CN113831102A - Continuous basalt fiber reinforced phosphate group geopolymer composite material and preparation method thereof - Google Patents
Continuous basalt fiber reinforced phosphate group geopolymer composite material and preparation method thereof Download PDFInfo
- Publication number
- CN113831102A CN113831102A CN202111162475.7A CN202111162475A CN113831102A CN 113831102 A CN113831102 A CN 113831102A CN 202111162475 A CN202111162475 A CN 202111162475A CN 113831102 A CN113831102 A CN 113831102A
- Authority
- CN
- China
- Prior art keywords
- basalt fiber
- continuous basalt
- composite material
- geopolymer
- phosphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002748 Basalt fiber Polymers 0.000 title claims abstract description 160
- 229920000876 geopolymer Polymers 0.000 title claims abstract description 147
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 48
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 42
- 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
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000005011 phenolic resin Substances 0.000 claims abstract description 31
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 26
- 238000005336 cracking Methods 0.000 claims abstract description 25
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 16
- 238000007639 printing Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000004381 surface treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 83
- 239000010452 phosphate Substances 0.000 claims description 82
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 82
- 239000004744 fabric Substances 0.000 claims description 51
- 238000001723 curing Methods 0.000 claims description 28
- 238000005470 impregnation Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003763 carbonization Methods 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 229920002050 silicone resin Polymers 0.000 claims description 14
- 238000002791 soaking Methods 0.000 claims description 13
- 238000004132 cross linking Methods 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 238000007650 screen-printing Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000012423 maintenance Methods 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 238000005187 foaming Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052710 silicon Inorganic materials 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 20
- 238000001816 cooling Methods 0.000 description 15
- 238000005452 bending Methods 0.000 description 13
- 238000004321 preservation Methods 0.000 description 11
- 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
- 235000019441 ethanol Nutrition 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 239000010959 steel 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
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 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
- 239000012190 activator Substances 0.000 description 3
- 239000012300 argon atmosphere Substances 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
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000007865 diluting 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
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009413 insulation 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
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229920001523 phosphate polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001550 time effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- 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
- 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
-
- 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
-
- 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
- C04B41/60—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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a continuous basalt fiber reinforced phosphate group geopolymer composite material and a preparation method thereof, wherein the preparation method comprises the pretreatment of basalt fibers; vacuum impregnating the pretreated basalt fiber with a phenolic resin solution, and carbonizing and cracking at high temperature to prepare the basalt fiber with a surface interface layer; calcining kaolin powder to obtain metakaolin powder; uniformly mixing metakaolin powder and a phosphoric acid solution to obtain phosphate group geopolymer slurry; printing phosphate group geopolymer slurry on basalt fibers with a surface interface layer, and then stacking the basalt fibers layer by layer on a prefabricated mold to form a rough blank; curing, demolding and maintaining; and carrying out surface treatment on the silicon resin solution to obtain the composite material. The prepared composite material is composed of phosphate group geopolymer and continuous basalt fiber dispersed in the phosphate group geopolymer. The composite material has excellent mechanical property and high temperature resistance, and the preparation method has the advantages of low energy consumption cost, environment-friendly and simple process.
Description
Technical Field
The invention belongs to the technical field of fiber reinforced inorganic polymer composite materials, and particularly relates to a continuous basalt fiber reinforced phosphate polymer composite material with excellent mechanical properties, high temperature resistance, low temperature resistance and high temperature oxidation resistance and a preparation method thereof.
Background
The geopolymer is an inorganic polymer with a three-dimensional network structure formed by using acid or alkali with certain concentration to excite the copolymerization of aluminosilicate with certain activity. The composite material has the advantages of low density, thermal conductivity and thermal expansion coefficient, excellent chemical and high-temperature stability, wide raw material source, low preparation energy consumption cost and the like, and is widely applied to heat insulation and load bearing structures in the fields of aerospace and civil engineering.
At present, the reported research literature on geopolymers shows that phosphate geopolymers have better high temperature resistance and mechanical properties compared with base geopolymers, and therefore, the phosphate geopolymers are worthy of more intensive and extensive research. However, the mechanical properties of phosphate-based geopolymers are still to be further improved, and especially the poor bending strength and toughness of the phosphate-based geopolymers greatly limit the application range of the phosphate-based geopolymers, so that the phosphate-based geopolymers need to be reinforced and toughened. The literature indicates that at present, the research on strengthening and toughening of geopolymers mainly focuses on basic geopolymers, and the research on strengthening and toughening of phosphate geopolymers is rarely reported. The main reason for this is that phosphate group geopolymers are developed late, resulting in much lower maturity of research development than base geopolymers. 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 basalt fiber reinforced phosphate geopolymer composite material with strong mechanical property, excellent high temperature resistance, low temperature resistance and high temperature oxidation 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 basalt fiber reinforced phosphate group geopolymer composite material comprises the following steps:
(1) pretreatment of continuous basalt fibers:
(1.1) cutting the continuous basalt fiber cloth into small pieces, then soaking the cut continuous basalt fiber cloth in an acetone solution, taking out the continuous basalt fiber cloth after the soaking is finished, airing the continuous basalt fiber cloth, and further drying the continuous basalt fiber cloth;
(1.2) putting the dried continuous basalt fiber cloth into a phenolic resin solution for vacuum impregnation, taking out and airing after the impregnation is finished, further drying to remove the solvent and enable the phenolic resin to be cured and crosslinked, finally performing carbonization and cracking, and repeating the steps of vacuum impregnation, airing, drying and carbonization and cracking for 3-4 times.
