CN116874237A - Modified carbon fiber reinforced inorganic composite material and preparation method thereof - Google Patents
Modified carbon fiber reinforced inorganic composite material and preparation method thereof Download PDFInfo
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- CN116874237A CN116874237A CN202310811448.0A CN202310811448A CN116874237A CN 116874237 A CN116874237 A CN 116874237A CN 202310811448 A CN202310811448 A CN 202310811448A CN 116874237 A CN116874237 A CN 116874237A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 199
- 229910003471 inorganic composite material Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 153
- 239000004917 carbon fiber Substances 0.000 claims abstract description 153
- 239000004568 cement Substances 0.000 claims abstract description 84
- 239000002002 slurry Substances 0.000 claims abstract description 78
- 238000004513 sizing Methods 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 238000007789 sealing Methods 0.000 claims abstract description 12
- 238000007605 air drying Methods 0.000 claims abstract description 9
- 238000012423 maintenance Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000003638 chemical reducing agent Substances 0.000 claims description 27
- 229910021487 silica fume Inorganic materials 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 229920001169 thermoplastic Polymers 0.000 claims description 14
- 229920001567 vinyl ester resin Polymers 0.000 claims description 14
- 239000003822 epoxy resin Substances 0.000 claims description 12
- 239000010408 film Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229920000647 polyepoxide Polymers 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 150000001721 carbon Chemical class 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- 239000013039 cover film Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 11
- 238000005470 impregnation Methods 0.000 abstract description 10
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 238000012360 testing method Methods 0.000 description 35
- 239000002131 composite material Substances 0.000 description 27
- 229910052760 oxygen Inorganic materials 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 239000004567 concrete Substances 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010586 diagram Methods 0.000 description 13
- 238000013001 point bending Methods 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910052729 chemical element Inorganic materials 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 229920002554 vinyl polymer Polymers 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005452 bending Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 5
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000004451 qualitative analysis Methods 0.000 description 4
- 238000004445 quantitative analysis Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910001294 Reinforcing steel Inorganic materials 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The application provides a modified carbon fiber reinforced inorganic composite material and a preparation method thereof, wherein the preparation method comprises the following steps: providing a cement-based slurry; providing a carbon fiber bundle with a sizing agent on the surface, placing cement-based slurry in a slurry tank, and alternately passing the carbon fiber bundle up and down through a roller in the slurry tank to obtain a carbon fiber bundle impregnated with the cement-based slurry; the outlet end of the slurry tank is provided with a conical nozzle; passing the carbon fiber bundles impregnated with the cement-based slurry through a conical nozzle to form rod-shaped carbon fibers; and vertically hanging the rod-shaped carbon fibers in air for air drying, covering the carbon fibers with a film for constant temperature maintenance after the carbon fibers are hardened into carbon fiber rods, and then placing the carbon fiber rods into a sealing bag for constant temperature maintenance to obtain the modified carbon fiber reinforced inorganic composite material. The application can effectively improve the combination degree of the carbon fiber and the cement impregnated matrix and improve the impregnation effect of the cement coating.
Description
Technical Field
The application relates to the technical field of carbon fiber composite materials, in particular to a modified carbon fiber reinforced inorganic composite material and a preparation method thereof.
Background
The carbon fiber is mainly composed of carbon atoms and has the advantages of high strength, high rigidity, high chemical resistance, high temperature resistance, low thermal expansion and the like. Unlike traditional polymer impregnated carbon fiber composite material, the superfine cement impregnated carbon fiber composite material is a novel concrete reinforcement material, has the advantages of high tensile strength, light weight, high strength, corrosion resistance, high temperature resistance and the like, and has wide application prospects in the fields of building reinforcement, building light-weight thin-shell building components, building complex building shapes and the like.
However, the adhesion between the surface of the pure carbon fiber and the cement matrix is poor, and the hydrophobic nature of the carbon fiber material itself makes the impregnation process of the cement-based slurry extremely difficult. Therefore, in order to solve the problem of interfacial bonding of cement-impregnated carbon fiber composite materials, it is necessary to study a modified carbon fiber-reinforced inorganic composite material.
Disclosure of Invention
Aiming at the defects in the prior art, the application aims to provide a modified carbon fiber reinforced inorganic composite material and a preparation method thereof.
According to an aspect of the present application, there is provided a method for preparing a modified carbon fiber reinforced inorganic composite material, comprising:
providing a cement-based slurry;
providing a carbon fiber bundle, wherein a sizing agent is arranged on the surface of the carbon fiber bundle, the cement-based slurry is contained in a slurry tank, and the carbon fiber bundle passes through a roller in the slurry tank alternately up and down to obtain the carbon fiber bundle impregnated with the cement-based slurry; the outlet end of the slurry tank is provided with a conical nozzle, and the large opening end of the conical nozzle is close to the slurry tank; passing the carbon fiber bundles impregnated with the cement-based slurry through the conical nozzle, and forming rod-shaped carbon fibers under the action of a drawing force;
and vertically hanging the rod-shaped carbon fibers in air for air drying, covering a film for constant temperature maintenance after the rod-shaped carbon fibers are hardened into carbon fiber rods, and then placing the carbon fiber rods into a sealing bag for constant temperature maintenance to obtain the modified carbon fiber reinforced inorganic composite material.
