CN113800837A - Continuous carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof - Google Patents
Continuous carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof Download PDFInfo
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- CN113800837A CN113800837A CN202111162408.5A CN202111162408A CN113800837A CN 113800837 A CN113800837 A CN 113800837A CN 202111162408 A CN202111162408 A CN 202111162408A CN 113800837 A CN113800837 A CN 113800837A
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- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 156
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 156
- 229920000876 geopolymer Polymers 0.000 title claims abstract description 142
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000002131 composite material Substances 0.000 title claims abstract description 104
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 49
- 238000010438 heat treatment Methods 0.000 claims abstract description 44
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 17
- 229920002050 silicone resin Polymers 0.000 claims abstract description 17
- 238000007639 printing Methods 0.000 claims abstract description 16
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 13
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 13
- 238000007650 screen-printing Methods 0.000 claims abstract description 10
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 230000004913 activation Effects 0.000 claims abstract description 6
- 238000004381 surface treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000007865 diluting Methods 0.000 claims abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 65
- 239000010452 phosphate Substances 0.000 claims description 65
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 65
- 238000001723 curing Methods 0.000 claims description 41
- 239000004744 fabric Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 239000011159 matrix material Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000004132 cross linking Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000005284 excitation Effects 0.000 claims description 3
- 238000005187 foaming Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
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- 230000000630 rising effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 18
- 229910052681 coesite Inorganic materials 0.000 description 10
- 229910052906 cristobalite Inorganic materials 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229910052682 stishovite Inorganic materials 0.000 description 10
- 229910052905 tridymite Inorganic materials 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000001976 improved effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical class [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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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
- 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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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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
- 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
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/82—Coating or impregnation with organic materials
- C04B41/84—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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
The invention discloses a continuous carbon fiber reinforced phosphate group geopolymer composite material and a preparation method thereof, wherein the preparation method comprises the following steps: carrying out vacuum heat treatment on the carbon fibers; activation pretreatment of an aluminum-silicon source: calcining the superfine kaolin powder to prepare metakaolin powder; diluting concentrated phosphoric acid into a phosphoric acid solution; uniformly mixing metakaolin powder and a phosphoric acid solution to prepare phosphate group geopolymer slurry; preparing and pretreating a mould; and (3) forming the continuous carbon fiber reinforced phosphate group geopolymer composite material: uniformly printing the slurry on the pretreated carbon fibers in a screen printing mode, and then stacking the carbon fibers on a prefabricated mold layer by layer to form a rough blank; curing, demolding and maintaining; and (5) carrying out surface treatment on the silicone resin solution. The prepared composite material is composed of the phosphate group geopolymer and continuous carbon fibers uniformly distributed in the phosphate group geopolymer. The composite material has the advantages of excellent mechanical property, outstanding high and low temperature resistance, low energy consumption cost of the preparation method and simple process.
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 continuous carbon fiber-reinforced phosphate group geopolymer composite material with excellent mechanical properties and outstanding high-temperature resistance and low-temperature resistance and a preparation method thereof.
Background
The phosphate-based geopolymer is a P-Al-Si-O inorganic polymer with a three-dimensional network structure formed by exciting the copolymerization of aluminosilicate with certain activity by using a certain concentration of phosphoric acid. The flame-retardant material has the advantages of excellent chemical and high-temperature stability, lower density, thermal conductivity and thermal expansion coefficient, good sealing property and oxidation resistance, adjustable dielectric property and friction property, wide raw material source, lower preparation energy consumption cost and the like, and is expected to be widely applied in the fields of high-temperature flame retardance of civil buildings, heat insulation protection of aerospace, insulation packaging of electronic components, brake braking of heavy-duty automobiles, bulletproof and impact resistance of tank armors and the like.
However, the poor flexural strength and toughness of phosphate-based geopolymers greatly limit their application range, and therefore, it is necessary to reinforce and toughen them. At present, the research on phosphate group geopolymers is carried out earlier abroad, and the research on the reinforcing and toughening aspects of geopolymers is carried out by a small number of colleges and universities and research institutes at home, and a certain progress is made. However, the research target is mainly focused on the reinforcing and toughening of the basic geopolymer, and the work on the reinforcing and toughening of the phosphate geopolymer is reported in the literature. The main reason for this is that phosphate-based geopolymers are formed later than base geopolymers and develop shorter than base geopolymers, and therefore develop much less well than base geopolymers, and even the polymerization mechanism is not uniform. The reinforcing and toughening problem of the phosphate geopolymer is a key engineering technical problem to be solved urgently at present and is also an important scientific problem.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a continuous carbon fiber reinforced phosphate polymer composite material with excellent mechanical property, high temperature resistance and low temperature resistance and a preparation method thereof.
In order to solve the technical problems, the invention adopts the following technical scheme.