(2) Activation pretreatment of an aluminum-silicon source: calcining kaolin powder with micron-sized particle size to remove bound water therein 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) forming the continuous basalt fiber reinforced phosphate group geopolymer composite material: printing the phosphate group geopolymer slurry prepared in the step (3) on the continuous basalt fiber pretreated in the step (1) in a screen printing mode, controlling the thickness of slurry on the surface of the continuous basalt fiber in a repeated printing mode so as to control the volume fraction of the continuous basalt fiber and a phosphate group geopolymer matrix, finally stacking the continuous basalt fiber coated with the phosphate group geopolymer slurry on a mold layer by layer, and pressing and folding the molds on the two sides to form a compact continuous basalt fiber reinforced phosphate group geopolymer rough blank;
(5) curing, demolding and maintaining: placing the rough blank formed in the step (4) at 60-100 ℃, preserving heat for 12-36 h, carrying out primary curing, then demolding, heating the demolded continuous basalt fiber reinforced phosphate group geopolymer preform to 250-400 ℃, preserving heat for 1-3 h, and carrying out maintenance to further complete the polymerization reaction of the substrate;
(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 basalt fiber reinforced phosphate group geopolymer composite material.
Preferably, in the step (1.1), the continuous basalt fiber is soaked in acetone for 12-24 hours, the drying temperature is 60-100 ℃, and the drying time is 4-10 hours.
Preferably, in the step (1.2), the solvent of the phenolic resin solution is alcohol, the mass ratio of the phenolic resin to the alcohol is 1: 10-30, the phenolic resin is boron phenolic resin, and the relative molecular mass of the boron phenolic resin is 400-800.
Preferably, in the preparation method of the continuous basalt fiber reinforced phosphate-based geopolymer composite material, in the step (1.2), the vacuum pressure of the vacuum impregnation is 103Pa～104Pa, the vacuum impregnation time is 2-6 h, the drying is sequentially performed at 60 ℃ for 2-3 h, 120 ℃ for 1-2 h, 150 ℃ for 1-2 h and 180 ℃ for 1-2 h, the carbonization cracking is performed in an argon environment or a nitrogen environment, the carbonization cracking temperature is 450-550 ℃, the carbonization cracking time is 0.5-1 h, and the temperature rise rate and the temperature drop rate of the carbonization cracking are respectively controlled at 1-5 ℃/min.
Preferably, in the step (2), the particle size of the kaolin powder is less than or equal to 5 μm, the calcining temperature is 600-800 ℃, the calcining time is 5-6 h, the calcining temperature rise rate is 10-15 ℃/min, and the calcining temperature drop rate is 1-3 ℃/min.
The preparation method of the continuous basalt fiber reinforced phosphate group geopolymer composite material is superior to that of the continuous basalt fiber reinforced phosphate group geopolymer composite materialOptionally, in the step (3), the concentration of the phosphoric acid solution is 8-12 mol/L, and the mass ratio of the phosphoric acid solution to the metakaolin powder is 0.8-1.2: 1. The phosphoric acid solution consists of 85 wt% concentrated H3PO4Diluting and stirring for 24-48 h.
Preferably, in the step (4), the inner surface of the mold is coated with a water-based release agent, the water-based release agent is a PE release agent, the mesh number of the screen in the screen printing is 200-400 meshes, and the number of times of repeated printing is 2-6 times.
Preferably, in the step (5), the temperature rising rate of the maintaining is 1-3 ℃/min, the temperature reducing rate of the maintaining is 3-5 ℃/min, and the microcrack defects caused by uneven heating in the process are reduced as much as possible at the slower temperature rising and reducing rate.
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 6-8 h, and the airing time is 12-18 h. 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 120-180 ℃, and the time of the crosslinking reaction is 1-3 h.
As a general technical concept, the invention also provides a continuous basalt fiber reinforced phosphate geopolymer composite material prepared by the preparation method of the continuous basalt fiber reinforced phosphate geopolymer composite material.
Preferably, the continuous basalt fiber reinforced phosphate-based geopolymer composite material is composed of continuous basalt fibers and phosphate-based geopolymer, and the continuous basalt fibers are uniformly dispersed in a phosphate-based geopolymer matrix.
Preferably, the volume fraction of the continuous basalt fiber in the composite material is 10-50%.
Preferably, the porosity of the continuous basalt fiber reinforced phosphate geopolymer composite material is 2% -10%.
In the present invention, it is preferable that SiO is contained in the phosphate-based geopolymer2With Al2O3Preferably 1.98: 1, the SiO2With PO in phosphoric acid4 3+The molar ratio of (A) to (B) is 0.5-1.5: 1.
In the present invention, preferably, in step (1), the continuous basalt fiber cloth is a basalt fiber two-dimensional cloth, and is of a plain cloth, a twill cloth or a satin cloth type, the monofilament diameter of the basalt fiber two-dimensional cloth is 13 μm to 17 μm, and the cloth cover density of the basalt fiber two-dimensional cloth is 100g/m2～400g/m2。
At present, relevant work related to continuous basalt fiber reinforced phosphate geopolymer is not found in domestic and foreign documents, and only a preparation method of a general phosphate geopolymer is provided. However, for the continuous basalt 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 comprise how to uniformly distribute the continuous basalt fibers in the phosphate-based geopolymer, how to design an interface between the basalt fibers and a phosphate-based geopolymer matrix to ensure that the basalt fibers are not reacted by phosphoric acid, how to ensure that the formed continuous basalt fiber reinforced phosphate-based geopolymer is sufficiently compact, how to perform forming and curing, 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 basalt fiber reinforced phosphoric acid geopolymer composite material provided by the invention combines the advantages of a continuous basalt fiber reinforced phase and a phosphoric acid geopolymer together for the first time, so that the continuous basalt fiber reinforced phosphoric acid geopolymer composite material with excellent mechanical properties is obtained. The continuous basalt fiber is utilized to provide excellent mechanical properties, and particularly, the mechanical properties of the composite material are greatly improved by combining the continuous basalt fiber with phosphate group geopolymer in the aspect of improving the bending and fracture toughness.