Optionally, the providing a cement-based slurry includes:
sequentially adding water, an aqueous solution of silica fume and a first water reducing agent, mixing and stirring to disperse the aqueous solution of silica fume to obtain the solution of silica fume;
then slowly mixing the superfine cement and the superfine blast furnace slag, continuously stirring, and then adding a water reducing agent II to uniformly disperse the superfine cement and the superfine blast furnace slag in the silica fume solution to form mixed slurry;
and uniformly stirring the mixed slurry to obtain cement-based slurry.
Optionally, water, silica fume aqueous solution and water reducer I are sequentially added for mixing and stirring, wherein: 23-25 parts of silica fume water solution, 0.9-1.5 parts of water reducer and 22-23 parts of water.
Optionally, the superfine cement and the superfine blast furnace slag are slowly mixed and continuously stirred, and then the water reducer II is added, wherein: 23-25 parts of superfine cement, 23-25 parts of superfine blast furnace slag and 1.3-1.8 parts of water reducer II.
Optionally, the mixing slurry is stirred uniformly, wherein: stirring for 2-5 min at 6000-8000 rpm.
Optionally, the slurry tank has three to five rolls.
Optionally, the surface of the carbon fiber bundle has a sizing agent, wherein: the sizing agent adopts any one of thermoplastic polymer, epoxy resin and vinyl ester.
Optionally, the rod-shaped carbon fiber is vertically hung in air for air drying, wherein: the air drying time is 1-2 hours.
Optionally, the covering film is subjected to constant temperature curing, and then is put into a sealing bag for constant temperature curing, wherein: covering the film, and maintaining the film for 3 to 7 days at the constant temperature of 20 to 30 ℃; and maintaining the mixture in a sealed bag at a constant temperature of 20-30 ℃ for 33-43 days.
According to another aspect of the application, a modified carbon fiber reinforced inorganic composite material is provided, and the modified carbon fiber reinforced inorganic composite material is prepared by the preparation method of the modified carbon fiber reinforced inorganic composite material.
Compared with the prior art, the application has at least one of the following beneficial effects:
1. according to the modified carbon fiber reinforced inorganic composite material and the preparation method thereof, the carbon fiber bundles with the sizing agent on the surfaces can be used, so that the combination degree of carbon fibers and a cement impregnation matrix can be effectively improved, and the impregnation effect of a cement coating can be improved.
2. The modified carbon fiber reinforced inorganic composite material provided by the application has the advantages of simple formula, high mechanization degree of the preparation method and contribution to automatic production, thereby improving the preparation efficiency of carbon fiber concrete and further popularizing the application of the carbon fiber concrete material.
3. According to the modified carbon fiber reinforced inorganic composite material and the preparation method thereof, the sizing agent coating on the surface of the carbon fiber bundle has a good modification effect on a carbon fiber interface, the mechanical property of the modified carbon fiber reinforced inorganic composite material can be optimized, and the problem of poor dipping effect of the cement coating is solved. The modified carbon fiber reinforced inorganic composite material prepared by the method has excellent bending strength and corrosion resistance, is hopeful to replace reinforcing steel bars, and becomes one of main materials in the future building field.
Drawings
Other features, objects and advantages of the present application will become more apparent upon reading of the detailed description of non-limiting embodiments, given with reference to the accompanying drawings in which:
FIG. 1 is a schematic diagram of a slurry tank in example 1 of the present application; in fig. 1: 1 is a slurry tank, 2 is a roller, and 3 is a conical nozzle;
FIG. 2 is a schematic diagram showing the morphology of the modified carbon fiber reinforced inorganic composite product of example 1 of the present application;
FIG. 3 is a schematic diagram of a three-point bending test structure in example 1 of the present application;
FIG. 4 is a carbon element valence diagram of a modified carbon fiber reinforced inorganic composite treated with a thermoplastic polymer in example 1 of the present application;
FIG. 5 is a diagram showing the valence of oxygen element of the modified carbon fiber reinforced inorganic composite material treated with thermoplastic polymer in example 1 of the present application;
FIG. 6 is a carbon element valence diagram of an epoxy resin treated modified carbon fiber reinforced inorganic composite of example 2 of the present application;
FIG. 7 is a graph of oxygen valence of an epoxy resin treated modified carbon fiber reinforced inorganic composite material in example 2 of the present application;
FIG. 8 is a carbon element valence diagram of a modified carbon fiber reinforced inorganic composite treated with vinyl ester in example 3 of the present application;
FIG. 9 is a graph showing the valence of oxygen in the modified carbon fiber reinforced inorganic composite material treated with vinyl ester in example 3 of the present application.
