; at least one of a ceramic precursor, a porous material of a carbonizable organic compound, or a porous material of a mixture of carbonizable organic compounds.
The carbon material precursor is at least one of graphene oxide, modified carbon nanotubes, modified carbon nanofibers, modified graphite, modified carbon black, modified carbon fibers, and carbonizable organics or a mixture of carbonizable organics. Modified carbon nanotubes, modified carbon nanofibers, modified graphite, modified carbon black, modified carbon fibers refer to carbon materials pretreated by, for example, using a dispersant or a surfactant, or grafting hydrophilic groups to improve the dispersibility of these carbon materials in water or an organic solvent to obtain a stable dispersion; all of these pretreatment means are pretreatment means for improving dispersibility in the prior art. The carbon materials subjected to the above pretreatment such as graphene aqueous dispersion, graphene ethanol dispersion, graphene aqueous slurry, graphene oily slurry, graphene oxide aqueous dispersion, graphene oxide ethanol dispersion, graphene oxide N-methylpyrrolidone dispersion, carbon nanotube aqueous dispersion, carboxylated carbon nanotube aqueous dispersion, carbon nanotube ethanol dispersion, carbon nanotube dimethylformamide dispersion, carbon nanotube N-methylpyrrolidone slurry and the like may also be obtained by commercially available methods.
The solvent of the carbon material or the precursor solution or dispersion thereof in the step a can be selected from one or a combination of benzene, toluene, xylene, trichlorobenzene, trichloromethane, cyclohexane, ethyl caproate, butyl acetate, carbon disulfide, ketone, acetone, cyclohexanone, tetrahydrofuran, dimethylformamide, water or alcohols;
wherein the alcohol is preferably at least one selected from propanol, n-butanol, isobutanol, ethylene glycol, propylene glycol, 1, 4-butanediol, isopropanol and ethanol;
the carbon material precursor for loading in the preparation method of the porous composite material is preferably a precursor which can be dissolved or dispersed in a solvent friendly to human body and environment before loading, so that the preparation process is green. The solvent friendly to human body and environment is at least one selected from ethanol, water and a mixture of the ethanol and the water. I.e. the solvent in step a is more preferably a solvent comprising water and/or ethanol; further preferred are water and/or ethanol.
The solution or dispersion of step a may be sufficient to dissolve or disperse the carbon material and/or carbon material precursor in the solvent, and may be generally in a concentration of 0.001 to 1g/mL, preferably 0.002 to 0.8g/mL, and more preferably 0.003 to 0.5g/mL.
More specifically:
in the preparation method of the porous composite material, when the carbon material loaded on the inorganic porous skeleton is graphene, a graphene oxide aqueous solution is preferably used in the step a.
In the method for preparing a porous composite material according to the present invention, when the carbon material supported on the inorganic porous skeleton is carbon nanotubes, the dispersion of carbon nanotubes is preferably used in step a.
When the carbon material precursor for load is thermosetting plastic, the step a is required to prepare a proper curing system according to a curing formula commonly used in the prior art of the selected thermosetting plastic; to the curing system, optionally one or more additives selected from the group consisting of: curing accelerators, dyes, pigments, colorants, antioxidants, stabilizers, plasticizers, lubricants, flow modifiers or adjuvants, flame retardants, drip retardants, antiblocking agents, adhesion promoters, conductive agents, polyvalent metal ions, impact modifiers, mold release aids, nucleating agents, and the like; the dosage of the additive is conventional, or is adjusted according to the actual requirement. When the carbon material precursor for loading is thermosetting plastic, the thermosetting resin serving as the carbon material precursor is cured after heating in the subsequent step c, and is loaded on the inorganic porous skeleton.
When the thermosetting plastic is selected as the carbon material precursor for loading in the preparation method of the porous composite material, the corresponding good solvent in the prior art is selected in the step a to dissolve the thermosetting plastic and the curing system thereof, so as to obtain the carbon material precursor solution for loading.
When the carbon material precursor for load is thermoplastic plastics, the solution of the carbon material precursor for load can be added with common additives in the prior art in the plastic processing process, such as antioxidants, auxiliary antioxidants, heat stabilizers, light stabilizers, ozone stabilizers, processing aids, plasticizers, softeners, anti-blocking agents, foaming agents, dyes, pigments, waxes, extenders, organic acids, flame retardants, coupling agents and the like. The dosage of the auxiliary agent is conventional dosage or is adjusted according to the actual condition.
In step b of the method for producing a porous composite material of the present invention, the pores of the inorganic porous skeleton may be filled with the carbon material for supporting or the carbon material precursor solution or dispersion by pressing several times or not pressing at all.
In the method for preparing a porous composite material according to the present invention, after the porous material obtained in step b is taken out in step c, the excess carbon material for supporting or the precursor solution or dispersion of the carbon material in the porous material obtained in step b may be removed with or without any means including, but not limited to, one or both of extrusion and centrifugation.
The heating in steps c and d of the preparation method of the porous composite material in the present invention may preferably be microwave heating, which is not only efficient but also uniformly heated, specifically: the power of the microwaves in the step c is 1W-100KW, preferably 500W-10KW, and the microwave time is 2-200min, preferably 20-200min.
The microwave power in the step d is changed into 100W-100KW, preferably 700W-20KW; the microwave time is 0.5-200min, preferably 1-100min.
The heating in step d of the process for the preparation of a porous composite material according to the invention is carried out under an inert gas atmosphere, selected from inert gas atmospheres commonly used in the art, preferably nitrogen.