2. The preparation method provided by the invention uses the basalt fiber with extremely low cost to reinforce and toughen the phosphate group geopolymer, so that the raw material cost of the composite material is greatly reduced, and the problem that the basalt fiber is damaged due to the corrosion of phosphoric acid molecules in a phosphate group geopolymer matrix in the preparation process is effectively solved through the modification protection of the phenolic resin on the surface of the basalt fiber, and the problem of chemical compatibility between the basalt fiber and the phosphate group geopolymer is solved.
3. The preparation method of the invention uses the kaolin mineral as the original aluminum-silicon source material, has the remarkable characteristics of wide source, low energy consumption and price cost and the like, and particularly has the outstanding lubricating effect to ensure that the formed slurry has outstanding flowing property, thereby being beneficial to the even distribution of the kaolin mineral in the composite material.
4. The preparation method of the invention uses a screen printing mode, and can effectively adjust the thickness and uniformity of the substrate on the surface of the fiber cloth by controlling the mesh number, the printing frequency and the like, so as to obtain the continuous basalt fiber reinforced phosphate group geopolymer composite material with uniform distribution of the reinforcement fibers and the substrate and controllable volume fraction of the reinforcement fibers and the substrate.
5. The preparation method provided by the invention adopts a mode of combining low temperature and high temperature curing, effectively overcomes the defects of long single low temperature curing time and easy cracking of single high temperature curing, greatly improves the curing and curing efficiency of the continuous basalt fiber reinforced phosphoric acid geopolymer composite material, and simultaneously plays a role in reducing cracks generated in the curing process.
6. In order to reduce the unstable change of the performance of each aspect of force and heat power caused by the water absorption of the material after the complete maintenance, the preparation method can form an organic resin coating with the thickness of about dozens of nanometers on the surface by adopting the silicone resin with the concentration of 5-10 wt% for the subsequent atmospheric pressure impregnation, effectively solves the problems of environmental and time effects caused by the storage of the continuous basalt fiber reinforced phosphate geopolymer composite material, and can further improve the mechanical property of the phosphate geopolymer composite material due to the good caking property of the organic resin.
In conclusion, the invention provides a complete and simple preparation method for preparing the continuous basalt fiber reinforced phosphoric acid geopolymer composite material starting from the aspects of pretreatment of raw materials, preparation and printing of slurry, volume fraction control of fibers and a matrix, mould pressing and forming of the composite material, solidification and maintenance in the later period and the like.
Drawings
FIG. 1 is a flow chart of a preparation process of the continuous basalt fiber reinforced phosphoric acid geopolymer composite material.
Fig. 2 is a diagram of a continuous basalt fiber reinforced phosphoric acid geopolymer composite material prepared in example 1 of the present invention.
Fig. 3 is a microscopic structural view of the cross section (enlarged by 100 times) of the continuous basalt fiber reinforced phosphoric acid geopolymer composite material manufactured in example 1 of the present invention.
Fig. 4 is a microscopic structural view of the cross section (enlarged 1000 times) of the continuous basalt fiber reinforced phosphoric acid geopolymer composite material manufactured 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 basalt fiber reinforced phosphate-based geopolymer composite material disclosed by the invention comprises the following steps as shown in figure 1:
(1) pretreatment of basalt fibers:
(1.1) two fiber bundles are selected to be interwoven into basalt plain cloth with an included angle of 90 degrees, the monofilament diameter is 13 mu m, and the surface density range is 100g/m2Cutting basalt fiber plain cloth into square shapes with the side length of 12cm, then putting the square shapes into an acetone solution, soaking the square shapes for 12 hours, taking out the square shapes, airing the square shapes, and then placing the square shapes in a 60 ℃ oven for further heat preservation for 10 hours.
(1.2) preparing an interface layer on the surface of the basalt fiber: selecting boron phenolic resin with the relative molecular mass of 400, preparing phenolic resin solution with the mass fraction of 5 wt% by using the phenolic resin and absolute ethyl alcohol according to the mass ratio of 5: 95, then placing the basalt fiber cloth obtained in the step (1) into the prepared phenolic resin for vacuum impregnation, wherein the vacuum impregnation pressure is 1000Pa, taking out and drying after impregnating for 2h, then placing the cloth into an oven for heat preservation for 2h at 60 ℃, for heat preservation for 1h at 120 ℃, for heat preservation for 1h at 150 ℃ and for heat preservation for 1h at 180 ℃ in sequence to complete the removal of the solvent and the solidification and crosslinking of the phenolic resin, finally placing the cloth into a cracking furnace for carbonization and cracking for 1h at 450 ℃ under the argon atmosphere, wherein the cracking heating rate and the cooling rate are both controlled at 3 ℃/min, and repeating the process in the step (1.2) for 4 times.
(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 to prepare metakaolin powder for later use.
The calcination in this step is carried out in a vacuum environment with a pressure of less than 500Pa, and the vacuum calcination temperature is selected so as to remove part of the structural water in the kaolin to form a metakaolin powder with acid-activated activity.
(3) Preparation of phosphate-based geopolymer slurry: slowly adding the activated aluminum-silicon active powder obtained in the step (2) into an activator 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.
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, standing for 24 hours to completely release heat, and obtaining a phosphoric acid solution with the concentration of 10mol/L for later use.