A preparation method of a continuous carbon fiber reinforced phosphate group geopolymer composite material comprises the following steps:
(1) pretreatment of continuous carbon fibers: cutting the two-dimensional continuous carbon fiber cloth into small pieces, then carrying out vacuum heat treatment on the cut continuous carbon fiber cloth to remove organic glue on the surface of the continuous carbon fiber for later use, and then cooling to room temperature;
(2) activation pretreatment of an aluminum-silicon source: calcining the kaolin powder with micron-sized particle size to remove the bound water to form metakaolin powder with acid excitation activity;
(3) preparation of phosphate-based geopolymer slurry: uniformly mixing the metakaolin powder obtained in the step (2) with a phosphoric acid solution to obtain phosphate group geopolymer slurry;
(4) and (3) forming the continuous carbon fiber reinforced phosphate group geopolymer composite material: uniformly printing the phosphate group geopolymer slurry prepared in the step (3) on the continuous carbon fiber pretreated in the step (1) in a screen printing mode, controlling the thickness of slurry on the surface of the continuous carbon fiber in a repeated printing mode so as to control the volume fraction of the continuous carbon fiber and a phosphate group geopolymer matrix, finally stacking the continuous carbon fiber uniformly coated with the phosphate group geopolymer slurry on a pretreated mold layer by layer, and pressing and folding the molds on two sides to form a compact continuous carbon fiber reinforced phosphate group geopolymer rough blank;
(5) curing, demolding and maintaining: preliminarily curing the compact rough blank formed in the step (4), demolding, heating the demolded continuous carbon fiber reinforced phosphate group geopolymer preform, and further curing to further complete the polymerization reaction of the matrix;
(6) surface treatment: and (3) soaking the composite material cured and demoulded and maintained in the step (5) in a silicone resin solution, taking out the composite material after the soaking is finished, airing the composite material, and carrying out a crosslinking reaction to obtain the continuous carbon fiber reinforced phosphate group geopolymer composite material.
Preferably, in the step (1), the temperature of the vacuum heat treatment is 1400-1800 ℃, the time duration of the vacuum heat treatment is 0.5-1 h, the temperature rise rate of the vacuum heat treatment is 1-5 ℃/min, and the temperature drop rate of the vacuum heat treatment is 1-3 ℃/min.
Preferably, in the step (2), the particle size of the kaolin is less than or equal to 5 μm, the calcination temperature is 650-750 ℃, the time is 4-6 h, the temperature rise rate is 5-15 ℃/min, and the temperature drop rate is 1-5 ℃/min.
Preferably, in the step (2), the particle size of the kaolin is less than or equal to 5 μm, the calcination temperature is 650-750 ℃, the time is 4-6 h, the temperature rise rate is 5-15 ℃/min, and the temperature drop rate is 1-5 ℃/min.
Preferably, in the step (3), the phosphoric acid solution is obtained by diluting concentrated phosphoric acid with a mass fraction of 85 wt%, stirring is required for 24-48 h in the dilution process, the concentration of the phosphoric acid solution is 4-12 mol/L, and the mass ratio of the phosphoric acid solution to the metakaolin powder is 0.6-1.0: 1.
In the above method for preparing the continuous carbon fiber reinforced phosphate-based geopolymer composite material, preferably, in the step (4), a layer of release agent is coated on the inner surface of the mold for pretreatment, and the release agent is an aqueous release agent. More preferably, the aqueous release agent is a PE release agent.
In the above preparation method of the continuous carbon fiber reinforced phosphate-based geopolymer composite material, preferably, in the step (4), the mesh number of the screen in the screen printing manner is 100 to 400 meshes, and the number of times of repeated printing is 2 to 10 times.
In the preparation method of the continuous carbon fiber reinforced phosphate group geopolymer composite material, preferably, in the step (5), the primary curing temperature is 40-80 ℃, and the primary curing time is 24-72 hours.
Preferably, in the step (5), the further curing temperature is 150-400 ℃, the further curing time is 1-5 h, the temperature rising rate is 1-5 ℃/min, and the temperature reduction rate after the further curing is finished is 1-3 ℃/min.
Preferably, in the step (6), the silicone resin is low-foaming hydrophobic silicone resin, the solvent used in the silicone resin solution is alcohol, the concentration of the silicone resin solution is 5-10 wt%, the impregnation is carried out under atmospheric pressure, the impregnation time is 4-6 h, and the airing time is 12-24 h. More preferably, the low-foaming hydrophobic silicone resin is SR249 silicone resin or MK silicone resin.
Preferably, in the step (6), 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 continuous carbon fiber reinforced phosphate group geopolymer composite material prepared by the preparation method of the continuous carbon fiber reinforced phosphate group geopolymer composite material.
Preferably, the composite material is composed of continuous carbon fibers and phosphate-based geopolymer, and the continuous carbon fibers are uniformly distributed in a phosphate-based geopolymer matrix.
Preferably, the content of the continuous carbon fiber in the continuous carbon fiber reinforced phosphate group geopolymer composite material is 10-55% by volume fraction.
Preferably, the porosity of the continuous carbon fiber reinforced phosphate-based geopolymer composite material is 8.8-14.5%.
