CN113831101A - Chopped carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof - Google Patents
Chopped carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof Download PDFInfo
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- CN113831101A CN113831101A CN202111162456.4A CN202111162456A CN113831101A CN 113831101 A CN113831101 A CN 113831101A CN 202111162456 A CN202111162456 A CN 202111162456A CN 113831101 A CN113831101 A CN 113831101A
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- 239000004917 carbon fiber Substances 0.000 title claims abstract description 185
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 173
- 229920000876 geopolymer Polymers 0.000 title claims abstract description 144
- 239000002131 composite material Substances 0.000 title claims abstract description 125
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 92
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 92
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- 239000000843 powder Substances 0.000 claims abstract description 50
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- 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
- C04B28/34—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 containing cold phosphate binders
- C04B28/342—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 containing cold phosphate binders the phosphate binder being present in the starting composition as a mixture of free acid and one or more reactive oxides
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
- C04B14/062—Microsilica, e.g. colloïdal silica
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- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/30—Oxides other than silica
- C04B14/303—Alumina
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- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
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- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/495—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as oligomers or polymers
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/62—Coating or impregnation with organic materials
- C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
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- 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
Abstract
The invention discloses a chopped carbon fiber reinforced phosphate group geopolymer composite material and a preparation method thereof, wherein the preparation method comprises the following steps: preparation of SiO2‑Al2O3Sol precursor, preparing the precursor into gel, drying, calcining the dried gel to obtain SiO2‑Al2O3Active powder; mixing the pretreated chopped carbon fiber with SiO2‑Al2O3Active powder mixing ballGrinding and drying to obtain SiO containing short carbon fiber2‑Al2O3Composite powder; SiO containing chopped carbon fiber2‑Al2O3Adding the composite powder into a phosphoric acid solution and uniformly mixing; injection molding and curing; demolding and maintaining; and (4) carrying out surface treatment by using a silicone resin solution. The prepared composite material is composed of phosphate group geopolymer and chopped carbon fiber dispersed in the phosphate group geopolymer. The composite material has the advantages of ultrahigh ductility, low water absorption, high temperature resistance, low cost and the like, and the preparation method is simple to operate and low in cost.
Description
Technical Field
The invention belongs to the technical field of environment-friendly high-temperature-resistant fiber-reinforced inorganic polymer composite materials, and particularly relates to a short carbon fiber-reinforced phosphate-based geopolymer composite material with ultrahigh ductility and heat resistance and a preparation method thereof.
Background
The geopolymer is a novel environment-friendly high-temperature-resistant inorganic polymer material, and has the advantages of excellent chemical and high-temperature stability, good thermophysical properties, extremely large specific surface area, wide raw material source, low preparation energy consumption cost and the like, so the geopolymer is widely used for binders for civil construction and construction, heat-proof layers for aerospace, electronic packaging materials and the like.
The geopolymer can be divided into an alkali-activated geopolymer and an acid-activated geopolymer according to the excitation form, and compared with the acid-activated geopolymer, the alkali-activated geopolymer is earlier in initial research, more rapid in development, more mature in application and relatively complete in research and development. Acid-based geopolymers, which are relatively slow to develop due to their relatively slow discovery and research initiation time, have some unique advantages in some aspects compared with alkali-activated geopolymers, such as difficulty in weathering cracking, no need of steam curing, superior mechanical and high temperature resistance, less dielectric loss, and the like, and thus are also paid attention and researched by more scholars in more fields. Currently, the existing acid-activated geopolymer research center mainly aims at the research of phosphate-based geopolymers (PBG).
At present, the research work on phosphate group geopolymers at home and abroad is mainly focused on the last 5 to 10 yearsThe research of the literature shows that the mechanical property of the phosphate group geopolymer is not ideal, and particularly in the aspects of bending property, fracture property and the like, the bending strength is generally 5MPa to 10MPa, and the fracture toughness is only 1.0 MPa.m1/2～2.0MPa·m1/2. As such, the poor mechanical properties greatly limit the range of application and the prospects of phosphate-based geopolymers as structural materials. Particularly, when the phosphate-based geopolymer composite material is applied in an environment with high requirements on mechanical properties of the structural material, such as mechanical impact load, cyclic load and the like, the phosphate-based geopolymer composite material needs to be reinforced and toughened, and how to rapidly prepare the phosphate-based geopolymer composite material with excellent properties and simple process is a key problem to be solved urgently.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the chopped carbon fiber reinforced phosphate group geopolymer composite material which has strong mechanical property, high temperature resistance, low cost and environmental protection and the preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme.