(4) Forming the continuous basalt fiber reinforced phosphate group geopolymer composite material: selecting a screen device with 200 meshes, uniformly printing the slurry obtained in the step (3) on the fiber cloth pretreated in the step (1) in a screen printing mode, repeatedly printing for 4 times, finally stacking the basalt fiber cloth with the surface uniformly coated with the phosphate geopolymer slurry layer by layer on a prefabricated mold, and pressurizing and folding the steel molds at two sides according to the requirement that each 1cm of thickness contains 4 layers of basalt fiber cloth to form a compact rough blank in a primary forming mode.
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.
(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, placing the demolded basalt fiber reinforced phosphate group geopolymer preform in a muffle furnace for curing, wherein the heating rate of the muffle furnace is 3 ℃/min, keeping the temperature for 1h after the temperature is raised to 250 ℃, then cooling at 3 ℃/min, and taking out after cooling to room temperature.
(6) Surface treatment: and (3) further putting the composite material cured and demoulded and cured 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 an 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 prepared continuous basalt fiber reinforced phosphate geopolymer composite material is composed of continuous basalt fibers and phosphate geopolymer, and the continuous basalt fibers are uniformly dispersed in a phosphate geopolymer matrix. In the composite material, the content of basalt fibers is 30 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 the basalt fiber reinforced phosphate group geopolymer composite material is 1.3: 1, and the porosity of the continuous basalt fiber reinforced phosphate group geopolymer composite material is 8.8 percent.
Fig. 2 is a real object diagram of the continuous basalt fiber reinforced phosphate-based geopolymer composite material prepared in the embodiment. Through detection, the bending strength of the continuous basalt fiber reinforced phosphate group geopolymer composite material is 124.9MPa, and the fracture toughness is 5.4 MPa-m1/2. Compared with single phosphate geopolymer without basalt fiber reinforcement, the bending strength and the fracture toughness of the polymer are improved by 10-20 times. The basalt fiber reinforced phosphate geopolymer has low sensitivity to temperature, the strength retention rate is 98.8% after the polymer is circulated at high and low temperatures of-50-180 ℃ for 720h, and the strength (bending strength) retention rate of more than 60% can still be maintained in an air environment at 600 ℃.
Fig. 3 is a cross-sectional microstructure diagram of the continuous basalt fiber reinforced phosphate-based geopolymer composite material prepared in this example, and it can be seen that after sufficient curing, curing and forming, the phosphate-based geopolymer matrix is uniformly filled in the fiber bundle and in the gaps between the fiber bundles.
Fig. 4 is a microstructure diagram of a fracture of the continuous basalt fiber-reinforced phosphate-based geopolymer material prepared in this embodiment, and it can be seen that when the continuous basalt fiber-reinforced phosphate-based geopolymer composite material is fractured under the action of an external force, a large amount of fibers are pulled out and debonded at the fracture, which also indicates that the bending strength and fracture toughness of the composite material of this embodiment are significantly improved.
Example 2:
the preparation method of the continuous basalt fiber reinforced phosphate-based geopolymer composite material disclosed by the invention comprises the following steps as shown in figure 1:
(1) pretreatment of basalt fibers:
(1.1) basalt twill cloth is selected, the monofilament diameter of the basalt twill cloth is 15 mu m, and the area density range is 200g/m2Cutting the basalt fiber twill cloth into a square shape with the side length of 12cm, then putting the basalt fiber twill cloth into an acetone solution, soaking for 15h, taking out, airing, and then putting the basalt fiber twill cloth into a 60 ℃ oven for further heat preservation for 10 h.
(1.2) preparing an interface layer on the surface of the basalt fiber: selecting boron phenolic resin with the relative molecular mass of 400, preparing a phenolic resin solution with the mass fraction of 7 wt% by using the phenolic resin and absolute ethyl alcohol according to the mass ratio of 7: 93, then placing the basalt fiber cloth obtained in the step (1) into the prepared phenolic resin for vacuum impregnation, wherein the vacuum impregnation pressure is 1000Pa, taking out the basalt fiber cloth after 2h of impregnation, drying the basalt fiber cloth, then placing the basalt fiber cloth into an oven for heat preservation at 60 ℃ for 2h, 120 ℃ for 1h, 150 ℃ for 1h and 180 ℃ for 1h in sequence to complete the removal of the solvent and the solidification and crosslinking of the phenolic resin, finally placing the basalt fiber cloth into a cracking furnace for carbonization and cracking at 500 ℃ under the argon atmosphere, wherein the cracking time is 1h, and the cracking temperature rise rate and the cooling rate are respectively controlled at 5 ℃/min. And the process of step (1.2) was repeated 3 times.
(2) Activation pretreatment of an aluminum-silicon source: placing superfine kaolin powder with the average particle size of 2.5 mu m in a muffle furnace for heat treatment at 650 ℃ 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.
The calcination in this step is carried out in a vacuum environment with a pressure of less than 500Pa, and the vacuum calcination temperature is selected so as to remove part of the structural water in the kaolin to form a metakaolin powder with acid-activated activity.
(3) Preparation of phosphate-based geopolymer slurry: slowly adding the activated aluminum-silicon active powder obtained in the step (2) into an activator 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.
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.
(4) Forming the continuous basalt fiber reinforced phosphate group geopolymer composite material: selecting a screen device with 200 meshes, uniformly printing the slurry obtained in the step (3) on the fiber cloth pretreated in the step (1) in a screen printing mode, repeatedly printing for 4 times, finally stacking the basalt fiber cloth with the surface uniformly coated with phosphate geopolymer slurry layer by layer on a prefabricated mold, and pressurizing and folding the steel molds at two sides according to the requirement that each 1cm of thickness contains 3 layers of basalt fiber cloth to form a compact rough blank in a primary forming mode.