In the present invention, SiO is contained in the phosphate group geopolymer2With Al2O3Preferably 1.98: 1, the SiO2With PO in phosphoric acid4 3+The molar ratio of (A) to (B) is 0.7-2: 1.
In the invention, in the step (1), the carbon fiber structure is in a two-dimensional cloth form, the type of the carbon fiber structure comprises plain cloth, twill cloth, satin cloth and the like, and the volume fraction of the fibers distributed in the phosphate-based geopolymer matrix is 10-55%.
At present, no research report about continuous carbon fiber reinforced phosphate group geopolymer is found in domestic and foreign documents. The preparation method of the phosphate group geopolymer only comprises the steps of firstly selecting natural kaolin minerals with low cost and wide sources from raw materials as aluminum silicon sources, then uniformly mixing the natural kaolin minerals with the aluminum silicon sources by taking phosphoric acid with a certain concentration as an activator to form precursor slurry with certain fluidity, and finally curing and curing under certain conditions to form the phosphate group geopolymer composite material. However, for the continuous carbon fiber reinforced phosphate-based geopolymer composite material, on the premise of considering the preparation characteristics of the existing phosphate-based geopolymer, how to rapidly prepare the phosphate-based geopolymer composite material with excellent performance and simple process is a key problem to be solved, wherein the related key technical points include how to uniformly distribute the continuous carbon fibers in the phosphate-based geopolymer, how to ensure that the formed continuous carbon fiber reinforced phosphate-based geopolymer is sufficiently dense, how to form and maintain, and the like.
Continuous fibers are referred to herein as chopped fibers and are the industry term.
Compared with the prior art, the invention has the advantages that:
1. the continuous carbon fiber reinforced phosphoric acid geopolymer composite material provided by the invention combines the advantages of the continuous carbon fiber reinforced phase and the phosphate geopolymer matrix for the first time, so that the continuous carbon fiber reinforced phosphoric acid geopolymer composite material with excellent mechanical properties is obtained. The continuous carbon fiber is utilized to provide excellent mechanical properties, and particularly, the mechanical properties of the original phosphate group geopolymer composite material are greatly improved in the aspect of improving the bending and fracture toughness.
2. The preparation method of the invention uses the kaolin mineral as the original aluminum-silicon source material, and has the remarkable characteristics of wide source, lower price cost and the like, and particularly, the slurry formed by the kaolin mineral has very outstanding flowing property due to the outstanding lubricating effect, thereby being beneficial to the even distribution of the kaolin mineral in the composite material.
3. According to the preparation method, the mesh number, the printing frequency and the like are controlled by using a screen printing mode, so that the thickness and the uniformity of the matrix on the surface of the fiber cloth can be effectively adjusted, and the continuous carbon fiber reinforced phosphate group geopolymer composite material with the uniform distribution of the reinforcement fibers and the matrix and the controllable volume fraction of the reinforcement fibers and the matrix is obtained.
4. The preparation method of the invention carries out pretreatment on the carbon fiber in a vacuum high-temperature heat treatment mode, which mainly achieves two purposes, one is to remove organic glue on the surface of the carbon fiber; secondly, high temperature vacuum heat treatment is favorable to further volatilizing the inside ash content impurity of carbon fiber, promotes the inside carbon atom structure of arranging of carbon fiber and progressively to the orderly transition by the turbostratic graphite structure to promote the graphitization degree and the surface smoothness degree of carbon fiber and fibrous elastic modulus, make it can combine with phosphate group geopolymer better, give play to carbon fiber ground reinforcing effect in phosphate group geopolymer composite as far as possible.
5. The preparation method provided by the invention effectively overcomes the defects of long single low-temperature curing time and easy cracking of single high-temperature curing by adopting a low-temperature and high-temperature combined curing mode, greatly improves the curing and curing efficiency of the carbon fiber reinforced phosphate-based geopolymer composite material, and simultaneously has the effect of reducing cracks generated in the curing process.
6. In order to reduce unstable performance changes in all aspects of force, heat and electricity caused by water absorption of the material after complete curing, the preparation method adopts the silicone resin with the concentration of 5-10 wt% to carry out subsequent atmospheric pressure impregnation, so that an organic resin coating with the thickness of about tens of nanometers can be formed on the surface, the problems of environmental and time effects caused by storage of the continuous carbon fiber reinforced phosphate group geopolymer composite material are effectively solved, and the mechanical property of the phosphate group geopolymer composite material can be further slightly improved due to good cohesiveness of the organic resin.
In conclusion, the invention provides a complete and simple preparation method for preparing the continuous carbon fiber reinforced phosphate group geopolymer composite material from the aspects of pretreatment of raw materials, preparation and printing of slurry, volume fraction control of fibers and a matrix, compression molding and forming of the composite material, later curing and maintenance and the like, and the preparation method has low energy consumption and cost and simple process. The prepared composite material not only has excellent mechanical property, but also can resist ultrahigh temperature due to the complementation of the advantages of the carbon fiber and the phosphate group geopolymer matrix.