The equipment adopted in the preparation method of the porous composite material is common equipment.
As described above, the preparation method of the porous composite material combines the inorganic porous skeleton and the carbon material to prepare the porous composite material with excellent mechanical properties, and can generate electric arcs in a microwave field so as to quickly generate high temperature, for example, the porous composite material can generate electric arcs in a 900w microwave field so as to raise the temperature of the porous composite material to more than 1000 ℃, the porous composite material is resistant to high temperature, the process flow is simple and easy to implement, and the large-scale preparation is easy to realize.
According to the present invention, the microwave irradiation conditions in the preparation method of the chopped carbon fiber have a wide selection range, and in a preferred embodiment of the present invention, the microwave irradiation conditions include: the power of the microwave irradiation is 300 to 2000W, preferably 500 to 1500W, more preferably 700 to 1000W.
According to the present invention, the time conditions of the microwave irradiation in the preparation method of the chopped carbon fiber are selected to be wide, and in a preferred embodiment of the present invention, the time of the microwave irradiation is 5 to 120 minutes, preferably 10 to 60 minutes, more preferably 10 to 30 minutes, for example, 10 minutes, 20 minutes, 30 minutes, and any interval of any number or any two numbers.
According to the preparation method of the chopped carbon fiber, a flowing nitrogen atmosphere is needed, and the inventor of the invention discovers through researches that the flowing nitrogen can discharge a gas phase product generated by polymer cracking in the carbon fiber composite material, and simultaneously enables nitrogen in a system to participate in a reaction to generate pyridine salt on the surface of the chopped carbon fiber.
According to the present invention, the flow rate of nitrogen in the flowing nitrogen atmosphere is selected to be wide in a preferred embodiment of the present invention, and the flow rate of nitrogen in the flowing nitrogen atmosphere is 10 to 1000ml/min, preferably 50 to 500ml/min, more preferably 50 to 200ml/min, for example, 50ml/min, 100ml/min, 150ml/min, 200ml/min, and any interval of any number or any two of the numbers, relative to 10g of the carbon fiber composite material. The nitrogen flow rate in the preferred embodiments 1-3 of the invention can ensure that the nitrogen concentration in the whole system meets the requirement that the pyridine salt content on the surface of the prepared chopped carbon fiber is more than or equal to 3 percent, and can ensure that the surface temperature of the carbon fiber meets the surface I of the chopped carbon fiber D /I G The average value is not less than 0.92.
In the above preferred embodiments of the present invention, the preferred nitrogen flow rate has better technical effects, and the inventor of the present invention considers that the cause may be: when the flow rate of nitrogen is too low, gas phase products generated by polymer pyrolysis in the carbon fiber composite material cannot be discharged rapidly, so that the nitrogen concentration in the whole system is reduced, and the pyridine salt content on the surface of the prepared chopped carbon fiber is reduced; when the flow rate of the nitrogen is too high, the flow of the nitrogen can take away heat, so that the surface temperature of the carbon fiber is reduced, and the graphitization degree of the prepared chopped carbon fiber is reduced. In the preferred embodiment, the advantages of the nitrogen gas participating in the reaction and maintaining the high temperature are achieved, and the obtained chopped carbon fiber has better performance.
In a preferred embodiment of the present invention, the chopped carbon fibers are obtained by preferably using a carbon fiber composite as a raw material, preferably using the porous composite described in the invention patent CN111100322a (i.e. CN 201811264420.5) to initiate self-heating of carbon fibers in the raw material by microwave irradiation under flowing nitrogen atmosphere.
In a more preferred embodiment of the present invention, the preparation process of the chopped carbon fiber according to the present invention comprises the following steps:
a. Placing a carbon fiber composite material on the surface of the porous composite material;
b. placing the carbon fiber composite material and the porous composite material in a heat preservation container;
c. and carrying out microwave irradiation on the carbon fiber composite material in the heat preservation container under the flowing nitrogen atmosphere to obtain the chopped carbon fiber.
More specifically, the carbon fiber composite material selected in the step a of the preparation process of the chopped carbon fiber requires: the carbon fiber length in the carbon fiber composite material is less than or equal to 50mm, preferably less than or equal to 25mm, more preferably less than or equal to 15mm; the mass fraction of the carbon fiber in the carbon fiber composite material is higher than 65%, preferably 65-85%, preferably 65-75%; the carbon fiber composite material may be selected from various thermosetting carbon fiber composite materials, various thermoplastic carbon fiber composite materials, and various carbon fiber prepregs.
The heat-insulating container in the step b of the preparation process of the chopped carbon fiber can be selected from various containers or pipelines which can be penetrated by microwaves and can resist the high temperature of more than 1000 ℃ in the prior art, such as a quartz crucible, a quartz reactor, a quartz tube, an alumina crucible, an alumina reactor, an alumina tube and the like.
The microwave irradiation in the step c of the preparation process of the chopped carbon fiber can adopt various microwave devices in the prior art, such as a household microwave oven, industrialized microwave devices, a microwave generator and the like.
In a third aspect, the present invention provides a chopped carbon fiber prepared by the preparation method described above.
The surface I of the chopped carbon fiber prepared by the preparation method of the invention D /I G Average value, carbon fiber interior I D /I G The standard deviation, the pyridinium content, the BET specific surface area and other comprehensive properties are better, the graphitization degree is higher, the pyridinium content is high, and the properties are better.
The chopped carbon fiber can be applied to thermosetting polymers and thermoplastic polymers without surface treatment to prepare chopped carbon fiber modified polymer composite materials.