FIG. 10 is a carbon element valence diagram of a modified carbon fiber reinforced inorganic composite without sizing treatment in a comparative example of the present application;
FIG. 11 is a graph showing the valence of oxygen element of the modified carbon fiber reinforced inorganic composite without the sizing agent treatment in the comparative example of the present application.
Detailed Description
The present application will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present application, but are not intended to limit the application in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present application.
The embodiment of the application provides a preparation method of a modified carbon fiber reinforced inorganic composite material, which comprises the following steps:
s1, providing cement-based slurry;
s2, providing a carbon fiber bundle, wherein a sizing agent is arranged on the surface of the carbon fiber bundle, cement-based slurry is contained in a slurry tank, and the carbon fiber bundle alternately passes through a roller in the slurry tank up and down to obtain a carbon fiber bundle impregnated with the cement-based slurry; the outlet end of the slurry tank is provided with a conical nozzle, and the large opening end of the conical nozzle is close to the slurry tank; passing the carbon fiber bundles impregnated with the cement-based slurry through a conical nozzle, and forming rod-shaped carbon fibers under the action of a drawing force;
s3, vertically hanging the rod-shaped carbon fibers in air for air drying, covering the carbon fibers to form carbon fiber rods after the carbon fiber rods are hardened, maintaining the carbon fiber rods at constant temperature, and then placing the carbon fiber rods in a sealing bag for maintaining the carbon fiber rods at constant temperature to obtain the modified carbon fiber reinforced inorganic composite material.
The cement-based slurry in the step S1 is used for impregnating the carbon fiber, and comprises the following components in parts by weight: 23 to 25 parts of superfine cement, 23 to 25 parts of superfine blast furnace slag, 23 to 25 parts of silica fume aqueous solution, 0.9 to 1.5 parts of water reducer I, 1.3 to 1.8 parts of water reducer II and 22 to 23 parts of water; the first water reducing agent and the second water reducing agent can be the same substances. In some embodiments, a cement-based slurry is provided comprising the steps of: sequentially adding water, an aqueous solution of silica fume and a first water reducing agent, mixing and stirring, and fully dispersing micron silicon particles in the aqueous solution of silica fume by using the first water reducing agent to disperse the aqueous solution of silica fume to obtain the aqueous solution of silica fume; then slowly mixing the superfine cement and the superfine blast furnace slag, continuously stirring, adding a water reducing agent II, and fully dispersing the superfine cement and the superfine blast furnace slag particles by using the water reducing agent II to uniformly disperse the superfine cement and the superfine blast furnace slag in the silica fume solution to form mixed slurry; and uniformly stirring the mixed slurry to obtain cement-based slurry.
In some embodiments, water, an aqueous solution of silica fume and a first water reducing agent are added in sequence for mixing and stirring, wherein: 23-25 parts of silica fume water solution, 0.9-1.5 parts of water reducer and 22-23 parts of water.
In some embodiments, ultra-fine cement and ultra-fine blast furnace slag are slowly incorporated and continuously stirred, followed by the addition of a water reducer II, wherein: 23-25 parts of superfine cement, 23-25 parts of superfine blast furnace slag and 1.3-1.8 parts of water reducer II. Preferably, the average particle diameter of the ultra-fine cement and the ultra-fine blast furnace slag is 5 μm or less. The interval between the carbon fiber filaments is below 10 microns, and the superfine cement and superfine blast furnace slag use average particle size below 5 microns, so that solid particles of the cement-based suspension can pass through the outermost carbon fibers and enter the inside of the carbon fiber multifilament.
Because of the difficult stirring of the superfine cement and the superfine blast furnace slag, the solid particles cannot be uniformly dispersed by low-speed stirring. In some embodiments, the mixed slurry is stirred uniformly, wherein: stirring for 2-5 min at 6000-8000 rpm to disperse the cement-base slurry particles effectively for homogeneous impregnation of carbon fiber.
In the above embodiment, if the number of rolls in the slurry tank is too small, the carbon fiber bundle impregnation effect is poor; if the number of rollers is too large, the resistance to the carbon fiber bundle is increased, and the carbon fiber bundle is easily damaged, preferably, the slurry tank in the step S2 has three to five rollers, so that good impregnation effect can be realized and the carbon fiber bundle is not damaged.
In some embodiments, the sizing agent on the surface of the carbon fiber bundles adopts any one of thermoplastic polymer, epoxy resin and vinyl ester, respectively, so as to improve the hydrophilicity of the carbon fibers.