Drawings
FIG. 1 is a flow chart of a preparation process of the continuous carbon fiber reinforced phosphoric acid geopolymer composite material.
FIG. 2 is a physical diagram of a continuous carbon fiber reinforced phosphoric acid geopolymer composite material prepared in example 1 of the present invention.
FIG. 3 is a microscopic structure view of the cross section (200 times magnification) of the continuous carbon fiber reinforced phosphoric acid geopolymer composite material prepared in example 1 of the present invention.
FIG. 4 is a microscopic structure view of the cross section (magnified 5000 times) of the continuous carbon fiber reinforced phosphoric acid geopolymer composite material prepared 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 continuous carbon fiber reinforced phosphate-based geopolymer composite material disclosed by the invention is shown in figure 1 and comprises the following steps of:
(1) pretreatment of carbon fibers: selecting two fiber bundles to interweave into carbon fiber plain cloth with an included angle of 90 degrees, cutting the carbon fiber plain cloth into a square shape with the side length of 10cm, then placing the carbon fiber plain cloth into a cracking furnace for vacuum heat treatment to remove organic glue on the surface of carbon fiber, heating to 1600 ℃, preserving heat for 1h, wherein the heating rate of the heat treatment is 5 ℃/min, the cooling rate is 3 ℃/min, and after cooling to the room temperature, finishing the pretreatment of the carbon fiber.
(2) Activation pretreatment of an aluminum-silicon source: placing the superfine kaolin powder with the average particle size of 2.5 mu m in a muffle furnace for heat treatment at 700 ℃ for 5h, wherein the heating rate of the heat treatment is 10 ℃/min, the cooling rate is 5 ℃/min, and cooling to room temperature along with the furnace after the heat treatment is finished to obtain the metakaolin powder. The process can ensure that the slurry has fine particle size and enables the reaction to be uniform, and the selection of the calcination temperature aims to remove part of bound water in the kaolin to convert the kaolin structure into a metakaolin structure with acid excitation activity.
(3) Preparation of an activating agent: weighing 85 wt% of concentrated phosphoric acid according to the mass ratio of the concentrated phosphoric acid to the deionized water of 3.53: 1, dropwise adding the concentrated phosphoric acid into the deionized water, fully and uniformly stirring, preparing a phosphoric acid solution with the concentration of 10mol/L, standing for 24 hours to ensure that the phosphoric acid solution is uniformly ionized and fully released, and standing for later use after the heat release is complete.
Preparation of phosphate-based geopolymer slurry: slowly adding the activated aluminum-silicon active powder obtained in the step (2) into a phosphoric acid solution according to the mass ratio of the metakaolin powder to the phosphoric acid solution of 1: 1, and then fully and uniformly stirring to form uniform and stable phosphate group geopolymer slurry with excellent fluidity.
(4) Preparation and pretreatment of a mold: cleaning the inner surfaces of the two steel molds by using alcohol, then coating a layer of PE release agent to avoid the difficulty in the later release process of the composite material, and standing by after the release agent is cured and molded.
And (3) forming the continuous carbon fiber reinforced phosphate group geopolymer composite material: selecting a 200-mesh silk screen device, uniformly printing the slurry obtained in the step (3) on the carbon fiber pretreated in the step (1) in a silk screen printing mode, repeatedly printing for 4 times, controlling the thickness of slurry on the surface of the fiber cloth in a repeated printing mode, so as to control the volume fraction of the carbon fiber and the phosphate group geopolymer matrix, finally stacking the carbon fiber cloth uniformly coated with the phosphate group geopolymer slurry on a pretreated mold layer by layer, and pressurizing and folding the steel molds on two sides according to the requirement that each 1cm of the carbon fiber cloth comprises 4 layers of carbon fiber cloth to form a compact rough blank in an initial molding mode;
(5) curing, demolding and maintaining: and (3) placing the compact rough blank formed in the step (4) in an oven to keep the temperature at 60 ℃ for a certain time, namely keeping the temperature for 24 hours to finish primary curing, then demoulding, and further placing the carbon fiber reinforced phosphate group geopolymer prefabricated body after demoulding in a muffle furnace for curing to further finish the polymerization reaction of the matrix and improve the mechanical property of the composite material. Wherein the heating rate of the muffle furnace is 3 ℃/min, the muffle furnace is kept warm for 1h after being heated to 250 ℃, then the muffle furnace is cooled at the same rate of 3 ℃/min, the defects of uneven heating microcracks caused in the process can be reduced as much as possible by the slower heating and cooling rate, and the muffle furnace is taken out after being cooled to the room temperature.
(6) Surface treatment: and (3) further putting the composite material subjected to demolding and curing in the step (5) into an MK silicone resin alcohol solution with the concentration of 6 wt%, soaking for 4 hours under the normal atmospheric pressure, taking out and airing for 15 hours, further moving into a drying oven, and keeping the temperature of 120 ℃ for crosslinking for 3 hours to hydrophobize the surface of the composite material, so that performance fluctuation caused by water absorption during later storage is avoided.