A fourth aspect of the invention provides the use of the chopped carbon fibres of the first or third aspect as a modified filler in a polymer composite.
Surface I of chopped carbon fiber in the present invention D /I G Average value, carbon fiber interior I D /I G The standard deviation, the pyridine salt content, the BET specific surface area and other comprehensive properties are better. The chopped carbon fiber has stronger reinforcing effect on the polymer in the application of serving as a modified filler.
The polymer matrix in the polymer composite according to the present invention is of a wide range of choices, such as, but not limited to, thermosetting polymers or thermoplastic polymers.
In a preferred embodiment of the present invention, the polymer matrix in the polymer composite is a thermosetting polymer or a thermoplastic polymer.
In a more preferred embodiment of the present invention, the thermosetting polymer is selected from at least one of epoxy resin, phenolic resin, maleic anhydride resin, polyacrylic resin, polyurethane resin, and cycloolefin resin.
In a more preferred embodiment of the present invention, the thermoplastic polymer is at least one selected from the group consisting of polyamide resin, polyester resin, polycarbonate resin, polyether ketone resin, polyphenylene sulfide resin, polysulfone resin, polyvinyl chloride resin, polyacrylic resin, polyethylene resin, polypropylene resin, alkyd resin, polystyrene resin, polyimide resin, and ABS resin.
The fourth aspect of the invention provides an application of the preparation method of the third aspect in recycling carbon fibers in waste carbon fiber composite materials.
By adopting the preparation method, the chopped carbon fibers recovered from the composite material can replace commercial chopped carbon fibers without surface treatment, and therefore, the preparation method disclosed by the invention fundamentally solves the problem that the chopped carbon fibers recovered from the composite material are poor in performance, and the obtained chopped carbon fibers are better in performance.
Compared with the prior art, the invention has the following advantages:
(1) The surface I of the carbon fiber material provided by the invention D /I G The average value, the pyridinium content and other comprehensive properties are superior to those of the original carbon fiber added into the carbon fiber composite material and the existing commercial carbon fiber, and the chopped carbon fiber obtained by the invention has higher graphitization degree, high pyridinium content and better performance.
(2) The chopped carbon fiber can be applied to polymers without surface treatment to prepare the chopped carbon fiber modified polymer composite material, and the chopped carbon fiber has stronger reinforcing effect on the polymers when being used as modified filler.
(3) The invention fundamentally solves the problem of poor performance of the chopped carbon fiber recovered in the composite material, and the obtained chopped carbon fiber has better performance.
The inventors of the present invention have found through studies that the chopped carbon fibers of the present invention can be obtained by using the carbon fiber composite material of the present invention in a specific content and the specific flowing nitrogen atmosphere and the porous composite material. The chopped carbon fibers have the advantages, and the inventor of the present invention has proved through a great deal of research, and considers that the reason may be that: the carbon fiber composite material consists of carbon fibers and polymers, and when the mass fraction of the carbon fibers in the carbon fiber composite material exceeds 65%, the distance between the carbon fibers in the carbon fiber composite material is reduced to be within 200 mu m. Therefore, when such a carbon fiber composite material is decomposed by microwave irradiation under a nitrogen atmosphere using a porous composite material, a microporous structure having a distance of less than 200 μm is formed between carbon fibers, and this microporous structure can also generate plasma under microwaves. The plasma generated by the carbon fiber can self-heat the carbon fiber, so that the graphitization degree of the carbon fiber is improved. Meanwhile, the plasmas can also modify the surface of the carbon fiber to form a pyridinium structure on the surface of the carbon fiber, so that the polarity of the surface of the carbon fiber is improved, and the carbon fiber is easier to disperse in a polar polymer, so that a composite material with better performance is obtained when the carbon fiber is applied as a filler.
Drawings
FIG. 1-1 shows Raman spectrum I of the surface of the original carbon fiber D /I G Is a distribution of (3);
FIGS. 1-2 are Raman spectra I of the surface of chopped carbon fibers prepared in example 1 D /I G Is a distribution of (3);
FIGS. 1-3 are Raman spectra I of commercial chopped carbon fiber surfaces D /I G Is a distribution of (3);
FIG. 2-1 shows the Raman spectrum I of the inside of the original carbon fiber D /I G Is a distribution of (3);
FIG. 2-2 shows the Raman spectrum I of the inside of the chopped carbon fiber prepared in example 1 D /I G Is a distribution of (3);
FIGS. 2-3 are Raman spectra I of the interior of commercial chopped carbon fibers D /I G Is a distribution of (3);
FIG. 3 is an X-ray photoelectron spectrum of a commercial chopped carbon fiber, a virgin carbon fiber, and a chopped carbon fiber prepared in example 1.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention. The invention is further illustrated by the following examples; the present invention is not limited by these examples.
Experimental data in the examples were measured using the following instrument and assay method:
1. Raman Spectroscopy I of the chopped carbon fibers obtained in the examples D /I G ：
The physical diameter of the light spot is 1 μm, the step size is 0.5 μm, and the length is 400-3000cm by using an inViaQontor microscopic confocal Raman spectrometer manufactured by Renisshaw company and using a 532nm wavelength laser light source -1 Raman shift, 50X 50 μm under optical microscope field of view 2 The surface of the chopped carbon fiber obtained in the example was subjected to Raman surface scanning within a range of 25X 25. Mu.m, under the field of view of an optical microscope 2 The inside of the chopped carbon fiber obtained in the example was subjected to raman surface scanning within the range. Carrying out batch processing on spectrum data obtained by Raman surface scanning by utilizing Matlab software to obtain I of the chopped carbon fiber obtained in the embodiment D /I G Distributing images and calculating I D /I G Mean and standard deviation of the values.