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.
(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 demolded basalt fiber reinforced phosphate group geopolymer preform in a muffle furnace for curing, wherein the heating rate of the muffle furnace is 3 ℃/min, keeping the temperature for 1h after the temperature is raised to 250 ℃, then cooling at 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 basalt fiber reinforced phosphate-based geopolymer composite material prepared by the embodiment is composed of continuous basalt fibers and phosphate-based geopolymer, and the continuous basalt fibers are uniformly dispersed in a phosphate-based geopolymer matrix. In the composite material, the content of basalt 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 PO in phosphoric acid4 3+The molar ratio of the basalt fiber reinforced phosphate group geopolymer composite material is 1.3: 1, and the porosity of the continuous basalt fiber reinforced phosphate group geopolymer composite material is 9.2 percent.
Through detection, the bending strength of the continuous basalt fiber reinforced phosphate geopolymer composite material prepared by the embodiment is 143.6MPa, and the fracture toughness is 6.7 MPa.m1/2. Compared with single phosphate geopolymer without basalt fiber reinforcement, the bending strength and the fracture toughness of the polymer are improved by 10-20 times. The basalt fiber reinforced phosphate geopolymer has low sensitivity to temperature, the retention rate of strength (bending strength) is 99.2% after the polymer is circulated at high and low temperatures of-50-180 ℃ for 720h, and the retention rate of strength of more than 60% can still be maintained in an air environment at 600 ℃.
Example 3:
the preparation method of the continuous basalt fiber reinforced phosphate-based geopolymer composite material disclosed by the invention comprises the following steps as shown in figure 1:
(1) pretreatment of basalt fibers:
(1.1) basalt satin cloth is selected, the monofilament diameter of the basalt satin cloth is 17 mu m, and the area density range is 300g/m2Cutting basalt fiber satin cloth into a square shape with the side length of 12cm, and putting the square shape into an acetone solutionSoaking for 24h, taking out, air drying, and further placing in a 60 ℃ oven for 10 h.
(1.2) preparing an interface layer on the surface of the basalt fiber: selecting boron phenolic resin with the relative molecular mass of 400, preparing phenolic resin solution with the mass fraction of 4 wt% by using the phenolic resin and absolute ethyl alcohol according to the mass ratio of 4: 96, then placing the basalt fiber cloth obtained in the step (1) into the prepared phenolic resin for vacuum impregnation, wherein the vacuum impregnation pressure is 1000Pa, taking out and drying after 2h of impregnation, then placing the cloth into an oven for heat preservation at 60 ℃ for 2h, at 120 ℃ for 1h, at 150 ℃ for 1h and at 180 ℃ for 1h in sequence to complete the removal of the solvent and the solidification and crosslinking of the phenolic resin, finally placing the cloth into a cracking furnace for carbonization and cracking at 550 ℃ under the argon atmosphere, wherein the cracking time is 1h, the cracking heating rate and the cooling rate are respectively controlled at 3 ℃/min, and the process of the step (1.2) is repeated for 4 times.
(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 750 ℃ 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.
The calcination in this step is carried out in a vacuum environment with a pressure of less than 500Pa, and the vacuum calcination temperature is selected so as to remove part of the structural water in the kaolin to form a metakaolin powder with acid-activated activity.
(3) 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.
Preparation of an activating agent: according to the mass ratio of concentrated phosphoric acid to deionized water of 3.53: 1, weighing 85 wt% of concentrated phosphoric acid, dropwise adding the concentrated phosphoric acid into 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.
(4) Forming the continuous basalt fiber reinforced phosphate group geopolymer composite material: selecting a screen printing device with 200 meshes, uniformly printing the slurry obtained in the step (3) on the fiber cloth pretreated in the step (1) in a screen printing mode, repeatedly printing for 4 times, finally, stacking the basalt fiber cloth with the surface uniformly coated with phosphate geopolymer slurry on the prefabricated die in the step (6) layer by layer, and pressurizing and folding the steel dies on two sides according to the requirement that each 1cm of thickness contains 2 layers of basalt fiber cloth to form a compact rough blank in a primary forming mode.
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.
(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 demolded basalt fiber reinforced phosphate group geopolymer preform in a muffle furnace for curing, wherein the heating rate of the muffle furnace is 3 ℃/min, keeping the temperature for 1h after the temperature is raised to 250 ℃, then cooling at 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 a SR 249-silicone alcohol solution with the concentration of 7 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 150 ℃ for crosslinking for 2h to hydrophobize the surface of the composite material, so that performance fluctuation caused by water absorption during later storage is avoided.
The continuous basalt fiber reinforced phosphate-based geopolymer composite material prepared by the embodiment is composed of continuous basalt fibers and phosphate-based geopolymer, and the continuous basalt fibers are uniformly dispersed in a phosphate-based geopolymer matrix. In the composite material, the content of basalt fiber is 40 percent by volume fraction, and the phosphate group geopolymer is formed by Al2O3、SiO2And phosphoric acid, SiO2With Al2O3In a molar ratio of 1.98: 1, SiO2With PO in phosphoric acid4 3+The molar ratio of the basalt fiber reinforced phosphate base is 1.3: 1, and the basalt fiber reinforced phosphate base is continuousThe porosity of the polymer composite was 9.4%.
Through detection, the bending strength of the continuous basalt fiber reinforced phosphate group geopolymer composite material prepared by the embodiment is 147.8MPa, and the fracture toughness is 6.1 MPa-m1/2. Compared with single phosphate geopolymer without basalt fiber reinforcement, the bending strength and the fracture toughness of the polymer are improved by 10-20 times. The basalt fiber reinforced phosphate geopolymer has low sensitivity to temperature, the retention rate of strength (bending strength) is 99.5% after the polymer is circulated at high and low temperatures of-50-180 ℃ for 720h, and the retention rate of strength of more than 60% can still be maintained in an air environment at 600 ℃.