In some embodiments, in step S4, the air drying time is 1 to 2 hours, so that the strength of the carbon fiber reinforced inorganic composite material satisfies the movement requirement, and is not damaged during the movement.
In the embodiment, because the carbon fiber reinforced inorganic composite material just produced is longer and has lower bending strength, the hardness of the carbon fiber reinforced inorganic composite material can be increased by curing the cover film, the carbon fiber reinforced inorganic composite material is cured in the sealing bag after cutting after the cutting hardness requirement is met, the space for sealing and curing can be reduced, and the problems that the hydration process of the cement-based material is influenced and the bending strength of the carbon fiber reinforced inorganic composite material is reduced due to excessive volatilization of water in the cement matrix are avoided. Preferably, the covering film is maintained for 3 to 7 days at a constant temperature of 20 to 30 ℃; maintaining the cement-based material in a sealed bag at a constant temperature of 20-30 ℃ for 33-43 days to enable the cement-based material to be hydrated rapidly and meet the strength requirement.
Another embodiment of the present application provides a modified carbon fiber reinforced inorganic composite material, which is prepared by the preparation method of the modified carbon fiber reinforced inorganic composite material. According to the modified carbon fiber reinforced inorganic composite material, the carbon fiber bundles with sizing agents on the surfaces can be used, so that the combination degree of carbon fibers and a cement impregnation matrix can be effectively improved, and the impregnation effect of a cement coating is improved; thereby solving the problem of insufficient strength of the carbon fiber composite material caused by hydrophobic carbon fiber surface and the problem of difficult mineral coating impregnation process. The modified carbon fiber reinforced inorganic composite material provided by the embodiment of the application has the advantages of simple formula, high mechanical degree of the preparation method and contribution to automatic production, so that the preparation efficiency of the carbon fiber concrete is improved, and the application of the carbon fiber concrete material is further promoted.
The technical scheme of the application is further described in the following specific examples and comparative examples.
Example 1
The preparation method of the modified carbon fiber reinforced inorganic composite material provided by the embodiment comprises the following steps:
step 1, preparing cement-based slurry
The preparation method comprises the steps of firstly preparing materials required for preparing cement-based slurry, wherein the materials comprise the following components in parts by weight: 25 parts of superfine cement, 25 parts of superfine blast furnace slag, 25 parts of silica fume water solution, 0.9 part of a water reducer I, 1.3 parts of a water reducer II and 23 parts of water. The cement-based slurry formulation is shown in table 1.
Table 1 cement-based slurry formulation
Firstly, mixing and stirring the silica fume aqueous solution, a water reducing agent and water to disperse the silica fume aqueous solution; then slowly mixing the superfine cement and the superfine blast furnace slag and continuously stirring to uniformly disperse the superfine cement and the superfine blast furnace slag in the silica fume solution to form slurry; finally, the mixed slurry is stirred for 2-5 minutes at 6000-8000 rpm, and the cement-based slurry used for impregnating the carbon fiber is obtained.
Step 2, preparing the modified carbon fiber reinforced inorganic composite material
Providing a carbon fiber bundle, wherein the surface of the carbon fiber bundle is provided with a thermoplastic polymer sizing agent, and the cement-based slurry for impregnating the carbon fibers is contained in a slurry tank 1, and the schematic structure of the slurry tank 1 is shown in fig. 1; five rolls 2 are provided in the slurry tank 1, and carbon fiber bundles alternately pass through the rolls 2 up and down. The outlet end of the slurry tank is provided with a conical nozzle 3, the large opening end of the conical nozzle 3 is close to the slurry tank 1, and the carbon fiber bundles pass through the conical nozzle 3 at the outlet end of the slurry tank and form rod-shaped carbon fibers after the action of drawing force;
finally, the impregnated carbon fiber bundles are vertically hung in the air for air drying for 2 hours, after the impregnated carbon fiber bundles are hardened into carbon fiber rods, the carbon fiber bundles are covered with a film for maintaining the carbon fiber bundles at the constant temperature of 20 ℃ for 7 days, and then the carbon fiber bundles are placed in a sealing bag for maintaining the carbon fiber bundles at the constant temperature of 20 ℃ for 33 days, so that the modified carbon fiber reinforced inorganic composite material is obtained, and the characterization result of an electron microscope is shown in figure 2.
After curing, a three-point bending test is performed, a schematic diagram of the three-point bending test is shown in fig. 3, 15 test pieces with the same length are obtained by cutting the modified carbon fiber reinforced inorganic composite material, and three-point bending test data of the modified carbon fiber reinforced inorganic composite material treated by the thermoplastic polymer sizing agent are shown in table 2.