In batch processing, the processing steps for each tensman spectrum are: (1) Using Savitzky-Golay method, under the parameter condition of window point number 21 and third-order polynomial, for 400-3000cm -1 Carrying out smoothing treatment on Raman spectrum data in a range; (2) Smoothing coefficients 10 using adaptive iterative re-weighting penalty least squares (airPLS) -7 Punishment parameter/fitting frequency 2, weight 0.1, asymmetry 0.05, maximum iteration frequency 20 for 1000-1800cm -1 Baseline subtraction was performed for raman spectra within range; (3) Calculation I D /I G Values.
2. The method for measuring the content of pyridinium on the surface of the chopped carbon fiber obtained in the embodiment comprises the following steps:
x-ray photoelectron spectroscopy was measured using ESCA-LAB 250X-ray spectrometer manufactured by Thermo Fisher company. Analysis was performed with a 300W power alkα X-ray source (hv= 1486.6 eV). The resulting photoelectron spectrum was calibrated for all peaks in the spectrum with a C1s peak of 284.8 eV.
Because the carbon element in the structural composition of the chopped carbon fiber accounts for the main component, the integral area of the C1s peak in the X-ray photoelectron spectrum is taken as 100 percent, and the percentage of the integral area of the fitted peak corresponding to the pyridinium to the integral area of the C1s peak in the X-ray photoelectron spectrum is calculated, namely the percentage of the pyridinium at the surface of the chopped carbon fiber.
The integral area calculation method of the C1s peak comprises the following steps: the integrated area of the C1s peak in the 293-276eV range was calculated after background subtraction using XPS peak 4.1 software on a Shirley+Linear model with slope 0 for the C1s peak in the 293-276eV range.
The fitted peak corresponding to the pyridinium is obtained by carrying out peak-by-peak fitting on the N1s peak in the range of 405-390eV in the X-ray photoelectron spectrum. The integral area calculation method of the fitting peak corresponding to the pyridinium comprises the following steps: background subtraction was performed using XPS peak 4.1 software on the Sherley+Linear model with slope 0 for the N1s peak in the 405-390eV range; reference "N 2 –H 2 plasma functionalization of carbon fiber fabric for polyaniline grafting sets fitting peaks at 398.8eV, 399.6eV, 400.5eV and 401.5eV, and performs iterative fitting calculation under the conditions that the deviation of the positions of the fitting peaks is smaller than +/-0.5 eV and the half-width of the fitting peaks is smaller than 2.7eV according to a Gaussian (80%) -Lorentzian (20%) function until the sum of the chi-square values of all the fitting peaks (Σχ 2 ) Fitting is completed when the number of the fitting points is less than or equal to 1.5; the integral area of the fitted peak at 401.5 + -0.5 eV is taken as the integral area of the fitted peak corresponding to the pyridinium salt.
3. The BET specific surface area calculation method of the chopped carbon fibers obtained in the examples comprises the following steps:
the chopped carbon fibers obtained in the examples were tested using Anton Paar company AutosorbIQ and the samples were vacuum degassed at 180 ℃ for 10 hours prior to testing.
4. Mechanical properties of chopped carbon fiber modified polymer composite material prepared from chopped carbon fibers obtained in the embodiment:
the flexural modulus and flexural strength of the chopped carbon fiber modified polymer composite material obtained in the examples were measured by performing a three-point bending test by an INSTRON3366 mechanical tester, and the specifications, the number, the test conditions and the like of test bars were in compliance with ISO178:2001.
The starting materials for the examples and comparative examples of the present invention were all commercially available. The raw carbon fiber refers to T300 carbon fiber (purchased from eastern japan); commercial carbon fiber refers to T700 chopped carbon fiber (CT 70CP006-PAY, 6mm in length, available from Toli Corp., japan).
Preparation example
Preparation of carbon fiber composite materials with different carbon fiber contents:
mixing epoxy resin (CDY-128 of Baling petrochemical Co., ltd.) and methyl tetrahydrophthalic anhydride (Allatin Co., ltd.) at a mass ratio of 10:9, and adding DMP-30 (accelerator) five thousandths of the total mass of the mixed solution to prepare the impregnating solution. After the original carbon fiber stack is placed into a hot-pressing mold, impregnating solution is injected into the hot-pressing mold according to the mass ratio of the carbon fiber to the composite material impregnating solution of (10:90), (30:70), (64:36), (65:35), (70:30), (75:25), (85:15). And the carbon fiber composite material with the carbon fiber accounting for 10 percent, 30 percent, 64 percent, 65 percent, 70 percent, 75 percent and 85 percent of the mass of the carbon fiber composite material is prepared by a hot pressing process of keeping the temperature of 90 ℃ for 1h, keeping the temperature of 130 ℃ for 2h, keeping the temperature of 160 ℃ for 3h and keeping the temperature of 180 ℃ for 0.5h under the pressure of 5 MPa.