A preparation method of a chopped carbon fiber reinforced phosphate group geopolymer composite material comprises the following steps:
(1) preparation of SiO2-Al2O3Sol precursor: mixing SiO2Sol and Al2O3Mixing the sol and the stabilizer to obtain SiO2-Al2O3Sol precursor, Al2O3With SiO2The molar ratio of (A) to (B) is 0.25-1: 1;
(2) and (3) gel drying: SiO obtained in the step (1)2-Al2O3Keeping the sol precursor at a constant temperature to form gel, and continuing to raise the temperature to dry the gel after the gel is solidified;
(3) and (3) calcining: calcining the dried gel obtained in the step (2) to remove organic active ingredients and crystal water in the gel to obtain SiO2-Al2O3Active powder;
(4) pretreatment of the chopped carbon fibers: placing the chopped carbon fibers in vacuum for heat treatment to remove organic glue on the surfaces of the carbon fibers, then soaking and activating the carbon fibers by using a nitric acid solution or hydrogen peroxide, filtering and drying to obtain pretreated chopped carbon fibers;
(5) preparation of SiO containing chopped carbon fibers2-Al2O3Composite powder: mixing the chopped carbon fiber pretreated in the step (4) and the SiO prepared in the step (3)2-Al2O3Mixing and ball-milling active powder, drying the obtained ball-milling slurry after the ball-milling is finished, and obtaining the SiO containing the short carbon fiber2-Al2O3Composite powder;
(6) preparing phosphate group geopolymer precursor slurry: SiO containing chopped carbon fibers in the step (5)2-Al2O3The composite powder and phosphoric acid solution are mixed into phosphate group geopolymer precursor slurry, and the SiO containing the short carbon fiber2-Al2O3SiO in composite powder2With H in the phosphoric acid solution3PO4The molar ratio of (A) to (B) is 0.7-1.5: 1;
(7) and (3) injection molding and curing: pouring the phosphate group geopolymer precursor slurry prepared in the step (6) into a mould, standing and curing;
(8) demolding and maintaining: demolding, preserving heat and maintaining the completely cured short carbon fiber reinforced geopolymer matrix composite material obtained in the step (7);
(9) surface treatment: and (3) putting the composite material subjected to demolding and curing in the step (8) into a silicone resin solution for dipping, taking out and airing after dipping, and performing crosslinking reaction to hydrophobize the surface of the composite material to obtain the chopped carbon fiber reinforced phosphate group geopolymer composite material.
In the preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material, preferably, in the step (1), the SiO is2-Al2O3The solid content of the sol precursor is 25 wt% -45 wt%, and the SiO is2-Al2O3The size of sol particles of the sol precursor is less than or equal to 30mm, and SiO is2The particle diameter of the sol particles is 20 nm-30 nm, Al2O3The particle diameter of the sol particle is 10nm to 30 nm.
Preferably, in the preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material, in the step (1), the stabilizer is polyethylene glycol, the number average molecular weight of the polyethylene glycol is 200, 400 or 600, and the polyethylene glycol and the SiO are mixed together2-Al2O3The mass ratio of the sol precursor is 5-8: 100.
Preferably, in the step (2), the heat preservation temperature is 60-80 ℃, and the heat preservation time is 12-24 hours; the temperature of the dried gel is 100-150 ℃, and the time of the dried gel is 2-6 h.
Preferably, in the step (3), the calcining temperature is 400-800 ℃, and the calcining time is 3-5 hours.
In the above preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material, preferably, in the step (4), the length of the chopped carbon fiber is 5mm to 15mm, and the diameter of the chopped carbon fiber is 5 μm to 7 μm.
Preferably, in the step (4), the heat treatment temperature is 1400-1800 ℃, the heat treatment time is 1-2 h, the heat treatment is performed in a vacuum environment, and the vacuum degree of the vacuum environment is 0-10 Pa.
Preferably, in the step (4), the nitric acid solution is concentrated nitric acid, the concentration of the concentrated nitric acid is 8-10 mol/L, and the time for immersion activation is 5-10 h.
Preferably, in the step (4), the drying temperature is 60-80 ℃, and the drying time is 10-12 hours.
Preferably, in the step (5), the ball milling medium is alcohol, the ball milling time is 5min to 6min, and the ball milling rotation speed is 100 r/min.
Preferably, in the step (5), the drying temperature is 60-70 ℃, and the drying time is 12-24 hours.
In the preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material, in the step (6), the concentration of the phosphoric acid solution is preferably 6-14 mol/L.
Preferably, in the step (7), the standing time is 2-3 h, the curing temperature is 40-80 ℃, and the curing time is 24-48 h.
Preferably, in the step (8), the temperature for heat preservation and maintenance is 60-80 ℃, and the time for heat preservation and maintenance is 7-28 days.
In the method for preparing the chopped carbon fiber reinforced phosphate-based geopolymer composite material, in the step (9), the silicone resin is preferably a low-foaming hydrophobic silicone resin, the low-foaming hydrophobic silicone resin comprises an SR249 series low-foaming hydrophobic silicone resin and/or an MK series low-foaming hydrophobic silicone resin, the solvent of the silicone resin solution is alcohol, and the concentration of the silicone resin solution is 5 wt% to 10 wt%.
Preferably, in the step (9), the impregnation is carried out under atmospheric pressure, the impregnation time is 4-6 hours, and the airing time is 12-24 hours.
Preferably, in the step (9), the temperature of the crosslinking reaction is 100-150 ℃, and the time of the crosslinking reaction is 2-6 h.
As a general technical concept, the invention also provides a chopped carbon fiber reinforced phosphate group geopolymer composite material prepared by the preparation method of the chopped carbon fiber reinforced phosphate group geopolymer composite material.
Preferably, the composite material is composed of chopped carbon fibers and phosphate group geopolymer, the phosphate group geopolymer is used as a substrate, the chopped carbon fibers are used as a reinforcement, and the chopped carbon fibers are dispersed in the phosphate group geopolymer substrate.
Preferably, the chopped carbon fiber reinforced phosphate group geopolymer composite material contains 1-15% of chopped carbon fibers in percentage by volume.
Preferably, the chopped carbon fiber reinforced phosphate-based geopolymer composite material is prepared from Al2O3、SiO2And phosphoric acid, said Al2O3With SiO2The molar ratio of (A) to (B) is 0.25-1: 1, and the SiO is2With PO in phosphoric acid4 3+The molar ratio of (A) to (B) is 0.7-1.5: 1.
Preferably, the porosity of the chopped carbon fiber reinforced phosphate-based geopolymer composite material is 2-10%.