Table 2 three point bend test data for thermoplastic polymer treated modified carbon fiber reinforced inorganic composites
In the production process of the modified carbon fiber reinforced inorganic composite material, the diameter of each test piece is different due to the discrete shape of the test piece, and the test piece cannot be a standard circular section, so that the bending strength and the breaking energy calculated by the three-point bending test are different.
Further, XPS test was performed on the modified carbon fiber reinforced inorganic composite material treated with the thermoplastic polymer, and qualitative and quantitative analysis of chemical elements and valence states of the chemical elements are shown in table 3, and corresponding valence state diagrams are shown in fig. 4 and 5, respectively.
TABLE 3 surface chemistry elements and valence State Table of thermoplastic Polymer treated modified carbon fiber reinforced inorganic composite Material
Example 2
The preparation method of the modified carbon fiber reinforced inorganic composite material provided by the embodiment comprises the following steps:
step 1, preparing cement-based slurry, wherein the concrete steps and the concrete processes are the same as in example 1;
step 2, preparing the modified carbon fiber reinforced inorganic composite material
Providing a carbon fiber bundle, wherein the surface of the carbon fiber bundle is provided with an epoxy resin sizing agent; the cement-based slurry for impregnating the carbon fibers is placed in a slurry tank, five rollers are arranged in the slurry tank, and carbon fiber bundles alternately pass through the rollers up and down. The outlet end of the slurry tank is provided with a conical nozzle, and the carbon fiber bundles pass through the conical nozzle at the outlet end of the slurry tank and form rod-shaped carbon fibers after the action of drawing force;
and finally, vertically hanging the impregnated carbon fiber bundles in air for 2 hours, covering a film for maintaining at a constant temperature of 20 ℃ for 7 days after the impregnated carbon fiber bundles are hardened into carbon fiber rods, and then placing the carbon fiber bundles in a sealing bag for maintaining at a constant temperature of 20 ℃ for 33 days.
After curing, a three-point bending test was performed to obtain 11 test pieces of the same length by cutting the modified carbon fiber-reinforced inorganic composite material, and three-point bending test data of the modified carbon fiber-reinforced inorganic composite material treated with the epoxy resin sizing agent are shown in table 4.
Table 4 three point bend test data for epoxy resin treated modified carbon fiber reinforced inorganic composites
| Test piece numbering | Flexural Strength (MPa) | Breaking energy (kN/m) |
| Epoxy resin-01 | 377.02 | 23.63 |
| Epoxy resin-02 | 478.25 | 35.65 |
| Epoxy resin-03 | 478.37 | 30.46 |
| Epoxy resin-04 | 288.67 | 21.81 |
| Epoxy resin-05 | 383.47 | 40.10 |
| Epoxy resin-06 | 478.82 | 39.73 |
| Epoxy resin-07 | 400.18 | 48.34 |
| Epoxy resin-08 | 288.57 | 21.04 |
| Epoxy resin-09 | 331.94 | 28.58 |
| Epoxy resin-10 | 430.08 | 55.15 |
| Epoxy resin-11 | 314.82 | 34.70 |
| Average value of | 386.38 | 34.47 |
Further, XPS test was performed on the modified carbon fiber reinforced inorganic composite material treated with the epoxy resin, and qualitative and quantitative analysis of chemical elements and valence states of the chemical elements are shown in table 5, and corresponding valence state diagrams are shown in fig. 6 and fig. 7, respectively.
TABLE 5 epoxy resin treated modified carbon fiber reinforced inorganic composite surface chemistry elements and valence states
Example 3
The preparation method of the modified carbon fiber reinforced inorganic composite material provided by the embodiment comprises the following steps:
step 1, preparing cement-based slurry, wherein the concrete steps and the concrete processes are the same as in example 1;
step 2, preparing the modified carbon fiber reinforced inorganic composite material
Providing carbon fiber bundles, wherein the surfaces of the carbon fiber bundles are provided with vinyl ester sizing agents; the cement-based slurry for impregnating the carbon fibers is placed in a slurry tank, five rollers are arranged in the slurry tank, and carbon fiber bundles alternately pass through the rollers up and down. The outlet end of the slurry tank is provided with a conical nozzle, and the carbon fiber bundles pass through the conical nozzle at the outlet end of the slurry tank and form rod-shaped carbon fibers after the action of drawing force;
and finally, vertically hanging the impregnated carbon fiber bundles in air for 2 hours, covering a film for maintaining at a constant temperature of 20 ℃ for 7 days after the impregnated carbon fiber bundles are hardened into carbon fiber rods, and then placing the carbon fiber bundles in a sealing bag for maintaining at a constant temperature of 20 ℃ for 33 days.
After curing, a three-point bending test was performed to obtain 9 test pieces of the same length by cutting the modified carbon fiber-reinforced inorganic composite material, and three-point bending test data of the modified carbon fiber-reinforced inorganic composite material treated with the vinyl ester sizing agent are shown in table 6.