Example 1
10g of a carbon fiber composite material with 70% of carbon fibers by mass fraction was cut into about 6X 3mm by using a cutter 3 Is a small block of (a). These small pieces were placed on the surface of 10g of the porous composite material prepared in example 1 of the invention patent CN 111100322A, and placed in an insulation can (outer diameter 60mm, inner diameter 40mm, height 80mm, bottom thickness 20 mm) made of alumina fiber, and then placed in a quartz can into which gas can be introduced. Placing quartz pot into microwave reactor (MKX-R1C 1B, qingdao Michaemaker) Manufacturing company, ltd.) under a nitrogen atmosphere at a flow rate of 70ml/min, microwave irradiation was performed at 800W power for 10 min. The porous composite material generates plasma to crack the carbon fiber composite material under microwave irradiation; the carbon fiber exposed to nitrogen after the polymer in the carbon fiber composite material is cracked can generate plasma, so that the surface temperature of the carbon fiber reaches more than 1000 ℃.
The inventor of the present invention found through research that, at this time, the plasmas continuously accelerate the pyrolysis of polymers in the carbon fiber composite material, and the plasmas heat the carbon fibers, so that the graphitization degree of the carbon fibers is improved, and in addition, the plasmas improve the physicochemical properties of the surfaces of the carbon fibers. And after the microwave irradiation is finished, carrying out Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption on the prepared chopped carbon fiber.
As shown in FIGS. 1-1 to 1-3, the surface of the chopped carbon fiber prepared in example 1 has a Raman spectrum I D /I G The values are significantly smaller than those of the original carbon fiber and the commercial chopped carbon fiber, the Raman surface scanning statistics corresponding to FIGS. 1-1 to 1-3 are shown in Table 1, and the surface I of the chopped carbon fiber prepared in example 1 D /I G Is less than 0.92, less than the original carbon fiber (0.95) and the commercial chopped carbon fiber (0.93). This illustrates that the chopped carbon fibers prepared in example 1 had a higher degree of surface graphitization than the virgin carbon fibers and the commercial chopped carbon fibers.
As shown in FIGS. 2-1 to 2-3, the internal Raman spectrum I of the chopped carbon fiber prepared in example 1 D /I G The distribution of values is more uniform than that of the original carbon fiber and the commercial chopped carbon fiber, the Raman scanning statistics corresponding to FIGS. 2-1 to 2-3 are shown in Table 1, and the surface I of the chopped carbon fiber prepared in example 1 D /I G Is 0.025, smaller than the original carbon fiber (0.068) and the commercial chopped carbon fiber (0.054). This illustrates that the internal graphitized structure uniformity of the chopped carbon fibers prepared in example 1 is higher than that of the virgin carbon fibers and the commercial chopped carbon fibers.
As shown in fig. 3, the nitrogen element composition of the surface of the chopped carbon fiber prepared in example 1 and the commercial chopped carbon fiber have significant differences, and as shown in table 1, the pyridinium content at the surface of the chopped carbon fiber is 3.3%, which is higher than that of the original carbon fiber (0.5%) and the commercial chopped carbon fiber (0.6%), so that the surface of the chopped carbon fiber has polarity enhanced, and thus is more compatible with polar group structures such as ether bonds, thioether bonds, ester bonds, amide bonds, urethane bonds and the like in the polymer, which indicates that the surface of the chopped carbon fiber prepared in example 1 is more compatible with the polymer.
As shown in Table 1, the BET specific surface area of the chopped carbon fiber prepared in example 1 was 2.4m 2 And/g is higher than that of the original carbon fiber (1.6 m 2 /g) and commercial chopped carbon fibers (1.4 m 2 /g), which illustrates that the chopped carbon fibers prepared in example 1 have a larger contact area with the polymer.
The specific results are shown in Table 1.
Example 2
Taking 10g of carbon fiber composite material with the mass percentage of 75%, and cutting the carbon fiber composite material into the shape of about 10 multiplied by 3mm by using a cutting machine 3 Is a small block of (a). These small pieces were placed on the surface of 20g of the porous composite material prepared in example 1 of invention patent CN 111100322A, and placed in an insulation can (outer diameter 60mm, inner diameter 40mm, height 80mm, bottom thickness 20 mm) made of alumina fiber, and then placed in a quartz can into which gas can be introduced. The quartz pot was placed in a microwave reactor (MKX-R1C 1B, manufactured by Qingdao Michaelwis instruments Co., ltd.) and subjected to microwave irradiation at 1000W for 30 minutes under a nitrogen atmosphere at a flow rate of 150 ml/min. After the microwave irradiation is finished, the obtained chopped carbon fiber is subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption. The specific results are shown in Table 1.
Example 3
10g of carbon fiber composite material with 65% of carbon fiber by mass percentage is taken, and the carbon fiber composite material is cut into the shape of 15 multiplied by 3mm by using a cutting machine 3 Is a small block of (a). These small pieces were placed on the surface of a 5g porous composite material prepared in example 1 of the invention patent 201811264420.5 (i.e., CN 111100322A), and placed in an insulated pot (outer diameter 60mm, inner diameter 40mm, height 80mm, bottom thickness 20 mm) made of alumina fibers, and the alumina fibers were further placed in the insulated potThe heat preservation tank is placed in a quartz tank into which gas can be introduced. The quartz pot was placed in a microwave reactor (MKX-R1C 1B, manufactured by Qingdao Michaelwis instruments Co., ltd.) and subjected to microwave irradiation at 700W for 20 minutes under a nitrogen atmosphere at a flow rate of 100 ml/min. After the microwave irradiation is finished, the obtained chopped carbon fiber is subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption. The specific results are shown in Table 1.
Comparative example 1
The porous composite material described in example 1 was removed, and the carbon fiber composite material was not thermally cracked after microwave irradiation for 10min in the same manner as in example 1. A porous composite must be used to illustrate the method of making the chopped carbon fibers.