Compared with the prior art, the invention has the advantages that:
1. according to the chopped carbon fiber reinforced phosphoric acid geopolymer composite material, the chopped carbon fibers and the phosphoric acid geopolymer are subjected to synergistic interaction for the first time, so that the chopped carbon fiber reinforced phosphoric acid geopolymer composite material with excellent mechanical properties is obtained. The chopped carbon fibers are utilized to provide excellent mechanical properties, and particularly, the defects of poor mechanical properties of the original phosphate group geopolymer composite material are overcome in the aspect of improving the bending and fracture toughness. Through will cut the even phosphate geological polymer of introducing of carbon fiber, the couplet effect of making full use of cuts the carbon fiber effectively reduces the base member fracture phenomenon that leads to because of environmental change in the maintenance process.
2. The inventionThe chopped carbon fiber reinforced phosphoric acid geopolymer composite material is prepared by using SiO with the particle size of 20 nm-30 nm2Sol and Al with grain size of 10-30 nm2O3Sol, and can obtain precursor SiO with ultrahigh activity2-Al2O3Powder and by conditioning SiO2Sol, Al2O3Sols and H3PO4The ratio of the components can realize the large-range adjustment of the atomic composition and the structural composition of Si, P and Al in the matrix component, thereby obtaining the phosphate group geopolymer with different thermal and mechanical properties.
3. The preparation method of the invention adopts a short-time low-speed ball milling dispersion method of the chopped carbon fibers, can reduce the mechanical damage of the dispersed carbon fibers as much as possible, and fully ensures the dispersion uniformity of the chopped carbon fibers in the phosphate geological polymer matrix, thereby effectively ensuring the excellent uniformity of the mechanical properties.
4. Because certain chemical inertness exists between the carbon fiber and the phosphate group geopolymer (namely, no chemical reaction occurs between the carbon fiber and the phosphate group geopolymer), the interface bonding between the surface of the fiber and the substrate is very weak, so that the substrate and the fiber of the composite material cannot effectively transfer and bear loads, and the mechanical property of the carbon fiber reinforced phosphate group geopolymer composite material is greatly reduced. According to the preparation method, the fiber surface is activated by dipping an activating agent (such as concentrated nitric acid, hydrogen peroxide and the like) with a certain strong oxidizing property, so that the number of C ═ O on the surface of the carbon fiber and the surface roughness of the fiber can be effectively increased, the wettability of the surface of the fiber and the phosphate geopolymer is increased, the interface combination between the carbon fiber and the phosphate geopolymer matrix is well improved, and the mechanical property of the carbon fiber reinforced phosphate geopolymer composite material is improved. The liquid-phase impregnation activation method is adopted to avoid the mechanical property damage to the fibers caused by activation methods such as high-temperature oxidation in the air.
5. In order to reduce unstable changes of force and heat performance in all aspects caused by water absorption of the material after complete curing, the preparation method can form an organic resin coating with the thickness of about tens of nanometers on the surface by adopting the silicone resin with the concentration of 5-10 wt% for subsequent atmospheric pressure impregnation, effectively solves the problems of environmental and time effects caused by storage of the chopped carbon fiber reinforced phosphate geopolymer composite material, and can further improve the mechanical property of the phosphate geopolymer composite material due to good caking property of the organic resin.
In conclusion, the invention starts from the aspects of high-activity precursor powder synthesis, fiber activation, fiber dispersion, injection molding maintenance and the like, provides a set of complete and simple preparation method for preparing the chopped carbon fiber reinforced phosphate geopolymer composite material, and the prepared composite material has excellent mechanical properties because the excellent properties of the carbon fibers are fully exerted in the phosphate geopolymer matrix.
Drawings
FIG. 1 is a flow chart of a process for preparing a chopped carbon fiber reinforced phosphate-based geopolymer composite material according to the present invention.
Fig. 2 is a physical diagram of the chopped carbon fiber reinforced phosphate-based geopolymer composite prepared in example 1 of the present invention.
FIG. 3 is SiO dispersion of chopped carbon fibers in example 1 of the present invention2-Al2O3Electron micrographs of the composite powder.
Fig. 4 is an XRD phase spectrum of the aluminum-silicon gel powder after calcination and activation at different temperatures in example 1 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention. The materials and equipment used in the following examples are commercially available.
Example 1:
the preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material disclosed by the invention comprises the following steps of:
(1) preparation of SiO2-Al2O3Sol precursor: mixing SiO2Sol and Al2O3Sol mixing, SiO2The particle diameter of the sol particles is 20 nm-30 nm, Al2O3The particle size of the sol particles is 10 nm-30 nm, and the electronic grade SiO with the solid phase content of 30 wt% and the sol particle size of less than or equal to 30mm is prepared2-Al2O3Adding PEG400 (polyethylene glycol with the number average molecular weight of 400) into the sol to obtain SiO with fine particle size, high solid content and stability2-Al2O3Sol precursor of SiO2With Al2O3The molar ratio of PEG400 to SiO is 1: 0.52-Al2O3The mass ratio of the sol precursor is 1: 20.
(2) And (3) gel drying: SiO prepared in the step (1)2-Al2O3And (3) transferring the sol precursor into an oven, preserving the heat for 12h at 60 ℃ to form uniform gel, continuing raising the temperature to 120 ℃ after the gel is solidified, preserving the heat for 4h, and further removing free water in the gel.
(3) And (3) calcining: transferring the gel dried in the step (2) to a muffle furnace to calcine for 4h at 750 ℃ to remove a small amount of organic active agent and crystal water in the gel to obtain uniform and pure SiO2-Al2O3And (3) active powder.
(4) Pretreatment of the chopped carbon fibers: placing the chopped carbon fibers with the length of 7mm and the diameter of 5-7 microns at 1400 ℃, carrying out heat treatment for 1h under a vacuum condition with the vacuum degree of 5Pa to remove organic glue on the surfaces of the chopped carbon fibers, then soaking the chopped carbon fibers in 10mol/L concentrated nitric acid for 8h, filtering the chopped carbon fibers after soaking is finished, and further drying at a low temperature of 60 ℃ for 10 h.