TABLE 6 three-point bend test data sheet for vinyl ester treated modified carbon fiber reinforced inorganic composites
| Test piece numbering | Flexural Strength (MPa) | Breaking energy (kN/m) |
| Vinyl ester-01 | 184.00 | 20.17 |
| Vinyl ester-02 | 239.43 | 30.31 |
| Vinyl ester-03 | 282.18 | 37.61 |
| Vinyl ester-04 | 229.52 | 21.62 |
| Vinyl ester-05 | 339.18 | 23.80 |
| Vinyl ester-06 | 370.39 | 34.38 |
| Vinyl ester-07 | 243.54 | 19.57 |
| Vinyl ester-08 | 184.39 | 26.50 |
| Vinyl ester-09 | 284.65 | 22.44 |
| Average value of | 261.92 | 26.27 |
Further, XPS test was performed on the modified carbon fiber reinforced inorganic composite material treated with vinyl ester, and qualitative and quantitative analysis of chemical elements and valence states of the chemical elements are shown in table 7, and corresponding valence state diagrams are shown in fig. 8 and fig. 9, respectively.
TABLE 7 surface chemistry elements and valence states of vinyl ester treated modified carbon fiber reinforced inorganic composites
Comparative example 1
Step 1: preparing cement-based slurry, wherein the concrete steps and the process are the same as in example 1;
step 2: preparation of modified carbon fiber reinforced inorganic composite material
Providing a carbon fiber bundle with no sizing agent on the surface, placing the cement-based slurry for impregnating the carbon fibers in a slurry tank, wherein five rollers are arranged in the slurry tank, and the carbon fiber bundle passes through the rollers alternately up and down. The outlet end of the slurry tank is provided with a conical nozzle, and the carbon fiber bundles pass through the conical nozzle at the outlet end of the slurry tank and form rod-shaped carbon fibers after the action of drawing force;
and finally, vertically hanging the impregnated carbon fiber bundles in air for 2 hours, covering a film for maintaining at a constant temperature of 20 ℃ for 7 days after the impregnated carbon fiber bundles are hardened into carbon fiber rods, and then placing the carbon fiber bundles in a sealing bag for maintaining at a constant temperature of 20 ℃ for 33 days.
After curing, a three-point bending test was performed, and 15 test pieces of the same length were obtained by cutting the modified carbon fiber reinforced inorganic composite material treated with the sizing agent, and three-point bending test data of the modified carbon fiber reinforced inorganic composite material without the sizing agent are shown in table 8.
TABLE 8 three-point flexural test data for modified carbon fiber reinforced inorganic composites without sizing treatment
Further, XPS test was performed on the modified carbon fiber reinforced inorganic composite material treated with no sizing agent, and qualitative and quantitative analysis was performed on the chemical elements and the valence states of the chemical elements on the surface of the sample, as shown in table 9, and the corresponding valence state diagrams are shown in fig. 10 and 11, respectively.
TABLE 9 modified carbon fiber reinforced inorganic composite surface chemistry elements and valence states without sizing agent treatment
Since C-C is the most stable and hardly reacts with concrete, the higher the C-C bond content, the poorer the adhesion of the carbon fiber to concrete. And C-O, C = O, OC =o can respectively form hydrogen bonds, chemical bonds and ionic bonds with concrete, so that the adhesion between the carbon fiber and the concrete is greatly improved.
Comparative example 1 differs from examples 1 to 3 in that the sizing treatment was not performed on the carbon fiber surface with the sizing agent, whereas examples 1 to 3 were each performed with the thermoplastic polymer, the epoxy resin, and the vinyl ester as the sizing agent.
The modified carbon fiber reinforced inorganic composite materials obtained in examples 1 to 3 and the composite material obtained in comparative example 1 were subjected to comparative analysis in terms of mechanical properties, chemical elements, and valence-state ratio principles, respectively.
From Table 8, according to the test results of the three-point bending test, comparative example 1 is a sizing-agent-free carbon fiber composite material having a flexural strength average value of 166.41MPa and a breaking energy average value of 11.97kN/m.
The modified carbon fiber-reinforced inorganic composite materials of examples 1 to 3 were improved in both flexural strength and fracture energy to different extents compared to comparative example 1. Of these, the flexural strength and the breaking energy were the highest in example 2.
According to the XPS test results of table 9, the composite of comparative example 1 has a carbon element content of 93.27%, wherein c—c is 75.8%, c—o is 11.6%, c=o is 4.0%, oc=o is 6.5%, pi-pi is 2.1%; oxygen element 4.43%, wherein c=o 22.7%, c—o 60.5%, and-OH 16.8%; the nitrogen element accounts for 2.30 percent. In comparative example 1, the carbon fiber without sizing agent had the largest number of surface carbon atoms relative to the carbon fiber modified with other sizing agents, while the carbon fiber without sizing agent had the smallest number of surface oxygen atoms relative to the carbon fiber modified with other sizing agents. The results show that the sizing-free carbon fiber surface has the least number of oxygen-containing functional groups. Since C-C is most stable and almost impossible to chemically bond to the concrete surface, the sizing-free carbon fiber presents an inert hydrophobic surface and the surrounding cement matrix cannot form an effective chemical bond, thus reducing flexural strength and fracture energy.
According to the XPS test results of table 3, the modified carbon fiber reinforced inorganic composite of example 1 has a carbon element content of 85.70%, wherein c—c is 77.1%, c—o is 7.5%, c=o is 10.9%, oc=o is 3.3%, pi-pi is 1.2%; oxygen element accounts for 12.38%, wherein C=O accounts for 34.1%, C-O accounts for 11.1%, and-OH accounts for 54.8%; the nitrogen element accounts for 1.92 percent. The composite material of example 1 has a smaller content of carbon element and a larger content of oxygen element than comparative example 1, and thus the flexural strength and breaking energy of example 1 are both greater than those of comparative example. The reason is that hydroxyl groups (C-O) on the surface of the carbon fiber can form hydrogen bonds with hydration products in the cement matrix, aldehyde groups (c=o) on the surface of the carbon fiber can form chemical bonds with the surrounding cement matrix, and meanwhile, the surface of the carbon fiber contains a small amount of carboxyl groups (oc=o) and can form ionic bonds with calcium elements in the surrounding cement matrix, so that the bonding degree of the carbon fiber and the concrete is greatly improved. The C-C content of example 1 was smaller than that of comparative example, so that the flexural strength and breaking energy of final example 1 were both greater than those of comparative example 1.
According to the XPS test results of table 7, the modified carbon fiber reinforced inorganic composite material of example 3 has a carbon element content of 80.05%, wherein c—c is 55.0%, c—o is 22.1%, c=o is 20.4%, oc=o is 2.1%, pi-pi is 0.4%; oxygen content 19.95%, wherein C=O 1.5%, C-O90.3%, and-OH 8.2%. The composite material of example 3 has a smaller content of carbon element and a larger content of oxygen element than comparative example 1, and thus the flexural strength and breaking energy of example 3 are both greater than those of comparative example. The reason is that hydroxyl groups (C-O) on the surface of the carbon fiber can form hydrogen bonds with hydration products in the cement matrix, aldehyde groups (c=o) on the surface of the carbon fiber can form chemical bonds with the surrounding cement matrix, and meanwhile, the surface of the carbon fiber contains a small amount of carboxyl groups (oc=o) and can form ionic bonds with calcium elements in the surrounding cement matrix, so that the bonding degree of the carbon fiber and the concrete is greatly improved.
According to the XPS test results of table 5, the modified carbon fiber reinforced inorganic composite of example 2 has a carbon element content of 76.78%, wherein c—c is 45.5%, c—o is 8.0%, c=o is 45.0%, oc=o is 1.3%, pi-pi is 0.2%; oxygen element accounting for 22.79 percent, wherein C=O accounts for 2.0 percent, C-O accounts for 89.5 percent, and-OH accounts for 8.5 percent; the nitrogen element accounts for 0.43 percent. Compared with example 1 and example 3, the carbon element content is the least, the oxygen element content is the greatest, and the functional group number is the greatest in example 2, wherein hydroxyl (C-O) groups on the surface of the carbon fiber can form hydrogen bonds with hydration products in the cement matrix, while aldehyde (c=o) groups on the surface of the carbon fiber are the most, can form chemical bonds with the surrounding cement matrix, and greatly increases the hydrophilicity of the surface of the carbon fiber. At the same time, the carbon fiber surface in example 2 also found a small amount of carboxyl groups (oc=o), which can form ionic bonds with the calcium element in the surrounding cement matrix. Therefore, the modified carbon fiber reinforced inorganic composite material of example 2 is best in bonding degree, and is maximum in flexural strength and fracture energy.
According to the three-point bending test, the flexural strength of example 3 is smaller than that of example 1, and the breaking energy of example 3 is smaller than that of example 1. However, example 3 has a greater oxygen content than example 1, and example 3 contains more oxygen-containing functional groups than example 1. This result is probably because the oxygen-containing functional groups in the thermoplastic polymer in example 1 are more reactive, while the oxygen-containing functional groups in the vinyl ester in example 3 are less reactive. Thus, example 1 can form more chemical bonds with the surrounding cement matrix than example 3, thereby promoting an increase in flexural strength and fracture energy of the carbon fiber reinforced inorganic composite.
The experiment shows that the sizing agent adopted in the embodiment of the application has the function of enhancing the interfacial bonding between the carbon fiber and the surrounding cement matrix. Among them, the epoxy resin sizing agent in example 2 has the most obvious oxygen content and activity enhancing effect on the surface of the carbon fiber, and is most suitable for producing carbon fiber reinforced cement impregnated composite materials. The thermoplastic polymer sizing agent is slightly better than the vinyl ester sizing agent, and both the thermoplastic polymer sizing agent and the vinyl ester sizing agent can have obvious enhancement effect on the bending strength of the carbon fiber reinforced inorganic composite material.
According to the modified carbon fiber reinforced inorganic composite material and the preparation method thereof, the sizing agent coating is adopted, so that the interface has a good modification effect, the mechanical property of the modified carbon fiber reinforced inorganic composite material can be improved, and the problem of poor dipping effect of the cement coating is solved. The modified carbon fiber reinforced inorganic composite material in the embodiment of the application has excellent bending strength and corrosion resistance, is hopeful to replace reinforcing steel bars, and becomes one of main materials in the future building field.
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the claims without affecting the spirit of the application. The above-described preferred features may be used in any combination without collision.
Claims (10)
1. The preparation method of the modified carbon fiber reinforced inorganic composite material is characterized by comprising the following steps:
providing a cement-based slurry;
providing a carbon fiber bundle, wherein a sizing agent is arranged on the surface of the carbon fiber bundle, the cement-based slurry is contained in a slurry tank, and the carbon fiber bundle passes through a roller in the slurry tank alternately up and down to obtain the carbon fiber bundle impregnated with the cement-based slurry; the outlet end of the slurry tank is provided with a conical nozzle, and the large opening end of the conical nozzle is close to the slurry tank; passing the carbon fiber bundles impregnated with the cement-based slurry through the conical nozzle, and forming rod-shaped carbon fibers under the action of a drawing force;
and vertically hanging the rod-shaped carbon fibers in air for air drying, covering a film for constant temperature maintenance after the rod-shaped carbon fibers are hardened into carbon fiber rods, and then placing the carbon fiber rods into a sealing bag for constant temperature maintenance to obtain the modified carbon fiber reinforced inorganic composite material.
2. The method of preparing a modified carbon fiber reinforced inorganic composite material according to claim 1, wherein the providing a cement-based slurry comprises:
sequentially adding water, an aqueous solution of silica fume and a first water reducing agent, mixing and stirring to disperse the aqueous solution of silica fume to obtain the solution of silica fume;
then slowly mixing the superfine cement and the superfine blast furnace slag, continuously stirring, and then adding a water reducing agent II to uniformly disperse the superfine cement and the superfine blast furnace slag in the silica fume solution to form mixed slurry;
and uniformly stirring the mixed slurry to obtain cement-based slurry.
3. The method for preparing a modified carbon fiber reinforced inorganic composite material according to claim 2, wherein water, an aqueous solution of silica fume and a water reducing agent are sequentially added to be mixed and stirred, wherein: 23-25 parts of silica fume water solution, 0.9-1.5 parts of water reducer and 22-23 parts of water.
4. The method for preparing a modified carbon fiber reinforced inorganic composite material according to claim 2, wherein the ultra-fine cement and the ultra-fine blast furnace slag are slowly mixed and continuously stirred, and then the water reducing agent II is added, wherein: 23-25 parts of superfine cement, 23-25 parts of superfine blast furnace slag and 1.3-1.8 parts of water reducer II.
5. The method for producing a modified carbon fiber-reinforced inorganic composite material according to claim 2, wherein the mixed slurry is stirred uniformly, wherein: stirring for 2-5 min at 6000-8000 rpm.
6. The method for producing a modified carbon fiber-reinforced inorganic composite material according to claim 1, wherein the slurry tank has three to five rolls.
7. The method for producing a modified carbon fiber-reinforced inorganic composite material according to claim 1, wherein the carbon fiber bundles have a sizing agent on the surfaces thereof, wherein: the sizing agent adopts any one of thermoplastic polymer, epoxy resin and vinyl ester.
8. The method for producing a modified carbon fiber-reinforced inorganic composite material according to claim 1, wherein the rod-shaped carbon fibers are vertically suspended in air and air-dried, wherein: the air drying time is 1-2 hours.
9. The method for preparing a modified carbon fiber reinforced inorganic composite material according to claim 1, wherein the cover film is cured at a constant temperature, and then is put into a sealing bag for curing at a constant temperature, wherein: covering the film, and maintaining the film for 3 to 7 days at the constant temperature of 20 to 30 ℃; and maintaining the mixture in a sealed bag at a constant temperature of 20-30 ℃ for 33-43 days.
10. A modified carbon fiber reinforced inorganic composite material, characterized in that the modified carbon fiber reinforced inorganic composite material is prepared by the preparation method of any one of claims 1-9.
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