Comparative example 2
The carbon fiber composite material of example 1 was replaced with a carbon fiber composite material having 10g of carbon fibers in a mass fraction of 10%, and the other preparation steps were the same as those of example 1. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
Comparative example 3
The carbon fiber composite material of example 1 was replaced with a carbon fiber composite material having a mass fraction of 10g of carbon fibers of 30%, and the other preparation steps were the same as those of example 1. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
As shown in Table 1, the Raman spectrum I of the surface of the chopped carbon fiber prepared in examples 1-3 D /I G Average value is equal to 0.92 or less, and Raman spectrum I of inside of chopped carbon fiber D /I G The standard deviation is less than or equal to 0.027, the pyridinium content at the surface of the chopped carbon fiber is more than or equal to 3%, and the BET specific surface area is more than or equal to 2.2m 2 In comparative examples 2 to 3, the carbon fiber composite material having a carbon fiber mass fraction of less than 65% was used as the raw material to prepare the Raman spectrum I of the chopped carbon fiber surface D /I G Average value is more than or equal to 0.96, and Raman spectrum I of inside of chopped carbon fiber D /I G Standard deviation is more than or equal to 0.061, chopped carbon fiberThe pyridine salt content at the surface of the fiber is less than or equal to 1.8%, and the BET specific surface area is less than or equal to 1.4m 2 Each index of the chopped carbon fibers obtained in comparative examples 2 to 3 was inferior to that of examples 1 to 3.
Comparative example 4
The procedure of example 1 was repeated except that the gas composition used for the microwave irradiation in example 1 was replaced with argon. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
In table 1, as can be seen from comparison of example 1 and comparative example 4, the pyridinium content of the chopped carbon fibers prepared by microwave irradiation under an argon atmosphere was 0.7% much smaller than that of the chopped carbon fibers prepared by microwave irradiation under a nitrogen atmosphere in example 1.
Example 4
Microwave irradiation was performed in the same manner as in example 1 except that the carbon fiber composite material was replaced with the carbon fiber composite material in the preparation example having a mass content of 85%. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
Example 5
Microwave irradiation was performed as in example 1, except that the flow rate of nitrogen was adjusted to 40ml/min. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
Comparative example 5
The carbon fiber composite material of example 1 was replaced with the same raw material as in example 16 of 10g CN 111100322A, namely, a carbon fiber reinforced epoxy resin composite material (carbon fiber content: 64wt% by carbon fiber composite material limited, changzhou city), and the other preparation steps were the same as those of example 1. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
Comparative example 6
Microwave irradiation was performed in the same manner as in example 1, except that the carbon fiber composite material was replaced with the carbon fiber composite material in the preparation example having a mass content of 64%. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
In Table 1, the Raman spectra I of the surfaces of the chopped carbon fibers prepared in comparative example 5 and comparative example 6 D /I G Average value is more than or equal to 0.95, and Raman spectrum I of inside of chopped carbon fiber D /I G The standard deviation is more than or equal to 0.048, the pyridinium content at the surface of the chopped carbon fiber is less than or equal to 1.8 percent, and the BET specific surface area is less than or equal to 1.7m 2 /g。
Comparative example 7
Microwave irradiation was performed as in example 1, except that the porous composite material was replaced with a conventional silicon carbide fiberboard (average pore size 100 μm, porosity 80%, jinan Dragon thermal ceramic Co., ltd.).
In Table 1, the Raman spectrum I of the surface of the chopped carbon fiber prepared in comparative example 7 D /I G Average value of 0.98, raman spectrum I of inside of chopped carbon fiber D /I G Standard deviation of 0.071, pyridinium content of 1.5% at the surface of chopped carbon fiber, BET specific surface area of 1.3m 2 And/g. The obtained chopped carbon fibers were subjected to Raman spectrum surface scanning, X-ray photoelectron spectroscopy analysis and BET adsorption, and specific results are shown in Table 1.
Example 6
Microwave irradiation was performed in the same manner as in example 1 except that the microwave irradiation time was changed to 7min.
In Table 1, comparison of example 1 and example 6 shows that the surface of the chopped carbon fiber prepared in example 6 has a Raman spectrum I D /I G Average value (0.93) and Raman spectrum I of the inside of the chopped carbon fiber D /I G The standard deviation (0.042) was greater than that of example 1, the pyridine salt content (2.7%) at the surface of the chopped carbon fiber was less than that of example 1, and the BET specific surface area (1.8 m 2 /g) is less than example 1.
TABLE 1
Preparation of a chopped carbon fiber modified polymer composite material:
example 7
10g of the chopped carbon fibers prepared in example 1 and 50g of nylon resin (YH 800) were dried and dehydrated in a forced air oven for 12 hours. After drying and dehydration are completed, the recovered carbon fiber and nylon 6 are mixed in a ratio of 1: and 5, mixing the materials according to the mass ratio, adding the mixture into a double-screw extruder for extrusion and pelleting, wherein the temperature of the double-screw extruder during extrusion is 280 ℃, and the extrusion speed is 50rpm. The extruded chopped carbon fiber/nylon 6 pellets were injection molded into a bend test specimen using an injection molding machine at an injection temperature of 320 ℃. The flexural modulus and flexural strength of the injection molded chopped carbon fiber modified nylon 6 composite were characterized using a universal tensile tester, and the results are summarized in table 2.