The continuous carbon fiber reinforced phosphate-based geopolymer composite material prepared by the embodiment is composed of continuous carbon fibers and phosphate-based geopolymer, and the continuous carbon fibers are uniformly distributed in a phosphate-based geopolymer matrix. In the composite material, the content of carbon fiber is 35 percent by volume fraction, and the phosphate group geopolymer is made of Al2O3、SiO2And phosphoric acid, SiO2With Al2O3In a molar ratio of 1.98: 1, SiO2With phosphoric acidPO4 3+The molar ratio of (1.3: 1) and the porosity of the continuous carbon fiber reinforced phosphate-based geopolymer composite material is 8.8%.
Fig. 2 is a photograph of a continuous carbon fiber reinforced phosphoric acid geopolymer composite material prepared in this example. Through detection, the bending strength of the continuous carbon fiber reinforced phosphate geopolymer composite material prepared by the embodiment is 248.5MPa, and the fracture toughness is 12.7 MPa.m1/2. After heat treatment for 30min in argon at the high temperature of 1000 ℃, the retention rate of the bending strength is 84.4 percent; the bending strength retention rate after 30min of cold treatment by low-temperature liquid nitrogen (-198 ℃) is 112.7%.
Fig. 3 is a sectional microstructure diagram of the continuous carbon fiber reinforced phosphate geopolymer composite material prepared in the embodiment, and a scanning electron microscope is adopted to observe the sectional microstructure of the continuous carbon fiber reinforced phosphate geopolymer composite material provided by the invention, so that the phosphate geopolymer is uniformly filled in carbon fiber bundles and gaps among the bundles after being fully cured, cured and formed.
Fig. 4 is a sectional microscopic structure diagram of the continuous carbon fiber reinforced phosphate geopolymer composite material prepared in the embodiment, and it can be seen that when the continuous carbon fiber reinforced phosphate geopolymer composite material is broken under the action of a high-load external force, a large amount of fibers are pulled out and debonded at the broken part, thereby also showing that the bending strength and the fracture toughness of the composite material of the embodiment are significantly improved.
Example 2:
the preparation method of the continuous carbon fiber reinforced phosphate-based geopolymer composite material disclosed by the invention comprises the following steps of:
(1) pretreatment of carbon fibers: selecting carbon fiber twill cloth, cutting the carbon fiber twill cloth into a square shape with the side length of 10cm, then placing the carbon fiber twill cloth in a cracking furnace for heat treatment to remove organic glue on the surface of the carbon fiber, wherein the temperature is 1400 ℃, the heat treatment heat preservation time is 1h, the heat treatment temperature rise rate is 5 ℃/min, the temperature reduction rate is 3 ℃/min, and after cooling to the room temperature, the carbon fiber pretreatment is completed.
(2) Activation pretreatment of an aluminum-silicon source: placing the superfine kaolin powder with the average particle size of 2.5 mu m in a muffle furnace for heat treatment at 700 ℃ for 5h, wherein the heating rate of the heat treatment is 10 ℃/min, the cooling rate is 5 ℃/min, and cooling to room temperature along with the furnace after the heat treatment is finished to obtain the metakaolin powder.
(3) Preparation of an activating agent: weighing 85 wt% of concentrated phosphoric acid according to the mass ratio of the concentrated phosphoric acid to the deionized water of 3.53: 1, dropwise adding the concentrated phosphoric acid into the deionized water, fully and uniformly stirring, preparing a phosphoric acid solution with the concentration of 10mol/L, standing for 24 hours, and standing for later use after complete heat release.
Preparation of phosphate-based geopolymer slurry: slowly adding the activated aluminum-silicon active powder obtained in the step (2) into a phosphoric acid solution according to the mass ratio of the metakaolin powder to the phosphoric acid solution of 1: 1, and then fully and uniformly stirring to form phosphate group geopolymer slurry with excellent fluidity.
(4) Preparation and pretreatment of a mold: cleaning the inner surfaces of the two steel molds by using alcohol, then coating a layer of PE release agent, and curing and forming the release agent for later use.
And (3) forming the continuous carbon fiber reinforced phosphate group geopolymer composite material: selecting a 200-mesh screen device, uniformly printing the slurry obtained in the step (3) on the carbon fiber pretreated in the step (1) in a screen printing mode, repeatedly printing for 4 times, finally, stacking the carbon fiber cloth with the surface uniformly coated with the phosphoric acid geopolymer slurry on a pretreated mold layer by layer, and pressurizing and folding the steel molds at two sides according to the requirement that each 1cm of the carbon fiber cloth contains 4 layers of carbon fiber cloth to perform primary molding to form a compact rough blank;
(5) curing, demolding and maintaining: and (3) placing the compact rough blank formed in the step (4) in a 60 ℃ oven for heat preservation for 24h to finish primary curing, then demolding, further placing the carbon fiber reinforced phosphate group geopolymer preform after demolding in a muffle furnace for curing, wherein the temperature rise rate of the muffle furnace is 3 ℃/min, keeping the temperature for 1h after the temperature rises to 250 ℃, then cooling at the same rate of 3 ℃/min, and taking out after cooling to room temperature.