(5) Preparation of SiO containing chopped carbon fibers2-Al2O3Composite powder: mixing the chopped carbon fibers pretreated in the step (4) with the SiO formed in the step (3)2-Al2O3Putting the active powder into a ball milling tank together, ball milling for 5min by taking alcohol as a ball milling medium, wherein the ball milling speed is 100r/min, taking out the slurry after the ball milling is finished, and drying at the drying temperature of 60 ℃ for 12h to obtain the geopolymer with high activity and uniformly dispersed short carbon fibersCompound precursor SiO2-Al2O3The composite powder is shown in FIG. 3.
Because the carbon fiber shows poor wettability to an aqueous solvent, if the aqueous solvent is adopted for dispersing the carbon fiber in the ball milling process, the carbon fiber is not uniformly dispersed in the geopolymer, and the dispersion of the geopolymer in performance is larger. The alcohol is used as a dispersion medium, and the short carbon fiber is dispersed by short-time low-speed ball milling, so that the mechanical damage of the dispersed carbon fiber can be reduced as much as possible, the dispersion uniformity of the short carbon fiber in the phosphate geological polymer matrix can be fully ensured, and the excellent uniformity of the mechanical property can be effectively ensured.
(6) Preparing phosphate group geopolymer precursor slurry: diluting 85 wt% concentrated phosphoric acid to 10mol/L with deionized water according to SiO in powder2And H3PO4The mol ratio is 4: 5, the SiO containing the chopped carbon fiber prepared in the step (5) is added2-Al2O3And adding the diluted phosphoric acid solution into the composite powder, and stirring for 5min to form uniform phosphate group geopolymer precursor slurry with good fluidity.
(7) And (3) injection molding and curing: and (4) pouring the slurry formed in the step (6) into a pre-fixed mould, standing for 2 hours at room temperature, and curing in an oven at the curing temperature of 60 ℃ for 24 hours after the slurry flows sufficiently.
(8) Demolding and maintaining: and (4) demolding the completely cured short carbon fiber reinforced geopolymer matrix composite material obtained in the step (7), and further placing the obtained product in an oven for curing at 60 ℃ for 7 days and 28 days to improve the mechanical property.
(9) Surface treatment: and (3) further putting the composite material subjected to demolding and curing in the step (8) into an SR 249-silicone alcohol solution with the concentration of 6 wt%, soaking for 4h under the common atmospheric pressure, taking out, airing for 15h, further moving into an oven, and keeping the temperature of 120 ℃ for carrying out a crosslinking reaction for 3h to obtain the chopped carbon fiber reinforced phosphate-based geopolymer composite material.
The surface treatment is to make the surface of the composite hydrophobic and avoid the performance fluctuation caused by water absorption during the later storage.
The chopped carbon fiber reinforced phosphate group geopolymer composite material prepared by the embodiment is composed of chopped carbon fibers and phosphate group geopolymer, wherein the phosphate group geopolymer is used as a base body, the chopped carbon fibers are used as a reinforcement body, and the chopped carbon fibers are dispersed in the phosphate group geopolymer base body. In the composite material, the content of the chopped carbon fibers is 10 percent by volume fraction, and the phosphate group geopolymer is made of Al2O3、SiO2With phosphoric acid, Al2O3With SiO2In a molar ratio of 0.5: 1, SiO2With PO in phosphoric acid4 3 +The molar ratio of (2) to (1) is 0.8: 1, and the porosity of the chopped carbon fiber reinforced phosphate-based geopolymer composite material is 5.3%.
According to the process steps, the chopped carbon fibers are not added, the common phosphate group geopolymer composite material which is not reinforced by the chopped carbon fibers is prepared, and the bending strength of the common phosphate group geopolymer composite material which is not reinforced by the chopped carbon fibers after 28 days of maintenance is only 9.3MPa and the maximum strain rate is only 0.13 percent. The bending strength of the chopped carbon fiber reinforced phosphate group geopolymer composite material obtained in the embodiment after 7-day curing is 11.4MPa, the maximum strain rate is 1.8%, the bending strength after 28-day curing is 14.7MPa, the maximum strain rate is 2.2%, and the strain rate is improved by one order of magnitude under the action of the chopped carbon fibers. After heat treatment for 1h in the high-temperature inert atmosphere at 1000 ℃, the retention rate of the strength (bending strength) of the composite material does not decrease and inversely increase and reaches 36.7 MPa.
Fig. 2 is a physical diagram of the chopped carbon fiber reinforced phosphate-based geopolymer composite prepared in the embodiment, and it can be seen from the physical diagram that the linear shrinkage during the curing process of the geopolymer is obviously reduced compared with the prior art, and no obvious crack is generated during the shrinkage due to the bridging effect of the fiber; furthermore, it can be seen from the figure that the carbon fibres are homogeneously dispersed in the geopolymer composite.
FIG. 3 shows the SiO dispersed in the chopped carbon fiber of this example2-Al2O3Electronic display of composite powderThe micro-mirror photo shows that after the short-time ball milling and drying at a low speed by taking alcohol as a dispersing agent, the chopped carbon fibers are uniformly and completely dispersed in the precursor powder, and the problem of non-uniform performance and structure caused by partial agglomeration of the chopped carbon fibers is effectively avoided due to the higher wettability of the alcohol on the chopped carbon fibers and the matrix and the advantages of the ball milling and mixing materials.
FIG. 4 is the XRD phase spectrum of the alumina-silica gel powder calcined and activated at different temperatures in this example, which shows that the SiO obtained in step (3) of this example is subjected to2-Al2O3Carrying out XRD detection on the active powder: the phase composition of the gel powder (molar ratio corresponding to the YAG crystal phase) was analyzed by X-ray diffractometer model D8 Advance. The test conditions were: CuK alpha rays, tube current 40mA, tube voltage 40KV, 2 theta 15-90 degrees and scanning speed 4 DEG/min. The detection result is shown in fig. 4, and it can be seen from the figure that: the map shows the peak characteristic of the steamed bread, and no sharp SiO appears2Or Al2O3Characteristic diffraction peak, showing SiO after drying at 750 deg.C2-Al2O3The gel powder is typically in an amorphous state, and the amorphous state has high surface energy, so that the reactivity in the polymerization process can be further improved, and the reaction temperature can be reduced.
Example 2:
the preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material disclosed by the invention comprises the following steps of:
(1) preparation of SiO2-Al2O3Sol precursor: passing SiO with particle size of 20 nm-30 nm2Sol and Al with particle size of 10-30 nm2O3Electronic grade SiO with 35 wt% solid phase content and less than or equal to 30mm sol particle size is prepared by mixing sol2-Al2O3Adding PEG600 (polyethylene glycol with number average molecular weight of 600) to obtain SiO with fine particle size, high solid content and stability2-Al2O3Precursor of SiO2With Al2O3In a molar ratio of 20: 13, PEG600 and SiO2-Al2O3Mass of sol precursorThe ratio of the amounts is 1: 16.
(2) And (3) gel drying: SiO prepared in the step (1)2-Al2O3And (3) transferring the sol precursor into an oven, preserving the heat for 15h at 60 ℃ to form uniform gel, continuing raising the temperature to 120 ℃ after the gel is solidified, preserving the heat for 4h, and further removing free water in the gel.
(3) And (3) calcining: transferring the gel dried in the step (2) to a muffle furnace to calcine for 4 hours at 700 ℃ to remove a small amount of organic active agent and crystal water in the gel to obtain uniform and pure SiO2-Al2O3And (3) active powder.
(4) Pretreatment of the chopped carbon fibers: and (2) placing the chopped carbon fibers with the length of 9mm and the diameter of 5-7 microns in a vacuum condition at 1600 ℃ for heat treatment for 1h with the vacuum degree of 1Pa to remove organic glue on the surfaces of the carbon fibers, then soaking the chopped carbon fibers in 10mol/L concentrated nitric acid for 5h, filtering the chopped carbon fibers after soaking is finished, and further drying at a low temperature of 70 ℃ for 12 h.
(5) Preparation of carbon fiber-containing SiO2-Al2O3Composite powder: mixing the chopped carbon fibers pretreated in the step (4) with the SiO formed in the step (3)2-Al2O3Putting the active precursor powder into a ball milling tank together, performing ball milling for 5min by taking alcohol as a ball milling medium, wherein the ball milling rotating speed is 100r/min, taking out the slurry after the ball milling is finished, and drying at the drying temperature of 60 ℃ for 18h to obtain a geopolymer precursor SiO with high activity and uniformly dispersed short carbon fibers2-Al2O3And (3) composite powder.
(6) Preparing phosphate group geopolymer precursor slurry: diluting 85 wt% concentrated phosphoric acid to 12mol/L with deionized water according to SiO in powder2And H3PO4The mol ratio is 1: 1, the carbon fiber-containing SiO prepared in the step (5)2-Al2O3And adding the diluted phosphoric acid solution into the active powder, and stirring for 5min to form uniform phosphate group geopolymer precursor slurry with good fluidity.
(7) And (3) injection molding and curing: and (4) pouring the slurry formed in the step (6) into a pre-fixed mould, standing for 2 hours at room temperature, and curing in an oven at the curing temperature of 80 ℃ for 36 hours after the slurry flows sufficiently.
(8) Demolding and maintaining: and (4) demolding the completely cured short carbon fiber reinforced geopolymer matrix composite material in the step (7), and further placing the composite material in an oven for curing at 60 ℃ for 7 days and 28 days to improve the mechanical property.
(9) Surface treatment: and (3) further putting the composite material subjected to demolding and curing in the step (8) into an SR 249-silicone alcohol solution with the concentration of 5 wt%, soaking for 6h under the common atmospheric pressure, taking out, airing for 20h, further moving into an oven, and keeping the temperature of 120 ℃ for carrying out a crosslinking reaction for 3h to obtain the chopped carbon fiber reinforced phosphate-based geopolymer composite material.
The surface treatment is to make the surface of the composite hydrophobic and avoid the performance fluctuation caused by water absorption during the later storage.
The chopped carbon fiber reinforced phosphate-based geopolymer composite material prepared by the embodiment is composed of chopped carbon fibers and phosphate-based geopolymer, wherein the phosphate-based geopolymer is used as a base body, the chopped carbon fibers are used as a reinforcement body, and the chopped carbon fibers are dispersed in the phosphate-based geopolymer base body. In the composite material, the content of the chopped carbon fibers is 12 percent by volume fraction, and the phosphate group geopolymer is made of Al2O3、SiO2With phosphoric acid, Al2O3With SiO2In a molar ratio of 0.75: 1, SiO2With PO in phosphoric acid4 3+The molar ratio of the short carbon fiber reinforced phosphate group geopolymer composite material is 1: 1, and the porosity of the short carbon fiber reinforced phosphate group geopolymer composite material is 5.0 percent.
The test shows that the bending strength of the chopped carbon fiber reinforced phosphate group geopolymer composite material obtained in the embodiment after 7-day curing is 12.8MPa, the maximum strain rate is 2.0%, the bending strength after 28-day curing is 15.3MPa, and the maximum strain rate is 2.5%. After heat treatment for 1h in the high-temperature inert atmosphere at 1000 ℃, the retention rate of the strength (bending strength) of the composite material does not decrease and inversely increase and reaches 45.5 MPa.
Example 3:
the preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material disclosed by the invention comprises the following steps of:
(1) preparation of SiO2-Al2O3Sol precursor: passing SiO with particle size of 20 nm-30 nm2Sol and Al with particle size of 10-30 nm2O3Mixing the sol to obtain electronic grade SiO with solid phase content of 35 wt% and sol particle size not greater than 30mm2-Al2O3Adding PEG600 (polyethylene glycol with molecular weight of 600) into the sol as precursor to obtain SiO with fine particle diameter, high solid content and stability2-Al2O3Sol precursor of SiO2With Al2O3The molar ratio is 1: 1, PEG600 and SiO2-Al2O3The mass ratio of the sol precursor is 1: 14.
(2) And (3) gel drying: SiO prepared in the step (1)2-Al2O3And (3) transferring the sol precursor into an oven, preserving the heat for 15h at 60 ℃ to form uniform gel, continuing raising the temperature to 120 ℃ after the gel is solidified, preserving the heat for 4h, and further removing free water in the gel.
(3) And (3) calcining: transferring the gel dried in the step (2) to a muffle furnace to calcine for 4 hours at 700 ℃ to remove a small amount of organic active agent and crystal water in the gel to obtain uniform and pure SiO2-Al2O3And (3) active powder.
(4) Pretreatment of the chopped carbon fibers: and (2) placing the chopped carbon fibers with the length of 12mm and the diameter of 5-7 microns in a vacuum condition of 1800 ℃ for heat treatment for 1h with the vacuum degree of 0.1Pa to remove organic glue on the surfaces of the chopped carbon fibers, then soaking the chopped carbon fibers in 10mol/L concentrated nitric acid for 5h, filtering the chopped carbon fibers after soaking is finished, and further drying at a low temperature of 80 ℃ for 12 h.
(5) Preparation of SiO containing chopped carbon fibers2-Al2O3Composite powder: forming the chopped carbon fibers pretreated in the step (4) and the chopped carbon fibers formed in the step (3)SiO of (2)2-Al2O3Putting the active powder into a ball milling tank together, performing ball milling for 5min by taking alcohol as a ball milling medium, wherein the ball milling rotating speed is 100r/min, taking out the slurry after the ball milling is finished, and drying at 60 ℃ for 24h to obtain a geopolymer precursor SiO with high activity and uniformly dispersed short carbon fibers2-Al2O3And (3) compounding the powder.
(6) Preparing phosphate group geopolymer precursor slurry: diluting 85 wt% concentrated phosphoric acid to 10mol/L with deionized water according to SiO in powder2And H3PO4The mol ratio is 1: 1, and the SiO containing the chopped carbon fiber prepared in the step (5) is added2-Al2O3And adding the diluted phosphoric acid solution into the active powder, and stirring for 5min to form uniform phosphate group geopolymer precursor slurry with good fluidity.
(7) And (3) injection molding and curing: and (4) pouring the slurry formed in the step (6) into a pre-fixed mould, standing for 2 hours at room temperature, and curing in an oven at the curing temperature of 80 ℃ for 36 hours after the slurry flows sufficiently.
(8) Demolding and maintaining: and (4) demolding the completely cured short carbon fiber reinforced geopolymer matrix composite material obtained in the step (7), and further placing the obtained product in an oven for curing at 60 ℃ for 7 days and 28 days to improve the mechanical property.
(9) Surface treatment: and (3) further putting the composite material subjected to demolding and curing in the step (8) into a SR 249-silicone alcohol solution with the concentration of 7 wt%, soaking for 6h under the common atmospheric pressure, taking out, airing for 20h, further moving into an oven, and keeping the temperature of 120 ℃ for carrying out a crosslinking reaction for 3h to obtain the chopped carbon fiber reinforced phosphate-based geopolymer composite material.
The surface treatment is to make the surface of the composite hydrophobic and avoid the performance fluctuation caused by water absorption during the later storage.
The chopped carbon fiber reinforced phosphate group geopolymer composite material is composed of chopped carbon fibers and a phosphate group geopolymer, wherein the phosphate group geopolymer is used as a base body, and the chopped carbon fibers are used as the base bodyThe chopped carbon fibers are dispersed in the phosphate group geopolymer matrix. In the composite material, the content of the chopped carbon fibers is 15 percent by volume fraction, and the phosphate group geopolymer is made of Al2O3、SiO2With phosphoric acid, Al2O3With SiO2In a molar ratio of 1: 1, SiO2With PO in phosphoric acid4 3+The molar ratio of the short carbon fiber reinforced phosphate group geopolymer composite material is 1: 1, and the porosity of the short carbon fiber reinforced phosphate group geopolymer composite material is 6.4%.
Through detection, the bending strength of the chopped carbon fiber reinforced phosphate group geopolymer composite material obtained in the embodiment after 7-day curing is 12.2MPa, the maximum strain rate is 2.3%, the bending strength after 28-day curing is 15.8MPa, and the maximum strain rate is 3.0%. After heat treatment for 1h in the high-temperature inert atmosphere at 1000 ℃, the retention rate of the strength (bending strength) of the composite material does not decrease and inversely increase and reaches 41.2 MPa.
From examples 1 to 3, the chopped carbon fiber reinforced phosphate-based geopolymer composite material prepared by the preparation method disclosed by the invention has the advantages of high mechanical strength, ultra-long strain and excellent high temperature resistance.
In conclusion, the invention provides a novel material system of the chopped carbon fiber reinforced phosphate geopolymer composite material based on the characteristics, the current research situation and the existing problems of the phosphate geopolymer and the advantages of the chopped carbon fiber and the phosphate geopolymer, and forms a preparation method capable of obtaining excellent performance.
In the preparation method, uniformly dispersed and stable SiO is obtained by adding PEG400, PEG600 or PEG800 additive2-Al2O3The composite sol provides reliable raw material guarantee for the preparation of the composite material, and then SiO with the solid phase content of 25-45 wt% is adopted2-Al2O3The composite sol (the particle size of the colloid is less than or equal to 30mm) is used as an initial raw material, and after low-temperature calcination and low-speed ball milling mixing, aluminum-silicon precursor powder which has ultrahigh activity and in which the chopped carbon fibers are uniformly dispersed is obtained. The ultrahigh activity powder can be polymerized with phosphoric acid at room temperature to formA chopped carbon fiber reinforced phosphate-based geopolymer composite. The composite material can obtain higher bending strength and ultralong strain after being cured for 7 days at low temperature (60 ℃). Compared with a phosphate group geopolymer material which is not enhanced by chopped carbon fibers, the bending strength of the method is obviously improved, particularly, the strain rate is improved by one order of magnitude, and the corresponding fracture ductility is also improved by several 10 times. Compared with steel fibers, quartz fibers and basalt fibers, the chopped carbon fibers selected by the invention have very high physical and chemical thermal stability, and can effectively avoid chemical damage of phosphoric acid to the fibers in the polymerization process, so that the reinforcing and toughening effects are greatly improved. And the traditional fiber reinforced concrete inorganic gelled composite materials such as steel fiber and the like begin to have obvious failure behaviors at the temperature of more than 300 ℃, both the fiber and the matrix, after the chopped carbon fiber reinforced phosphate group geopolymer composite material is subjected to heat treatment for 1 hour at the high temperature of 1400-1800 ℃ in an inert atmosphere, the strength retention rate does not decrease and inversely increases, and the strength retention rate reaches 36.7-45.5 MPa. Therefore, the chopped carbon fiber reinforced phosphate group geopolymer composite material has outstanding mechanical properties and extremely obvious high-temperature resistance.
In addition, the dispersion condition of the chopped carbon fibers in the precursor powder of the chopped carbon fiber reinforced phosphate-based geopolymer composite material is observed by using an optical microscope, as shown in fig. 3, it can be seen that in example 1, after low-speed short-time ball milling and drying are carried out by using alcohol as a dispersing agent, the chopped carbon fibers are uniformly and completely dispersed in the precursor powder, and the problem of non-uniformity of performance and structure caused by partial agglomeration of the chopped carbon fibers is effectively avoided due to higher wettability of the alcohol on the chopped carbon fibers and a base body and the advantages of ball milling and mixing materials. Therefore, the method of low-speed short-time ball milling by using alcohol as a dispersing agent ensures the dispersion uniformity of the chopped carbon fibers in the matrix, effectively reduces the damage to the chopped carbon fibers and ensures that the performance of the chopped carbon fibers can be fully exerted.
According to the invention, the interface bonding between the chopped carbon fiber and the phosphate geological polymer matrix is improved by removing the surface glue of the chopped carbon fiber in vacuum and then soaking and activating the surface of the chopped carbon fiber by using nitric acid, so that the cross-linking effect of the chopped carbon fiber can be more effectively exerted, and the mechanical property of the phosphate geological polymer is greatly improved.
Finally, in the sol used in the invention, SiO2-Al2O3Is in an amorphous state and is in a nanometer scale, and has high surface energy and high reactivity. The polymerization reaction can be completed even under the ordinary room temperature condition, and higher strength can be achieved. Meanwhile, compared with geopolymer precursor powder such as kaolin and the like, the powder is prepared by SiO2-Al2O3The adjustment and control of Si atom and Al atom components in the sol preparation process can obtain SiO with any chemical composition ratio2-Al2O3The precursor active powder can effectively regulate and control the mechanical property, high temperature resistance and the like of the phosphate group geopolymer and obtain various phosphate group geopolymer composite materials.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (10)
1. A preparation method of a chopped carbon fiber reinforced phosphate group geopolymer composite material is characterized by comprising the following steps:
(1) preparation of SiO2-Al2O3Sol precursor: mixing SiO2Sol and Al2O3Mixing the sol and the water to obtain a mixture,adding a stabilizer and mixing uniformly to obtain SiO2-Al2O3Sol precursor, Al2O3With SiO2The molar ratio of (A) to (B) is 0.25-1: 1;
(2) and (3) gel drying: SiO obtained in the step (1)2-Al2O3Keeping the sol precursor at a constant temperature to form gel, and continuing to raise the temperature to dry the gel after the gel is solidified;
(3) and (3) calcining: calcining the dried gel obtained in the step (2) to remove organic active ingredients and crystal water in the gel to obtain SiO2-Al2O3Active powder;
(4) pretreatment of the chopped carbon fibers: placing the chopped carbon fibers in vacuum for heat treatment to remove organic glue on the surfaces of the carbon fibers, then soaking and activating the carbon fibers by using a nitric acid solution or hydrogen peroxide, filtering and drying to obtain pretreated chopped carbon fibers;
(5) preparation of SiO containing chopped carbon fibers2-Al2O3Composite powder: mixing the chopped carbon fiber pretreated in the step (4) and the SiO prepared in the step (3)2-Al2O3Mixing and ball-milling active powder, drying the obtained ball-milling slurry after the ball-milling is finished, and obtaining the SiO containing the short carbon fiber2-Al2O3Composite powder;
(6) preparing phosphate group geopolymer precursor slurry: SiO containing chopped carbon fibers in the step (5)2-Al2O3The composite powder and phosphoric acid solution are mixed into phosphate group geopolymer precursor slurry, and the SiO containing the short carbon fiber2-Al2O3SiO in composite powder2With H in the phosphoric acid solution3PO4The molar ratio of (A) to (B) is 0.7-1.5: 1;
(7) and (3) injection molding and curing: pouring the phosphate group geopolymer precursor slurry prepared in the step (6) into a mould, standing and curing;
(8) demolding and maintaining: demolding, preserving heat and maintaining the completely cured short carbon fiber reinforced geopolymer matrix composite material obtained in the step (7);
(9) surface treatment: and (3) putting the composite material subjected to demolding and curing in the step (8) into a silicone resin solution for dipping, taking out and airing after dipping, and performing crosslinking reaction to hydrophobize the surface of the composite material to obtain the chopped carbon fiber reinforced phosphate group geopolymer composite material.
2. The method of making a chopped carbon fiber reinforced phosphate-based geopolymer composite of claim 1, wherein in step (1), the SiO is2-Al2O3The solid content of the sol precursor is 25 wt% -45 wt%, and the SiO is2-Al2O3The size of sol particles of the sol precursor is less than or equal to 30mm, and SiO is2The particle diameter of the sol particles is 20 nm-30 nm, Al2O3The particle size of the sol particles is 10 nm-30 nm;
and/or in the step (1), the stabilizing agent is polyethylene glycol, the number average molecular weight of the polyethylene glycol is 200, 400 or 600, and the polyethylene glycol and the SiO2-Al2O3The mass ratio of the sol precursor is 5-8: 100.
3. The method for preparing the chopped carbon fiber reinforced phosphate-based geopolymer composite material according to claim 1, wherein in the step (2), the temperature for heat preservation is 60-80 ℃, and the time for heat preservation is 12-24 h; the temperature of the dried gel is 100-150 ℃, and the time of the dried gel is 2-6 h.
4. The method for preparing a chopped carbon fiber reinforced phosphate-based geopolymer composite according to claim 1, wherein in the step (3), the calcination temperature is 400-800 ℃ and the calcination time is 3-5 h.
5. The method for preparing a chopped carbon fiber reinforced phosphate-based geopolymer composite according to claim 1, wherein in step (4), the chopped carbon fibers have a length of 5mm to 15mm and a diameter of 5 μm to 7 μm;
and/or in the step (4), the heat treatment temperature is 1400-1800 ℃, the heat treatment time is 1-2 h, the heat treatment is carried out in a vacuum environment, and the vacuum degree of the vacuum environment is 0-10 Pa;
and/or in the step (4), the nitric acid solution is concentrated nitric acid, the concentration of the concentrated nitric acid is 8-10 mol/L, and the time for impregnation and activation is 5-10 h;
and/or, in the step (4), the drying temperature is 60-80 ℃, and the drying time is 10-12 h.
6. The preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material according to any one of claims 1 to 5, wherein in the step (5), the ball milling medium is alcohol, the ball milling time is 5min to 6min, and the ball milling rotation speed is 100 r/min; and/or the drying temperature is 60-70 ℃, and the drying time is 12-24 h.
7. The method for preparing a chopped carbon fiber reinforced phosphate-based geopolymer composite according to any one of claims 1 to 5, wherein in the step (6), the concentration of the phosphoric acid solution is 6 to 14 mol/L;
and/or in the step (7), the standing time is 2-3 h, the curing temperature is 40-80 ℃, and the curing time is 24-48 h.
And/or in the step (8), the temperature for heat preservation and maintenance is 60-80 ℃, and the time for heat preservation and maintenance is 7-28 days.
8. The method for preparing a chopped carbon fiber reinforced phosphate-based geopolymer composite according to any one of claims 1 to 5, wherein in the step (9), the silicone resin is a low-foaming hydrophobic silicone resin, the low-foaming hydrophobic silicone resin comprises SR249 series low-foaming hydrophobic silicone resin and/or MK series low-foaming hydrophobic silicone resin, the solvent of the silicone resin solution is alcohol, and the concentration of the silicone resin solution is 5-10 wt%;
and/or in the step (9), the impregnation is carried out under atmospheric pressure, the impregnation time is 4-6 h, and the airing time is 12-24 h;
and/or in the step (9), the temperature of the crosslinking reaction is 100-150 ℃, and the time of the crosslinking reaction is 2-6 h.
9. The chopped carbon fiber reinforced phosphate-based geopolymer composite material prepared by the preparation method of the chopped carbon fiber reinforced phosphate-based geopolymer composite material as defined in any one of claims 1 to 8.
10. The chopped carbon fiber reinforced phosphate-based geopolymer composite according to claim 9, wherein the composite is composed of chopped carbon fibers and a phosphate-based geopolymer, the phosphate-based geopolymer is a matrix, the chopped carbon fibers are a reinforcement, the chopped carbon fibers are dispersed in the phosphate-based geopolymer matrix, the content of the chopped carbon fibers in the composite is 1-15% by volume fraction, and the phosphate-based geopolymer is made of Al2O3、SiO2And phosphoric acid, said Al2O3With SiO2The molar ratio of (A) to (B) is 0.25-1: 1, and the SiO is2With PO in phosphoric acid4 3+The molar ratio of the short carbon fiber reinforced phosphate group geopolymer to the short carbon fiber reinforced phosphate group geopolymer is 0.7-1.5: 1, and the porosity of the short carbon fiber reinforced phosphate group geopolymer composite material is 2% -10%.
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| CN114409286A (en) * | 2021-12-27 | 2022-04-29 | 武汉大学 | Preparation method of super-hydrophobic phosphate group geopolymer |
| CN114988912A (en) * | 2022-07-13 | 2022-09-02 | 华北水利水电大学 | Preparation method of polymer foam concrete for filling cold-formed thin-wall steel |
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