Comparative example 8
The other parameters and steps were the same as in example 7 without adding chopped carbon fibers. The flexural modulus and flexural strength of the injection molded chopped carbon fiber modified nylon 6 composite were characterized using a universal tensile tester, and the results are summarized in table 2.
Example 8
10g of the chopped carbon fibers prepared in example 1 were mixed with 100g of bisphenol A type epoxy resin (CYD-128) by three rolls to prepare a suspension dispersion of chopped carbon fibers/epoxy resin. To this dispersion was added 25.2g of p-diaminodiphenylmethane (curing agent), mixed at 90℃for 30 minutes to completely dissolve the p-diaminodiphenylmethane, and defoamed in a vacuum oven at 90℃for 1 hour. Pouring the cured system after the defoaming into a mold, and performing curing reaction by a process of keeping the temperature at 130 ℃ for 2 hours, keeping the temperature at 160 ℃ for 3 hours, keeping the temperature at 180 ℃ for 0.5 hour and finally naturally cooling. The short carbon fiber modified bisphenol A type epoxy resin composite material is prepared after the curing reaction is completed, the flexural modulus and the flexural strength of the material prepared in the embodiment are characterized by using a universal tensile testing machine, and the results are summarized in Table 2.
Comparative example 9
The other parameters and steps were the same as in example 8 without adding chopped carbon fibers. The flexural modulus and flexural strength of the materials prepared in this example were characterized using a universal tensile tester, and the results are summarized in Table 2.
Comparative example 10
The chopped carbon fibers used in example 8 were replaced with 10g of commercial chopped carbon fibers, and the other parameters and steps were the same as those in example 8. The flexural modulus and flexural strength of the materials prepared in this example were characterized using a universal tensile tester, and the results are summarized in Table 2.
Example 9
The chopped carbon fibers of example 5 were used instead, and the other parameters and steps were the same as those of example 8. The flexural modulus and flexural strength of the materials prepared in this example were characterized using a universal tensile tester, and the results are summarized in Table 2.
Comparative example 11
The other parameters and steps were the same as in example 8, except that the chopped carbon fibers in comparative example 3 were used instead. The flexural modulus and flexural strength of the materials prepared in this example were characterized using a universal tensile tester, and the results are summarized in Table 2.
TABLE 2
| Examples or comparative examples | Flexural modulus/GPa | Flexural Strength/MPa |
| Example 7 | 2.7 | 103 |
| Comparative example 8 | 2.1 | 87 |
| Example 8 | 4.4 | 144 |
| Comparative example 9 | 2.8 | 104 |
| Example 9 | 3.9 | 132 |
| Comparative example 10 | 3.8 | 128 |
| Comparative example 11 | 3.5 | 122 |
In Table 2, the flexural modulus and flexural strength of the composites of example 7 and comparative example 8, and example 8 and comparative example 9, respectively, and the comparison of the test results shows that the chopped carbon fibers prepared by the invention can be used as fiber modified fillers to enhance nylon resins and epoxy resins. Comparison of the flexural modulus and flexural strength test results of example 8 and comparative example 10 shows that the chopped carbon fibers prepared by the invention have better reinforcing effect on epoxy resin than commercial chopped fibers, indicating that the chopped carbon fibers prepared by the invention can replace commercial chopped carbon fibers without surface treatment.
The difference in flexural modulus and flexural strength of the resulting composites in example 8, example 9, comparative example 10, comparative example 11 also further illustrate the surface I in the added chopped carbon fibers D /I G Average value, carbon fiber interior I D /I G Standard deviation, pyridine salt content, BET specific surface area, etcUnder the condition of changing comprehensive properties, different chopped carbon fibers have different reinforcing contributions to the epoxy resin as modified fillers. On surface I D /I G Average value, carbon fiber interior I D /I G Under the condition that the comprehensive properties such as standard deviation, pyridinium content and BET specific surface area are better, the chopped carbon fiber has stronger reinforcing effect on the epoxy resin, so that the chopped carbon fiber has stronger reinforcing effect on the polymer when being applied as modified filler.
By adopting the preparation method, the chopped carbon fibers recovered from the composite material can replace commercial chopped carbon fibers without surface treatment, and therefore, the preparation method disclosed by the invention fundamentally solves the problem that the chopped carbon fibers recovered from the composite material are poor in performance, and the obtained chopped carbon fibers are better in performance.
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications which perform the same function.
All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference in their entirety. Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, definitions, will control.
When the specification derives materials, substances, methods, steps, devices, or elements and the like in the word "known to those skilled in the art", "prior art", or the like, such derived objects encompass those conventionally used in the art as the application suggests, but also include those which are not currently commonly used but which would become known in the art to be suitable for similar purposes.
The endpoints of the ranges and any values disclosed in this document are not limited to the precise range or value, and the range or value should be understood to include values approaching the range or value. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein. In the following, the individual technical solutions can in principle be combined with one another to give new technical solutions, which should also be regarded as specifically disclosed herein.
In the context of this specification, any matters or matters not mentioned are directly applicable to those known in the art without modification except as explicitly stated.
Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are all deemed to be part of the original disclosure or original description of the present application, and should not be deemed to be a new matter which has not been disclosed or contemplated herein, unless such combination is clearly unreasonable by those skilled in the art.
Claims (15)
1. A short cut carbon fiber is detected by Raman spectrum, and the Raman spectrum I of the surface of the short cut carbon fiber D /I G The average value is less than or equal to 0.94;
and detecting by adopting an X-ray photoelectron spectrum, wherein the integral area of a C1s peak in the X-ray photoelectron spectrum is taken as 100%, and the content of the pyridinium on the surface of the chopped carbon fiber is more than or equal to 2% by taking the integral area of a fitting peak corresponding to the pyridinium as the integral area.