From examples 1 to 3, the continuous basalt fiber reinforced phosphate-based geopolymer composite material prepared by the preparation method disclosed by the invention has low porosity, high mechanical property and excellent high-temperature oxidation resistance.
The invention provides a novel material system of continuous basalt fiber reinforced phosphate geopolymer composite material based on the characteristics of phosphate geopolymer, the research status and the existing problems, and combines the advantages of continuous basalt fiber and phosphate geopolymer, and forms a preparation method capable of obtaining excellent performance.
In the preparation method, firstly, natural kaolin minerals and basalt fibers with extremely low cost and wide sources are selected as raw materials, the problem of reliability of raw material sources required by the preparation of the composite material is fully guaranteed, then, a phosphoric acid solution formed by concentrated phosphoric acid and deionized water is used as an activator, the sliding characteristic between the lamellar structures of the superfine kaolin is fully utilized, the superfine kaolin is mixed with the kaolin minerals to form phosphate geopolymer slurry with excellent fluidity, the slurry is utilized to perform screen printing on the surface of the modified basalt fibers, and then, the phosphate geopolymer composite material reinforced by the continuous basalt fibers is formed in one step through curing, curing and die pressing. The porosity of the composite material is lower than 10%, the bending strength can reach 147.8MPa, and the fracture toughness can reach 6.7 MPa.m1/2. Compared with the non-basalt fiber reinforcedThe mechanical property of the phosphate group geopolymer material is greatly improved. Although not entirely comparable to continuous virtual basalt fiber-reinforced phosphate-based geopolymer composites prepared by other methods, it is comparable to existing chopped steel fibers and chopped organic fibers: firstly, the synthetic raw materials have low price and wide source; secondly, the reinforcing capacity of the continuous fibers is more outstanding, and the effect of improving the mechanical property is more obvious; compared with steel fibers and organic fibers, the basalt fibers have more outstanding extreme environment resistance, and particularly have more stable performance when cold and hot are alternated at extremely low temperature and high temperature; fourthly, aiming at the problem of chemical incompatibility between the fiber and the matrix, the problem is effectively solved by modifying the surface of the basalt fiber.
According to the invention, a low-concentration organic silicon resin solution is used as a precursor impregnation solution to carry out atmospheric pressure impregnation on the formed continuous basalt fiber reinforced phosphate group geopolymer composite material, so that on one hand, the organic silicon resin can further fill gaps and cracks in the composite material and can bond microcracks, and therefore, 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 that the continuous basalt fiber reinforced phosphate-based geopolymer composite material is contacted with water vapor in the air can be effectively isolated, the problem of performance instability caused by water absorption of the phosphate-based 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 basalt fiber reinforced phosphate group geopolymer composite material comprises the following steps:
(1) pretreatment of continuous basalt fibers:
(1.1) cutting the continuous basalt fiber cloth into small pieces, then soaking the cut continuous basalt fiber cloth in an acetone solution, taking out the continuous basalt fiber cloth after the soaking is finished, airing the continuous basalt fiber cloth, and further drying the continuous basalt fiber cloth;
(1.2) putting the dried continuous basalt fiber cloth into a phenolic resin solution for vacuum impregnation, taking out and airing after the impregnation is finished, further drying to remove the solvent and enable the phenolic resin to be cured and crosslinked, finally performing carbonization and cracking, and repeating the steps of vacuum impregnation, airing, drying and carbonization and cracking for 3-4 times.
(2) Activation pretreatment of an aluminum-silicon source: calcining kaolin powder with micron-sized particle size to remove bound water therein 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) forming the continuous basalt fiber reinforced phosphate group geopolymer composite material: printing the phosphate group geopolymer slurry prepared in the step (3) on the continuous basalt fiber pretreated in the step (1) in a screen printing mode, controlling the thickness of slurry on the surface of the continuous basalt fiber in a repeated printing mode so as to control the volume fraction of the continuous basalt fiber and a phosphate group geopolymer matrix, finally stacking the continuous basalt fiber coated with the phosphate group geopolymer slurry on a mold layer by layer, and pressing and folding the molds on the two sides to form a compact continuous basalt fiber reinforced phosphate group geopolymer rough blank;
(5) curing, demolding and maintaining: placing the rough blank formed in the step (4) at 60-100 ℃, preserving heat for 12-36 h, carrying out primary curing, then demolding, heating the demolded continuous basalt fiber reinforced phosphate group geopolymer preform to 250-400 ℃, preserving heat for 1-3 h, and carrying out maintenance to further complete the polymerization reaction of the substrate;
(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 basalt fiber reinforced phosphate group geopolymer composite material.
2. The preparation method of the continuous basalt fiber-reinforced phosphate-based geopolymer composite material according to claim 1, wherein in the step (1.1), the continuous basalt fiber is soaked in acetone for 12-24 h, the drying temperature is 60-100 ℃, and the drying time is 4-10 h.
3. The preparation method of the continuous basalt fiber-reinforced phosphate-based geopolymer composite material according to claim 1, wherein in the step (1.2), the solvent of the phenolic resin solution is alcohol, the mass ratio of the phenolic resin to the alcohol is 1: 10-30, the phenolic resin is boron phenolic resin, and the relative molecular mass of the boron phenolic resin is 400-800.