(6) Surface treatment: and (3) further putting the composite material subjected to demolding and curing in the step (5) into an MK silicone resin alcohol solution with the concentration of 8 wt%, soaking for 4 hours under the normal atmospheric pressure, taking out and airing for 15 hours, further moving into a drying oven, and keeping the temperature of 120 ℃ for crosslinking for 3 hours to hydrophobize the surface of the composite material, so that performance fluctuation caused by water absorption during later storage is avoided.
The continuous carbon fiber reinforced phosphate-based geopolymer composite material prepared by the embodiment is composed of continuous carbon fibers and phosphate-based geopolymer, and the continuous carbon fibers are uniformly distributed in a phosphate-based geopolymer matrix. In the composite material, the content of carbon fiber is 40 percent by volume fraction, and the phosphate group geopolymer is made of Al2O3、SiO2And phosphoric acid, SiO2With Al2O3In a molar ratio of 1.98: 1, SiO2With PO in phosphoric acid4 3+The molar ratio of (1.3: 1), and the porosity of the continuous carbon fiber reinforced phosphate-based geopolymer composite material is 12.4%.
Through detection, the bending strength of the continuous carbon fiber reinforced phosphate geopolymer composite material prepared in the embodiment is 283.2MPa, and the fracture toughness is 14.9 MPa.m1/2. After heat treatment for 30min in argon at the high temperature of 1000 ℃, the strength retention rate is 85.6 percent; the strength retention rate after 30min of cold treatment by low-temperature liquid nitrogen (-198 ℃) is 118.3%.
Example 3:
the preparation method of the continuous carbon fiber reinforced phosphate-based geopolymer composite material disclosed by the invention is shown in figure 1 and comprises the following steps of:
(1) pretreatment of carbon fibers: selecting carbon fiber satin cloth, cutting the carbon fiber satin cloth into a square shape with the side length of 10cm, then placing the carbon fiber satin cloth in a cracking furnace for heat treatment, heating to 1800 ℃, preserving heat for 1h, cooling to room temperature at the heating rate of 3 ℃/min and the cooling rate of 1 ℃/min, and finishing the carbon fiber pretreatment.
(2) Activation pretreatment of an aluminum-silicon source: placing the superfine kaolin powder with the average particle size of 2.5 mu m in a muffle furnace for heat treatment at 700 ℃ for 5h, wherein the heating rate of the heat treatment is 10 ℃/min, the cooling rate is 3 ℃/min, and cooling to room temperature along with the furnace after the heat treatment is finished for standby to obtain the metakaolin powder.
(3) Preparation of an activating agent: weighing 85 wt% of concentrated phosphoric acid according to the mass ratio of the concentrated phosphoric acid to the deionized water of 3.53: 1, dropwise adding the concentrated phosphoric acid into the deionized water, fully and uniformly stirring, preparing a phosphoric acid solution with the concentration of 10mol/L, standing for 24 hours, and standing for later use after complete heat release.
Preparation of phosphate-based geopolymer slurry: slowly adding the activated aluminum-silicon active powder obtained in the step (2) into a phosphoric acid solution according to the mass ratio of the metakaolin powder to the phosphoric acid solution of 1: 0.9, and then fully and uniformly stirring to form phosphate group geopolymer slurry with excellent fluidity.
(4) Preparation and pretreatment of a mold: cleaning the inner surfaces of the two steel molds by using alcohol, then coating a layer of PE release agent, and curing and forming the release agent for later use.
And (3) forming the continuous carbon fiber reinforced phosphate group geopolymer composite material: selecting a 200-mesh silk screen device, uniformly printing the slurry obtained in the step (3) on the fiber cloth pretreated in the step (1) in a silk screen printing mode, repeatedly printing for 4 times, finally stacking the carbon fiber cloth with the surface uniformly coated with the phosphoric acid geopolymer slurry on a pretreated mold layer by layer, and pressurizing and folding the steel molds at two sides according to the requirement that each 1cm of the thickness contains 4 layers of carbon fiber cloth to form a compact rough blank in an initial forming mode;
(5) curing, demolding and maintaining: and (3) placing the compact rough blank formed in the step (4) in a 60 ℃ oven for heat preservation for 24h to finish primary curing, then demolding, further placing the carbon fiber reinforced phosphate group geopolymer preform after demolding in a muffle furnace for curing, wherein the temperature rise rate of the muffle furnace is 3 ℃/min, keeping the temperature for 1h after the temperature rises to 300 ℃, then cooling at the same rate of 3 ℃/min, and taking out after cooling to room temperature.
(6) Surface treatment: and (3) further putting the composite material subjected to demolding and curing in the step (5) into an SR249 silicon resin alcohol solution with the concentration of 5 wt%, soaking for 6h under the normal atmospheric pressure, taking out and airing for 15h, further moving into a drying oven, and maintaining the temperature of 120 ℃ for crosslinking for 3h to hydrophobize the surface of the composite material, so that performance fluctuation caused by water absorption during later storage is avoided.
The continuous carbon fiber reinforced phosphate-based geopolymer composite material prepared by the embodiment is composed of continuous carbon fibers and phosphate-based geopolymer, and the continuous carbon fibers are uniformly distributed in a phosphate-based geopolymer matrix. In the composite material, the content of carbon fiber is 45 percent by volume fraction, and the phosphate group geopolymer is made of Al2O3、SiO2And phosphoric acid, SiO2With Al2O3In a molar ratio of 1.98: 1, SiO2With PO in phosphoric acid4 3+The molar ratio of (1.5: 1), and the porosity of the continuous carbon fiber reinforced phosphate-based geopolymer composite material is 14.5%.
Through detection, the bending strength of the continuous carbon fiber reinforced phosphate geopolymer composite material prepared in the embodiment is 285.6MPa, and the fracture toughness is 13.3 MPa.m1/2. After heat treatment for 30min in argon at the high temperature of 1000 ℃, the strength retention rate is 88.3 percent; the strength retention rate after 30min of cold treatment by low-temperature liquid nitrogen (-198 ℃) is 116.5%.
From examples 1 to 3, the continuous carbon fiber reinforced phosphate-based geopolymer composite material prepared by the preparation method disclosed by the invention has excellent mechanical properties and high and low temperature resistance, and is suitable for application under the condition of extreme conditions and with higher requirements on mechanical strength.
In conclusion, the invention provides a novel material system of continuous 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 carbon fiber and the phosphate geopolymer, and forms a preparation method capable of obtaining excellent performance.
In the preparation method, firstly, natural kaolin minerals with extremely low cost and wide sources are selected as raw materials, so that reliable raw material guarantee is provided for the preparation of the composite material, and then precursor active powder with high activity can be obtained through simple low-medium temperature calcination. Due to the frontThe special lamellar structure of the precursor powder and the hydrolysis of phosphoric acid generate protons, and the protons are combined with the phosphoric acid to generate surface repulsion, so that the phosphate group geopolymer precursor slurry obtained after the precursor powder and the phosphoric acid are blended and stirred has very good dispersibility and fluidity. And then, carrying out screen printing on the surface of the modified continuous carbon fiber cloth by using the slurry, and finally curing and curing the continuous carbon fiber cloth to form the continuous carbon fiber reinforced phosphate-based geopolymer composite material at one time by adopting the technical steps of lamination, mould pressing and the like. The porosity of the composite material is lower than 15%, the bending strength can reach 285.6MPa, and the fracture toughness is 14.9 MPa.m1/2After being subjected to heat treatment for 30min in argon at the high temperature of 1000 ℃, the strength retention rate is 84.4-88.3 percent; the strength retention rate is 112.7-118.3% after 30min of cold treatment by low-temperature liquid nitrogen (-198 ℃). Compared with a phosphate group geopolymer material which is not reinforced by continuous carbon fibers, the mechanical property of the phosphate group geopolymer material is greatly improved. While not entirely comparable to continuous carbon fiber reinforced phosphate-based geopolymer composites prepared by other methods, it is comparable to existing continuous steel fibers and continuous organic fibers: firstly, the reinforcing capacity of the continuous fibers is more outstanding, and the effect of improving the mechanical property is more obvious; secondly, the carbon fiber has wider temperature resistance range compared with steel fiber and organic fiber, and particularly has more stable performance when cold and hot are alternated at extremely low temperature and high temperature; compared with steel fibers and organic fibers, the continuous carbon fibers and the phosphate group geopolymer matrix have better chemical and physical stability; and fourthly, due to the high axial thermal conductivity and the low thermal expansion coefficient of the carbon fibers, the internal thermal stress of the continuous carbon fiber reinforced phosphate-based geopolymer composite material is more uniform in a higher or lower extreme environment, and the dimensional change of the material caused by a temperature environment is small.
According to the invention, the organic silicon resin solution with low concentration is used as the precursor impregnation liquid to carry out atmospheric pressure impregnation on the formed continuous carbon fiber reinforced phosphate group geopolymer composite material, on one hand, the organic silicon resin can further fill the gaps and cracks in the composite material and can bond microcracks, so that the mechanical property of the composite material is further improved; on the other hand, the organic silicon resin has better hydrophobic property after being dried and crosslinked, so that the problem of contact between the continuous carbon fiber reinforced phosphate group geopolymer composite material and water vapor in the air can be effectively isolated, the problem of performance instability caused by water absorption of the phosphate group geopolymer can be solved, and the problem of long-term storage after the composite material is prepared is properly solved.
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 continuous carbon fiber reinforced phosphate group geopolymer composite material comprises the following steps:
(1) pretreatment of continuous carbon fibers: cutting the two-dimensional continuous carbon fiber cloth into small pieces, then carrying out vacuum heat treatment on the cut continuous carbon fiber cloth to remove organic glue on the surface of the continuous carbon fiber for later use, and then cooling to room temperature;
(2) activation pretreatment of an aluminum-silicon source: calcining the kaolin powder with micron-sized particle size to remove the bound water to form metakaolin powder with acid excitation activity;
(3) preparation of phosphate-based geopolymer slurry: uniformly mixing the metakaolin powder obtained in the step (2) with a phosphoric acid solution to obtain phosphate group geopolymer slurry;
(4) and (3) forming the continuous carbon fiber reinforced phosphate group geopolymer composite material: uniformly printing the phosphate group geopolymer slurry prepared in the step (3) on the continuous carbon fiber pretreated in the step (1) in a screen printing mode, controlling the thickness of slurry on the surface of the continuous carbon fiber in a repeated printing mode so as to control the volume fraction of the continuous carbon fiber and a phosphate group geopolymer matrix, finally stacking the continuous carbon fiber uniformly coated with the phosphate group geopolymer slurry on a pretreated mold layer by layer, and pressing and folding the molds on two sides to form a compact continuous carbon fiber reinforced phosphate group geopolymer rough blank;
(5) curing, demolding and maintaining: preliminarily curing the compact rough blank formed in the step (4), demolding, heating the demolded continuous carbon fiber reinforced phosphate group geopolymer preform, and further curing to further complete the polymerization reaction of the matrix;
(6) surface treatment: and (3) soaking the composite material cured and demoulded and maintained in the step (5) in a silicone resin solution, taking out the composite material after the soaking is finished, airing the composite material, and carrying out a crosslinking reaction to obtain the continuous carbon fiber reinforced phosphate group geopolymer composite material.
2. The method for preparing the continuous carbon fiber reinforced phosphate-based geopolymer composite material according to claim 1, wherein in the step (1), the temperature of the vacuum heat treatment is 1400-1800 ℃, the time duration of the vacuum heat treatment is 0.5-1 h, the temperature rise rate of the vacuum heat treatment is 1-5 ℃/min, and the temperature drop rate of the vacuum heat treatment is 1-3 ℃/min.
3. The method for preparing the continuous carbon fiber reinforced phosphate-based geopolymer composite material according to claim 1, wherein in the step (2), the particle size of the kaolin is less than or equal to 5 μm, the calcination temperature is 650-750 ℃, the calcination time is 4-6 h, the temperature rise rate is 5-15 ℃/min, and the temperature decrease rate is 1-5 ℃/min.
4. The preparation method of the continuous carbon fiber reinforced phosphate-based geopolymer composite material according to claim 1, wherein in the step (3), the phosphoric acid solution is obtained by diluting concentrated phosphoric acid with a mass fraction of 85 wt%, stirring is required for 24-48 h in the dilution process, the concentration of the phosphoric acid solution is 4-12 mol/L, and the mass ratio of the phosphoric acid solution to the metakaolin powder is 0.6-1.0: 1.
5. The method for preparing the continuous carbon fiber reinforced phosphate-based geopolymer composite according to any one of claims 1 to 4, wherein in the step (4), the inner surface of the mold is pre-treated by coating a layer of release agent, and the release agent is an aqueous release agent.
6. The method for preparing the continuous carbon fiber reinforced phosphate-based geopolymer composite material according to any one of claims 1 to 4, wherein in the step (4), the mesh number of the screen in the screen printing manner is 100-400 meshes, and the number of times of repeated printing is 2-10 times.
7. The method for preparing the continuous carbon fiber reinforced phosphate-based geopolymer composite material according to any one of claims 1 to 4, wherein in the step (5), the temperature of the primary curing is 40 ℃ to 80 ℃, and the time of the primary curing is 24h to 72 h;
and/or in the step (5), the further curing temperature is 150-400 ℃, the further curing time is 1-5 h, the temperature rising rate is 1-5 ℃/min, and the temperature reduction rate after the further curing is finished is 1-3 ℃/min.
8. The method for preparing the continuous carbon fiber reinforced phosphate-based geopolymer composite material according to any one of claims 1 to 4, wherein in the step (6), the silicone resin is low-foaming hydrophobic silicone resin, the solvent used in the silicone resin solution is alcohol, the concentration of the silicone resin solution is 5 to 10 wt%, the impregnation is carried out under atmospheric pressure for 4 to 6 hours, and the airing time is 12 to 24 hours;
and/or in the step (6), the temperature of the crosslinking reaction is 100-150 ℃, and the time of the crosslinking reaction is 2-6 h.
9. The continuous carbon fiber reinforced phosphate-based geopolymer composite material prepared by the preparation method of the continuous carbon fiber reinforced phosphate-based geopolymer composite material as claimed in any one of claims 1 to 8.
10. The continuous carbon fiber reinforced phosphate-based geopolymer composite according to claim 9, wherein the composite is composed of continuous carbon fibers and a phosphate-based geopolymer, the continuous carbon fibers are uniformly distributed in the phosphate-based geopolymer matrix, the content of the continuous carbon fibers is 10-55% by volume fraction, and the porosity of the composite is 8.8-14.5%.
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