2. The chopped carbon fiber of claim 1, wherein:
raman spectrum detection is adopted, and Raman spectrum I of the surface of the chopped carbon fiber D /I G An average value of 0.93 or less, preferably 0.92 or less, more preferably 0.88 to 0.92; and/or the number of the groups of groups,
the content of the pyridinium on the surface of the chopped carbon fiber is more than or equal to 2.5%, preferably more than or equal to 3%, more preferably 3% -3.5% by adopting X-ray photoelectron spectroscopy detection, wherein the integral area of a C1s peak in the X-ray photoelectron spectroscopy is taken as 100%, and the integral area of a fitting peak corresponding to the pyridinium.
3. The chopped carbon fiber of claim 1, wherein:
raman spectrum detection is adopted, and Raman spectrum I inside the chopped carbon fiber D /I G The standard deviation is 0.045 or less, preferably 0.035 or less, more preferably 0.03 or less, still more preferably 0.02 to 0.03.
4. The chopped carbon fiber of claim 1, wherein:
the specific surface area of the chopped carbon fiber is more than or equal to 1.8m 2 Preferably 2m or more 2 Preferably 2.2m or more 2 Preferably still, it is 2.2-3m 2 /g; and/or the number of the groups of groups,
the length of the chopped carbon fibers is 50mm or less, preferably 25mm or less, and more preferably 15mm or less.
5. The chopped carbon fiber of any one of claims 1-4, wherein:
the chopped carbon fiber is prepared by the following method:
under flowing nitrogen atmosphere, irradiating the carbon fiber composite material contacted with the porous composite material by microwaves, and initiating self-heating of the carbon fiber composite material by using the porous composite material to crack and remove a polymer matrix in the carbon fiber composite material so as to obtain carbon fibers;
wherein the carbon fiber composite material contains carbon fibers, and the mass content of the carbon fibers in the carbon fiber composite material is more than 65%.
6. A method of making the chopped carbon fiber of any one of claims 1-5, comprising: under flowing nitrogen atmosphere, irradiating the carbon fiber composite material contacted with the porous composite material by microwaves, and initiating self-heating of the carbon fiber composite material by using the porous composite material to crack and remove a polymer matrix in the carbon fiber composite material so as to obtain carbon fibers;
Wherein the carbon fiber composite material contains carbon fibers, and the mass content of the carbon fibers in the carbon fiber composite material is more than 65%.
7. The method of manufacturing according to claim 6, wherein:
the mass content of the carbon fiber in the carbon fiber composite material is 65% -85%; and/or the number of the groups of groups,
the carbon fiber composite material is selected from at least one of the following composite materials which all contain carbon fibers: thermoset carbon fiber composites, thermoplastic carbon fiber composites, and carbon fiber prepregs; and/or the number of the groups of groups,
the length of the carbon fibers in the carbon fiber composite material is less than or equal to 50mm, preferably less than or equal to 25mm, more preferably less than or equal to 15mm; and/or the number of the groups of groups,
the dimensions of the carbon fiber composite material in the x, y and z spatial directions are all less than or equal to 50mm.
8. The method of manufacturing according to claim 6, wherein:
the mass ratio of the carbon fiber composite material to the porous composite material is (0.1-10): 1, preferably (0.2-5): 1, more preferably (0.5-2): 1.
9. the method of manufacturing according to claim 6, wherein:
the porous composite material comprises an inorganic porous skeleton and a carbon material loaded on the inorganic porous skeleton;
Preferably, the carbon material accounts for 0.001% -99% of the total mass of the porous composite material; and/or the inorganic porous skeleton is an inorganic material having a porous structure; preferably, the inorganic porous skeleton has an average pore diameter of 0.01 to 1000 μm; the porosity is 1% -99.99%.
10. The method of manufacturing according to claim 6, wherein:
the conditions of the microwave irradiation include:
the power of the microwave irradiation is 300-2000W, preferably 500-1500W, more preferably 700-1000W; and/or the number of the groups of groups,
the microwave irradiation time is 5 to 120 minutes, preferably 10 to 60 minutes, more preferably 10 to 30 minutes.
11. The method of manufacturing according to claim 9, wherein:
the flow rate of nitrogen in the flowing nitrogen atmosphere is 10 to 1000ml/min, preferably 50 to 500ml/min, more preferably 50 to 200ml/min, relative to 10g of the carbon fiber composite material.
12. Chopped carbon fibers prepared by the preparation method according to any one of claims 6 to 11.
13. Use of the chopped carbon fibers of one of claims 1 to 5 or claim 12 as modified filler in polymer composites.
14. The use according to claim 13, characterized in that:
The polymer matrix in the polymer composite is a thermosetting polymer or a thermoplastic polymer; preferably, the thermosetting polymer is selected from at least one of epoxy resin, phenolic resin, maleic anhydride resin, polyacrylic resin, polyurethane resin, and cycloolefin resin; and/or the thermoplastic polymer is selected from at least one of polyamide resin, polyester resin, polycarbonate resin, polyether ketone resin, polyphenylene sulfide resin, polysulfone resin, polyvinyl chloride resin, polyacrylic resin, polyethylene resin, polypropylene resin, alkyd resin, polystyrene resin, polyimide resin, and ABS resin.
15. Use of the preparation method according to any one of claims 6-11 for recycling carbon fibers in waste carbon fiber composite materials.
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