4. The method for preparing continuous basalt fiber-reinforced phosphate-based geopolymer composite according to claim 1, wherein the vacuum pressure of the vacuum impregnation in step (1.2) is 103Pa～104Pa, the vacuum impregnation time is 2-6 h, the drying is sequentially performed at 60 ℃ for 2-3 h, 120 ℃ for 1-2 h, 150 ℃ for 1-2 h and 180 ℃ for 1-2 h, the carbonization cracking is performed in an argon environment or a nitrogen environment, the carbonization cracking temperature is 450-550 ℃, the carbonization cracking time is 0.5-1 h, and the temperature rise rate and the temperature drop rate of the carbonization cracking are respectively controlled at 1-5 ℃/min.
5. The preparation method of the continuous basalt fiber-reinforced phosphate-based geopolymer composite material according to claim 1, wherein in the step (2), the particle size of the kaolin powder is less than or equal to 5 μm, the calcination temperature is 600-800 ℃, the calcination time is 5-6 h, the temperature rise rate of the calcination is 10-15 ℃/min, and the temperature drop rate of the calcination is 1-3 ℃/min.
6. The method for preparing the continuous basalt fiber-reinforced phosphate-based geopolymer composite material according to any one of claims 1 to 5, wherein in the step (3), the concentration of the phosphoric acid solution is 8mol/L to 12mol/L, and the mass ratio of the phosphoric acid solution to the metakaolin powder is 0.8 to 1.2: 1.
7. The preparation method of the continuous basalt fiber-reinforced phosphate-based geopolymer composite material according to any one of claims 1 to 5, wherein in the step (4), the inner surface of the mold is coated with a water-based release agent, the water-based release agent is a PE release agent, the mesh number of a screen in the screen printing is 200-400 meshes, and the number of times of repeated printing is 2-6 times;
and/or in the step (5), the temperature rising rate of the maintenance is 1-3 ℃/min, and the temperature reduction rate of the maintenance is 3-5 ℃/min.
8. The preparation method of the continuous basalt fiber-reinforced phosphate-based geopolymer composite material according to any one of claims 1 to 5, 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, the impregnation time is 6 to 8 hours, and the airing time is 12 to 18 hours;
and/or in the step (6), the temperature of the crosslinking reaction is 120-180 ℃, and the time of the crosslinking reaction is 1-3 h.
9. The continuous basalt fiber reinforced phosphate-based geopolymer composite material prepared by the preparation method of the continuous basalt fiber reinforced phosphate-based geopolymer composite material as claimed in any one of claims 1 to 8.
10. The continuous basalt fiber-reinforced phosphate-based geopolymer composite according to claim 9, wherein the composite is composed of continuous basalt fibers and a phosphate-based geopolymer, the continuous basalt fibers are uniformly dispersed in a phosphate-based geopolymer matrix, the volume fraction of the continuous basalt fibers in the composite is 10% to 50%, and the porosity of the composite is 2% to 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111162475.7A CN113831102B (en) | 2021-09-30 | 2021-09-30 | Continuous basalt fiber reinforced phosphate group geopolymer composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111162475.7A CN113831102B (en) | 2021-09-30 | 2021-09-30 | Continuous basalt fiber reinforced phosphate group geopolymer composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113831102A true CN113831102A (en) | 2021-12-24 |
| CN113831102B CN113831102B (en) | 2022-07-05 |
Family
ID=78967867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111162475.7A Active CN113831102B (en) | 2021-09-30 | 2021-09-30 | Continuous basalt fiber reinforced phosphate group geopolymer composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113831102B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ309669B6 (en) * | 2022-03-28 | 2023-06-28 | Univerzita Jana Evangelisty Purkyně V Ústí Nad Labem | Geopolymer suspension with nanoparticles for heat-resistant coatings and method of its production |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2904624A1 (en) * | 2006-08-04 | 2008-02-08 | Airbus France Sas | Preparing composite material made up of fibers dipped in geopolymeric sialate resin, useful in aircraft panel e.g. fire-proof panels, comprises removal of a part of lubrication from fibers before impregnating fibers with resin |
| CN101560071A (en) * | 2009-05-26 | 2009-10-21 | 广西大学 | Porous material of phosphate-based geopolymer and preparation method thereof |
| CN101628791A (en) * | 2009-06-25 | 2010-01-20 | 深圳航天科技创新研究院 | Geopolymer gel material for rush repairs and rush constructions |
| CN102456886A (en) * | 2010-10-26 | 2012-05-16 | 上海攀业氢能源科技有限公司 | Method for increasing bending strength of gas diffusion layer in fuel cell |
| CN103709592A (en) * | 2013-11-26 | 2014-04-09 | 武汉理工大学 | Method for improving ablation resistance of boron-containing phenolic resin-based composite material |
| CN104575894A (en) * | 2013-10-28 | 2015-04-29 | 深圳光启创新技术有限公司 | Light magnetic material, preparation method thereof and wave-absorbing plate |
| CN106883363A (en) * | 2017-03-09 | 2017-06-23 | 中国科学院化学研究所 | A kind of boron hydridization addition curable phenolic resin and its preparation method and application |
| CN109476544A (en) * | 2016-07-20 | 2019-03-15 | 西索斯公司 | For production geology polymer or the method for geopolymer composite material |
| CN110256082A (en) * | 2019-05-17 | 2019-09-20 | 浙江理工大学 | Reaction-sintered prepares monocrystalline silicon carbide nanofiber/carbon/silicon carbide ceramic matrix composite method |
| CN113320239A (en) * | 2021-06-15 | 2021-08-31 | 武汉中科先进技术研究院有限公司 | Basalt fiber reinforced wear-resistant composite material and preparation method thereof |
-
2021
- 2021-09-30 CN CN202111162475.7A patent/CN113831102B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2904624A1 (en) * | 2006-08-04 | 2008-02-08 | Airbus France Sas | Preparing composite material made up of fibers dipped in geopolymeric sialate resin, useful in aircraft panel e.g. fire-proof panels, comprises removal of a part of lubrication from fibers before impregnating fibers with resin |
| CN101560071A (en) * | 2009-05-26 | 2009-10-21 | 广西大学 | Porous material of phosphate-based geopolymer and preparation method thereof |
| CN101628791A (en) * | 2009-06-25 | 2010-01-20 | 深圳航天科技创新研究院 | Geopolymer gel material for rush repairs and rush constructions |
| CN102456886A (en) * | 2010-10-26 | 2012-05-16 | 上海攀业氢能源科技有限公司 | Method for increasing bending strength of gas diffusion layer in fuel cell |
| CN104575894A (en) * | 2013-10-28 | 2015-04-29 | 深圳光启创新技术有限公司 | Light magnetic material, preparation method thereof and wave-absorbing plate |
| CN103709592A (en) * | 2013-11-26 | 2014-04-09 | 武汉理工大学 | Method for improving ablation resistance of boron-containing phenolic resin-based composite material |
| CN109476544A (en) * | 2016-07-20 | 2019-03-15 | 西索斯公司 | For production geology polymer or the method for geopolymer composite material |
| CN106883363A (en) * | 2017-03-09 | 2017-06-23 | 中国科学院化学研究所 | A kind of boron hydridization addition curable phenolic resin and its preparation method and application |
| CN110256082A (en) * | 2019-05-17 | 2019-09-20 | 浙江理工大学 | Reaction-sintered prepares monocrystalline silicon carbide nanofiber/carbon/silicon carbide ceramic matrix composite method |
| CN113320239A (en) * | 2021-06-15 | 2021-08-31 | 武汉中科先进技术研究院有限公司 | Basalt fiber reinforced wear-resistant composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 曹海琳: "《玄武岩纤维》", 31 July 2017, 国防工业出版社 * |
| 杨涛: "碳纳米管修饰聚酰亚胺纤维增强磷酸基地质聚合物力学性能和介电性能的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ309669B6 (en) * | 2022-03-28 | 2023-06-28 | Univerzita Jana Evangelisty Purkyně V Ústí Nad Labem | Geopolymer suspension with nanoparticles for heat-resistant coatings and method of its production |
| WO2023187456A1 (en) * | 2022-03-28 | 2023-10-05 | Univerzita J. E. Purkyne V Usti Nad Labem | Geopolymer suspension containing nanoparticles for heat-resistant coatings and method of the production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113831102B (en) | 2022-07-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106699209B (en) | The preparation method of continuous alumina fiber enhancing alumina ceramic-base composites | |
| CN106977217B (en) | A kind of preparation method of high-strength and high-ductility silicon carbide fiber reinforced silicon carbide ceramic matric composite | |
| CN108658613B (en) | Method for preparing automobile brake disc by short fiber die pressing | |
| CN103553616B (en) | Growth in situ SiC nanowire strengthens C/SiC matrix material and preparation method thereof | |
| CN112341235B (en) | Multiphase coupling rapid densification method for ultrahigh-temperature self-healing ceramic matrix composite | |
| CN102976756B (en) | Continuous carbon fiber reinforced C-SiC binary base composite material and preparation method thereof | |
| CN107266075A (en) | A kind of C/C SiC ceramic matrix composite materials and its preparation method and application | |
| CN107417291A (en) | A kind of preparation method of quasi-isotropic SiC chopped mats toughening ceramic based composites | |
| CN103288468A (en) | Preparation method for fiber reinforced carbon-silicon carbide-zirconium carbide-based composite material | |
| CN111454071B (en) | Rock wool fiber reinforced silica-based high-strength heat insulation composite material and preparation method thereof | |
| Kotani et al. | Consolidation of polymer-derived SiC matrix composites: processing and microstructure | |
| CN111996473A (en) | Variable-structure ultrahigh-temperature ceramic matrix composite and preparation method thereof | |
| CN113800837B (en) | Continuous carbon fiber reinforced phosphate group geopolymer composite material and preparation method thereof | |
| CN103332943A (en) | Microstructure design and performance control method for preparing carbon-ceramic-based composite materials based on liquid silicon melt infiltration method | |
| CN108101566A (en) | The method that RTM technique auxiliary prepares carbon/silicon carbide ceramic matrix composite component | |
| CN104926347A (en) | Pantograph pan composite material for high-speed electric multiple units and preparation method of pantograph pan composite material | |
| CN109020588B (en) | Rapid preparation method of high-temperature-resistant structure wave-absorbing ceramic matrix composite | |
| CN108129156A (en) | A kind of carbon ceramic composite material and its precursor impregnation preparation method | |
| CN113831102B (en) | Continuous basalt fiber reinforced phosphate group geopolymer composite material and preparation method thereof | |
| CN104529499A (en) | Preparation method of self-healing silicon-carbide-fiber-reinforced silicon-boron-nitrogen-carbon composite material | |
| CN115417683A (en) | Preparation method of oxide continuous filament reinforced oxide ceramic matrix composite | |
| CN115744887A (en) | Enhanced reduced graphene oxide/carbon nanotube/pyrolytic carbon composite material and preparation method thereof | |
| CN108101543A (en) | A kind of silicon carbide-based carbon ceramic friction material and its molding preparation method | |
| CN113121253B (en) | Ultrahigh-temperature C/SiHfBCN ceramic matrix composite material and preparation method thereof | |
| CN104478460A (en) | Preparation method of fiber-enhanced silicon carbide composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |