CN116947450A - Inside and outside hydrophobic xonotlite type calcium silicate board and manufacturing method and application thereof - Google Patents
Inside and outside hydrophobic xonotlite type calcium silicate board and manufacturing method and application thereof Download PDFInfo
- Publication number
- CN116947450A CN116947450A CN202310560881.1A CN202310560881A CN116947450A CN 116947450 A CN116947450 A CN 116947450A CN 202310560881 A CN202310560881 A CN 202310560881A CN 116947450 A CN116947450 A CN 116947450A
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- China
- Prior art keywords
- calcium silicate
- hydrophobic
- xonotlite
- slurry
- silicate board
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- Pending
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- 239000000378 calcium silicate Substances 0.000 title claims abstract description 116
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 116
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 85
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000002002 slurry Substances 0.000 claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 85
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 239000002994 raw material Substances 0.000 claims abstract description 42
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 claims abstract description 34
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 17
- 238000004078 waterproofing Methods 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000843 powder Substances 0.000 claims description 143
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 90
- 239000000920 calcium hydroxide Substances 0.000 claims description 90
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 90
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 90
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 85
- 239000010453 quartz Substances 0.000 claims description 65
- 229920002545 silicone oil Polymers 0.000 claims description 61
- 239000000839 emulsion Substances 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 42
- 239000003365 glass fiber Substances 0.000 claims description 39
- 239000000835 fiber Substances 0.000 claims description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 31
- 229920001296 polysiloxane Polymers 0.000 claims description 30
- -1 polysiloxane Polymers 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 24
- 239000010881 fly ash Substances 0.000 claims description 24
- 239000012153 distilled water Substances 0.000 claims description 23
- 239000013078 crystal Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 229910052710 silicon Inorganic materials 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 238000004321 preservation Methods 0.000 claims description 15
- 239000005871 repellent Substances 0.000 claims description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002956 ash Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- 235000007164 Oryza sativa Nutrition 0.000 claims description 12
- 230000002940 repellent Effects 0.000 claims description 12
- 235000009566 rice Nutrition 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 239000011810 insulating material Substances 0.000 claims description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 4
- 229910021487 silica fume Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229920013822 aminosilicone Polymers 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 71
- 239000007787 solid Substances 0.000 description 37
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 12
- 241000209094 Oryza Species 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000003995 emulsifying agent Substances 0.000 description 7
- 238000001125 extrusion Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000012774 insulation material Substances 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 239000002120 nanofilm Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000004103 aminoalkyl group Chemical group 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 229920002313 fluoropolymer Polymers 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004795 extruded polystyrene foam Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010903 husk Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006327 polystyrene foam Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000007762 w/o emulsion Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/18—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 mixtures of the silica-lime type
- C04B28/186—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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step
- C04B28/188—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 mixtures of the silica-lime type containing formed Ca-silicates before the final hardening step the Ca-silicates being present in the starting mixture
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0259—Hardening promoted by a rise in pressure
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0263—Hardening promoted by a rise in temperature
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
-
- 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
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- 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
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses an inside and outside hydrophobic xonotlite type calcium silicate board and a preparation method and application thereof. The manufacturing method comprises the following steps: (1) preparing a siliceous material and a calcareous material; (2) Mixing and uniformly stirring the siliceous material and the calcareous material in water according to a required proportion; (3) Injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, and maintaining the temperature and pressure for 2-12 hours to obtain tobermorite slurry; (4) Adding reinforcing fibers and an organosilicon waterproofing agent into the tobermorite slurry obtained in the step (3), and then fully stirring; (5) And (3) extruding the slurry prepared in the step (4) in a die by using a hydraulic press, and drying to obtain the finished product.
Description
Technical Field
The invention relates to the technical field of inorganic heat preservation and insulation materials, in particular to an inside and outside hydrophobic xonotlite type calcium silicate board, a manufacturing method and application thereof.
Background
Organic thermal insulation materials such as molded polystyrene foam (EPS), extruded polystyrene foam (XPS) and the like cannot generally reach A-level incombustibility, and the conventional inorganic thermal insulation materials such as rock wool, thermal insulation mortar and the like have the problems of easy water absorption, unstable thermal conductivity and the like.
The xonotlite type calcium silicate heat-insulating material has good heat-insulating property, fire-resisting property and specific strength, and has wide application in the fields of heat insulation, fire prevention and the like of high-temperature kilns and equipment. The synthesis method has several methods, wherein the dynamic hydrothermal method is a wet chemical method completed in a closed container, and compared with other methods, the method has the advantages that crystal particles can be directly obtained without high-temperature sintering, so that hard agglomeration of particles is avoided, and grinding and impurities brought by the method are also omitted; the method is favorable for growing crystals with few defects and good orientation, and the synthesized product has high crystallinity and is easy to control the granularity of the product crystals. The obtained powder has high purity, good dispersibility, uniformity, narrow distribution, no agglomeration, good crystal form, controllable shape, and the like, and is beneficial to environmental purification.
The reaction for hydrothermally producing xonotlite is carried out in an aqueous solution throughout, and water is taken as a raw material to participate in the reaction, and provides a necessary reaction environment, plays an important role in synthesizing the xonotlite, so that the use amount of water as a solvent is large. The chemical molecular formula of the xonotlite is 6CaO6SiO 2 H 2 O, the crystal is fibrous or needle-shaped, under certain conditions they can cross-connect each other, forming chestnut-like spherical particles-secondary particles. From the structural formula of xonotlite, it can be seen that little water is required in synthesizing the xonotlite crystals. But in actual waterWhen the xonotlite is synthesized thermally, it is difficult to synthesize the xonotlite with too little water because the xonotlite needs to have a certain vapor pressure and fluidity. The water-to-solid ratio is the ratio of the mass of water to the total mass of solids in the slurry before reaction. The water-solid ratio is small, which is unfavorable for SiO 2 The slurry is too thick in the reaction process, which is unfavorable for the normal operation of the reaction, so that spherical agglomerates are difficult to form. The water-solid ratio is large, which is favorable for improving the reaction efficiency, but the water-solid ratio greatly reduces the production efficiency of the material and increases the energy consumption, and meanwhile, the generated tobermorite spherical aggregate structure is loose, so that the selection of the proper water-solid ratio is very important for synthesizing the tobermorite spherical aggregate. In the prior art, when the dynamic hydrothermal method is used for preparing the xonotlite, the water-solid ratio is at least more than 20, the water-solid ratio is at a low limit, and when the water-solid ratio is 20, the xonotlite can be only generated, but the reaction is incomplete, and the generated xonotlite has poor development. Journal "influence of water-solid ratio on hydrothermal synthesis of spherical aggregates of tobermorite", authors: ni Wen on page 2005.3 of the new construction materials P53-55, it is mentioned that when the water-solid ratio is 25, a certain amount of flocculent substances which do not develop into fibers exist on the surface of the synthesized sphere, and at the same time, the fibers do not develop well, and a large amount of bulk powdery colloid which corresponds to the incomplete reaction of the powdery quartz in the reaction product exists. Only when the water-solid ratio reaches 40, the pellets are better, the fiber morphology is clear, and the reaction products are completely reacted. Patent application publication No. JP09048653a, application publication No. 19970218, application name "production of water repellent calcium silicate-based molding" in which the water-solid ratio is 20-40. The current dynamic hydrothermal method has the defects that a large amount of water is required to be used and a large amount of wastewater is also generated, which is an important reason for restricting the popularization and application of the xonotlite products, and the difficult problem that how to reduce the use of water and the production water and wastewater to reduce pollution as much as possible is required to be solved for producing the xonotlite products on a large scale.
In addition, the xonotlite type calcium silicate board is not only a heat insulation material, but also an excellent fireproof material, and can be used as an ideal integrated material in the future. Many inner wall heat-insulating buildings in European and American countries use calcium silicate boards, and most of the buildings in China are heat-insulating outer walls, and the main reason for restricting the calcium silicate boards to be on the walls is that the materials are of microporous structures, are easy to absorb water, and cannot be used on the outer walls of the buildings. Once the plate absorbs water, the heat preservation effect is greatly weakened, and the temperature is lower than 0 ℃ and can cause freezing injury. At present, most of the manufacturing processes of waterproof calcium silicate boards in the market are to coat waterproof materials on the surfaces of boards, but the manufacturing method only enables the surfaces of the boards to have waterproof performance, the inside of the heat insulation materials still has strong water absorption, and once the waterproof layers on the surfaces are damaged, the waterproof effect is weakened or lost. Patent application publication number CN102825650a, application publication date 2012.12.19, application name "a high-strength light-weight integral hydrophobic xonotlite insulation fireproof board", though a large amount of inorganic glue is added, the addition amounts of inorganic glue and organic silicon are respectively up to 8% of the mass of slurry, although the water-solid ratio used is not mentioned in the document, according to the value of the common water-solid ratio and the condition of the slurry, the solid content of xonotlite in the slurry is about 10% at most, the addition amounts of inorganic glue and organic silicon are about equal to or even more than the amount of xonotlite, and the total mass of the two substances of the final product can far exceed the mass of xonotlite itself, which can seriously affect the performance of the product. The above-mentioned patent application publication No. JP09048653a, application publication date 19970218, filed under the name "production of water repellent calcium silicate-based molding", in which an organofluorine compound is added as a water repellent, is used in the form of an emulsion or in the form of a solution using a suitable hydrophilic organic solvent as a solvent. Therefore, the waterproof agent is easy to dissolve in a water system in the use process, and the waterproof agent is lost in a large amount along with water in the extrusion dehydration step of the later calcium silicate board. In addition, compounds with perfluoroalkyl chains having more than 7 carbon atoms are difficult to degrade in nature, have bioaccumulation and toxicity, have been banned in many countries, and long fluorocarbon chain-containing compounds are also subject to environmental safety concerns. It oxidizes in natural environment, and the product is one of the most difficult organic pollutants to degrade at present, which causes serious harm to human health and environment. In addition, the price of the organic fluorine material is higher than that of the organosilicon. The development of a xonotlite type calcium silicate board with good hydrophobic effect on the inner side and the outer side and no toxicity or harm becomes one of the technical problems to be solved in the field.
In order to solve the technical problems, the invention provides an internal and external hydrophobic xonotlite type calcium silicate board, and a manufacturing method and application thereof. The calcium silicate heat-insulating material produced by the method has the advantages of high temperature resistance, high strength, good heat-insulating effect, good water resistance, fire resistance, high safety, stable physicochemical property, good durability, simple and convenient construction, no toxicity, no harm and the like, and also saves a large amount of production water.
The invention aims at providing an inside and outside hydrophobic xonotlite type calcium silicate board, which comprises siliceous materials, calcareous materials, water and organosilicon waterproofing agents, wherein the organosilicon waterproofing agents are hydrophobic modified silicone oil or oily organosilicon emulsion, and the organosilicon waterproofing agents are added into slurry after the reaction of the siliceous materials and the calcareous materials for mixed use when the calcium silicate board is prepared.
Preferably, the organosilicon waterproofing agent is added in an amount of 0.1 to 10% by mass of the total mass of both the siliceous material and the calcareous material.
Preferably, when the water repellent is a hydrophobic modified silicone oil, it is added in an amount of 0.1% to 0.8% by mass of the total mass of both the siliceous material and the calcareous material.
The hydrophobic modified silicone oil can be any hydrophobic modified silicone oil, including but not limited to any one or a combination of the following: hydrophobic amino long-chain alkyl modified silicone oil, hydrophobic hydrogen-containing silicone oil, hydrophobic long-chain alkyl polysiloxane and hydrophobic amino silicone oil.
Preferably the siliceous material comprises quartz powder, silica fume or rice husk ash; the calcareous material comprises slaked lime slurry or slaked lime powder.
Preferably, the silicon atom and calcium atom molar ratio of the siliceous material and the calcareous material is 1:0.8 to 1.2.
The water is added in an amount of 5 to 40 times by mass of the total mass of the siliceous material and the calcareous material, preferably 8 to 12 times by mass of the total mass of the siliceous material and the calcareous material, and most preferably 10 times by mass of the total mass of the siliceous material and the calcareous material.
Preferably, the raw material further includes reinforcing fibers, and the reinforcing fibers are at least one of glass fibers, carbon fibers, pulp, lint, polyester fibers, and polyacrylonitrile fibers.
Preferably, the reinforcing fiber is added in an amount of 1 to 8% by mass based on the total mass of both the siliceous material and the calcareous material;
Preferably, the raw materials further comprise fly ash, and the addition amount of the fly ash is 0-40% of the total mass of the siliceous material and the calcareous material.
Another object of the present invention is to provide a method for manufacturing the inside and outside hydrophobic xonotlite-type calcium silicate board, comprising the following steps:
(1) Preparing a siliceous material and a calcareous material;
(2) Mixing and uniformly stirring the siliceous material and the calcareous material in water according to a required proportion;
(3) Injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 200-380 ℃, and starting to heat the reaction kettle to ensure that the temperature in the reaction kettle reaches 200-250 ℃ and the pressure is 1.5-3MPa, and preserving heat and pressure for 2-12 hours at the temperature and the pressure to obtain tobermorite slurry;
(4) Adding reinforcing fibers and an organosilicon waterproofing agent into the tobermorite slurry obtained in the step (3), and then fully stirring to fully contact and mix all substances in the slurry, wherein the organosilicon waterproofing agent is hydrophobic modified silicone oil or oily organosilicon emulsion;
(5) And (3) extruding the slurry prepared in the step (4) in a die by using a hydraulic press, and drying to obtain the inside and outside hydrophobic xonotlite type calcium silicate board.
Preferably, the specific steps are as follows:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) Injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 300-350 ℃, the reaction kettle starts to heat up, the heating rate is 1-2.5 ℃/min, the final temperature in the reaction kettle reaches 200-230 ℃, the pressure reaches 1.5-2.0MPa, and then, the slurry taking tobermorite crystals as main components is prepared after heat preservation and pressure maintaining for 6 hours; wherein the stirring speed in the kettle is 250-320r/min in the heating process, the stirring speed in the heat preservation process is 80-120r/min, and the stirring speed in the cooling process is 80-120r/min;
(4) Adding the xonotlite slurry obtained in the step (3) into the reinforcing fiber and the hydrophobic modified silicone oil and fully stirring for 10-20min until the reinforcing fiber and the hydrophobic modified silicone oil are fully and uniformly mixed with the slurry;
(5) And (3) extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the calcium silicate board with hydrophobicity on the whole inside and outside.
Preferably, in the step (4), fly ash is added in addition to the reinforcing fiber and the silicone waterproofing agent.
The xonotlite type calcium silicate board is used as an energy-saving heat-insulating material or is compounded with heat-insulating, fireproof and decorative materials to prepare a multifunctional composite heat-insulating material.
The slaked lime powder is calcium hydroxide powder.
Preferably, when the invention adopts oily organosilicon emulsion as the waterproofing agent, the preparation method of the calcium silicate board is as follows:
a manufacturing method of an inside and outside hydrophobic xonotlite type calcium silicate board comprises the following steps:
(1) Mixing and stirring siliceous material and calcareous material in water uniformly; wherein, the mol ratio of silicon atoms to calcium atoms in the siliceous material and the calcareous material is 1:0.8 to 1.2;
(2) Injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam to enable the temperature in the reaction kettle to reach 180-250 ℃ and the pressure to reach more than 1.5MPa, and then preserving heat and pressure; the method reaches chemical reaction conditions for generating the xonotlite, and the slurry taking the xonotlite crystal as a main component can be prepared through the step.
(3) Adding reinforcing fibers accounting for 1% -8% of the total mass of the solids into the tobermorite slurry obtained in the step (2), then adding the oily organic silicon emulsion, and fully stirring to enable the solids in the slurry to fully contact and mix with the oily organic silicon emulsion;
(4) And (3) extruding the slurry prepared in the step (3) in a die by using a hydraulic press, and drying to obtain the inside and outside hydrophobic xonotlite type calcium silicate board.
Wherein in the step (1), the siliceous material comprises quartz powder, silica fume, rice husk ash, or the like.
Wherein in the step (1), the calcareous material is slaked lime slurry or calcium hydroxide powder (slaked lime powder).
Wherein in the step (1), the water-solid ratio is 5-40:1.
wherein in the step (2), the temperature and the pressure are maintained for 2-12 hours.
In the step (3), the reinforcing fiber is at least one of glass fiber, carbon fiber, paper pulp, cotton velvet, polyester fiber and polyacrylonitrile fiber.
In the step (3), the oily organic silicon emulsion accounts for 1-10% of the total mass of the solid.
The emulsion is also called milk liquid, is an emulsifying system formed by two mutually incompatible phases and a specific emulsifying agent, has lower viscosity, can be poured under the action of gravity and can flow at normal temperature. Wherein fine droplets of one liquid are uniformly dispersed in another liquid, the former being referred to as the dispersed phase and the latter being referred to as the continuous phase. The organic liquid constituting the emulsion is conventionally referred to as "oil (O)". If the oil phase is dispersed in water (W), it is referred to as an oil-in-water emulsion (O/W); otherwise, it is called water-in-oil emulsion (W/O). The emulsion is unstable and phase separation is easy to occur, and the stability of the emulsion can be improved by adding the emulsifier. So generally whatever "emulsion" is composed of an oil phase and an emulsifier and a large amount of water. Wherein the emulsifier is a substance which enables a mixed liquid of two or more components different from each other to form a stable emulsion. The emulsifier is a surfactant, and has hydrophilic group and lipophilic group in the molecule.
Since many types of water repellent which are not hydrophilic, such as silicone oils and organic fluorine compounds, are hydrophobic, they are difficult to disperse in water systems, and it is widely known in the art that these water repellent which are hydrophobic must be used in the form of a hydrophilic emulsion or in the form of a solution using a suitable hydrophilic organic solvent as a solvent. The description of the above-mentioned patent application JP09048653A, page 1, section 0011, explicitly states that: "since the oily fluoropolymer is insoluble in water, it is used in the form of an emulsion or in the form of a solution using a suitable hydrophilic organic solvent as solvent. As can be seen from the above, the present application is not a pure oily fluoropolymer product, but a mixed solution of an emulsifier and a large amount of water or a hydrophilic solvent. From the foregoing, it can be seen that while the fluoropolymer used in this application is not hydrophilic, it is ultimately used in the form of a hydrophilic emulsion or mixed solution. It is demonstrated by the application of example 9 and comparative examples 1 and 2 that the use of a water repellent in the form of a hydrophilic emulsion causes a large amount of water loss of the water repellent, greatly affecting the water repellent effect.
At present, most of organosilicon emulsions on the market are water-based and are only suitable for manufacturing surface-hydrophobic calcium silicate boards, and the defects are three: firstly, the concentration of the emulsion is greatly reduced after the emulsion is diluted by water, so that the solid in the slurry is difficult to fully produce a waterproof effect; secondly, the consumption of the prepared completely hydrophobic material on the aqueous emulsion is great; thirdly, the emulsion is difficult to separate from water after being dissolved in water, and water pollution can be caused.
The oily organosilicon emulsion adopted by the invention is an emulsion which is changed into oily after the organosilicon emulsion is modified for one or more times, for example, the organosilicon emulsion taking amino fluoropropyl polysiloxane as a main component. Oil-based silicone emulsions produced by silicone oil manufacturers such as German Wake and American Dow Corning are suitable for producing hydrophobic xonotlite-type calcium silicate boards both inside and outside, although the production processes of the manufacturers are different.
The oily organosilicon emulsion of the invention is fully contacted and adsorbed with calcium silicate particles in slurry by stirring, so that a layer of organosilicon molecular film with extremely strong hydrophobicity is generated on the surface of the calcium silicate particles in microcosmic. After the slurry is dehydrated, the organic silicon molecular film still adheres to the surface of the calcium silicate particles, and the calcium silicate has hydrophobicity.
The oily organosilicon emulsion adopted by the application is insoluble in water, cannot be diluted by water, and cannot be discharged from a solid product along with water like the aqueous organosilicon emulsion, so that the application has higher utilization rate and better hydrophobic effect. Because the oily emulsion is not compatible with water, the production wastewater can be quickly separated from water after standing, thereby not only being convenient for recycling waterproof materials, but also avoiding the problem of water pollution. In the production process, the hydrophobic rate of the final product can reach more than 98 percent as long as the oily organosilicon emulsion is fully and uniformly mixed.
In addition, the application surprisingly discovers that the hydrophobic modified silicone oil is directly used in the preparation process, rather than being prepared into emulsion by re-preparing the modified silicone oil as in the prior art, so that the final result is that the waterproof agent is not dispersed poorly, but the waterproof effect is better, and the final hydrophobic rate of the product reaches almost hundred percent. The dosage of the waterproof agent is greatly reduced, and the waterproof agent is only required to occupy a few thousandths of the mass of the solid at least. Thus not only improving the water repellent rate, but also greatly reducing the usage amount of the water repellent. The water-proofing agent adopts the phenomenon that the emulsion type effect is inferior to that of directly adopting the hydrophobic modified silicone oil pure product, and one reason for analysis is that the emulsion is hydrophilic or oleophilic, and usually contains surfactants such as emulsifying agent, and the surfactants all have hydrophilic groups, and the xonotlite slurry contains a large amount of water, so that the whole slurry is in a very thin state, the surfactants can easily react with the water in the slurry so as to dissolve in the water, and the production of the calcium silicate board has extrusion molding steps, so that when the slurry is extruded and molded, the water extrusion is carried with a plurality of surfactants and the silicon-based water-proofing agent combined with the surfactants. Therefore, it is preferable that the surfactant-containing substance is not added to the raw material of the present application, since the use effect of the silicone waterproofing agent is affected by both the lipophilic and hydrophilic substances.
The application directly adopts hydrophobic modified silicone oil, and the modified silicone oil is fully contacted with calcium silicate particles in slurry for adsorption or chemical reaction by stirring, so that a layer of organic silicon molecular film with extremely strong hydrophobicity is generated on the surface of the calcium silicate particles in microcosmic. After the slurry is dehydrated, the organic silicon molecular film still adheres to the surface of the calcium silicate particles, and the calcium silicate has hydrophobicity. Meanwhile, through relevant performance tests, the application directly adopts the hydrophobic modified silicone oil, so that the compressive strength and the flexural strength of the prepared calcium silicate board are greatly improved. For analysis reasons, it can be seen from the electron microscope photographs (see fig. 6 and 7) of the internal cross section of the calcium silicate board that the cylindrical glass fiber in the calcium silicate board of fig. 7 of the present application is adhered with a large number of fibers, whereas the glass fiber surface of fig. 6 using the silicone oil waterproofing agent in the form of hydrophilic emulsion is smoother, and only a very small number of fibers are adhered thereto, and the main component of the fibers should be tobermorite. The modified silicone oil of the application not only tightly combines with the calcium silicate fiber, but also tightly combines with the glass fiber, so that the xonotlite fiber and the glass fiber are tightly combined together through the modified silicone oil, thus greatly improving the cohesive force between the materials, improving the mechanical property of the materials and preventing moisture from invading the interface between the glass fiber and the calcium silicate fiber. On the other hand, because it is also closely combined on the surface of the glass fiber, a layer of film is formed, so that the integrity of the surface of the fiber can be improved, the film also plays a role in protecting the fiber, the tensile strength of the fiber can be improved, and the fiber is prevented from being damaged in wiredrawing.
The added fly ash is fine ash collected from flue gas after coal combustion, and the fly ash is main solid waste discharged from a coal-fired power plant. Along with the development of the power industry, the emission of the fly ash of the coal-fired power plant is increased year by year, and the fly ash becomes one of industrial waste residues with larger current discharge capacity in China. A large amount of fly ash is not treated, so that dust can be generated and the atmosphere is polluted; drainage into water causes river silting, and toxic chemicals in the water can also cause harm to human bodies and organisms. The invention consumes solid waste by utilizing the fly ash, and reduces environmental pollution. And by adding the fly ash, the mechanical property and the fire resistance of the prepared calcium silicate board are obviously improved.
In the prior art, the water-solid ratio of the preparation of the xonotlite-type calcium silicate board is at least 20 in small-sized experiments in a laboratory even if the preparation is carried out on a large-sized industrial production device: 1 and basically when the water-to-solid ratio is more than 20, the fiber of the finally synthesized tobermorite does not develop well, and the sphere has a large amount of undeveloped floccules. Some are better to ball when the water-solid ratio reaches 40. The method adopts proper raw materials and scientific methods and process conditions, and scientifically designs the stirring rate from pressure to temperature to each stage, and the like, and when the water-solid ratio is only 8-12 times, the method successfully prepares the xonotlite type calcium silicate board with good fiber development and complete reaction.
The raw materials of the tobermorite-type calcium silicate board of the present invention include, but are not limited to, the above-mentioned parts, for example, for various needs, the raw materials of the calcium silicate board of the present invention may be further added with water glass, tobermorite seed crystal, etc., or with some metal ions, or with a small amount of a protein-based foaming agent, or with other auxiliary agents or binders such as cement-based for reinforcement.
After the tobermorite slurry of the present invention is prepared, post-forming methods include, but are not limited to, compression dehydration forming, any of the existing methods.
The xonotlite type calcium silicate board prepared by the invention can be independently used as an energy-saving heat-insulating material, and can also be compounded with other heat-insulating, fireproof and decorative materials such as stone, extruded sheets, vermiculite sheets and the like to prepare a multifunctional composite heat-insulating material.
The xonotlite-type calcium silicate board of the invention can also be used to change density or other parameters to achieve different properties according to the application in different fields. Density values for the xonotlite-type calcium silicate boards of the present invention include, but are not limited toThe several types provided in the examples can be used to produce calcium silicate boards of different densities to meet various needs by adjusting the amount of slurry added to the mold during the extrusion step of the manufacturing process. For example, a density of 170kg/m 3 、220kg/m 3 、250kg/m 3 、300kg/m 3 、400kg/m 3 Etc.
Advantageous effects
Compared with the prior art, the hydrophobic rate of the inside and outside hydrophobic xonotlite type calcium silicate boards prepared by the invention reaches more than 98 percent. The method solves the technical defect that the calcium silicate board in the prior art has stronger water absorption, and avoids the defect that the strength and the heat preservation effect of the calcium silicate board are poor due to a large amount of water absorption. The waterproof material used in the preparation method can generate sufficient adsorption and combination effects with the calcium silicate particles, and a waterproof layer is generated on the surfaces of the particles, so that the inside and outside of the calcium silicate product have hydrophobicity, and the waterproof effect is greatly improved. Particularly, the invention directly adopts the hydrophobic modified silicone oil as the waterproof agent, so that the hydrophobic rate is further improved to be nearly 100 percent under the condition that the dosage of the waterproof agent is greatly reduced. And the modified silicone oil also tightly combines the xonotlite fiber and the glass fiber together, so that the mechanical property of the material is greatly improved. In addition, the manufacturing method of the invention overcomes the technical prejudice that the water-solid ratio in the prior art is more than 20 by scientifically selecting raw materials and adopting a reasonable design technical scheme, and the water-solid ratio is only 8-12: under the condition of 1, the tobermorite with better balling and clear fiber morphology and complete reaction of the reaction product is prepared, so that the use of water for production is greatly reduced, the pollution problem of waste water is reduced as much as possible, and the production cost is saved.
Drawings
FIG. 1A is an electron micrograph of a ground calcium silicate plate obtained in example 7
FIG. 2 nuclear magnetic resonance spectrum of long-chain alkyl-modified polysiloxane used in example 8
FIG. 3 report of the hydrophobicity of the entirety of the calcium silicate board of example 8
FIG. 4 IR spectrum of hydrogen-containing silicone oil used in example 9
FIG. 5 Infrared Spectrometry of the Hydrogen-containing Silicone oil emulsion used in comparative example 1
FIG. 6 is an electron micrograph of the internal structure of a calcium silicate plate of comparative example 2
FIG. 7 is an electron micrograph of the internal structure of a calcium silicate board according to example 8
FIG. 8 IR spectrum of amino-modified silicone oil of example 11
Detailed Description
The present invention will be further described with reference to specific examples and drawings, by way of illustration, to thereby enable the invention to be practiced and to thereby enable those skilled in the art to make a more complete description of the invention. This invention may be embodied in many different forms of embodiments and its scope is not limited to the embodiments described herein, but rather the drawings and description are to be regarded as illustrative in nature and not as restrictive.
The experimental methods in the following examples are conventional methods unless otherwise specified.
The raw materials, reagents and equipment used in the examples described below, unless otherwise specified, are all commercially available or disclosed.
The nuclear magnetic resonance spectrometer is AVANCE III 600M type manufactured by BRUKER company, and deuterated chloroform is used as solvent.
The Fourier infrared spectrometer is 760 type manufactured by thermoelectric corporation in America, and adopts transmission scanning with 4000-400cm scanning interval -1 。
The electron microscope was manufactured by Chuiss, germany.
Example 1
A method for manufacturing an inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing quartz powder with the silicon dioxide content reaching 98% and the 400-mesh screen allowance not exceeding 5%; preparing slaked lime powder with calcium hydroxide content up to 90% and 325 mesh screen residue not more than 5%.
(2) Quartz powder and slaked lime powder are mixed according to the mole ratio of silicon atoms to calcium atoms of 1:1 are mixed in water and stirred uniformly.
(3) The evenly mixed raw materials are injected into a dynamic synthesis reaction kettle, high-temperature steam is introduced to enable the temperature in the reaction kettle to reach 220 ℃, the pressure to reach 1.8MPa, and then the temperature and the pressure are kept for 6 hours, so that the slurry taking the xonotlite crystal as a main component is prepared.
(4) Adding the tobermorite slurry obtained in the step (3) into glass fiber accounting for 3% of the total mass, then adding oily organosilicon emulsion accounting for 3% of the total mass of the slurry, and fully stirring.
(5) Extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain a calcium silicate board with hydrophobicity on the whole inside and outside, namely a sample A, wherein the density is 220kg/m 3 。
Example 2
A method for manufacturing an inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing silica fume with silica content up to 98% and 400 mesh sieve residue not exceeding 5%; preparing slaked lime powder with calcium hydroxide content up to 90% and 325 mesh screen residue not more than 5%.
(2) Quartz powder and slaked lime powder are mixed according to the mole ratio of silicon atoms to calcium atoms of 0.9:1 are mixed in water and stirred uniformly.
(3) The evenly mixed raw materials are injected into a dynamic synthesis reaction kettle, high-temperature steam is introduced to enable the temperature in the reaction kettle to reach 250 ℃, the pressure to reach 2.3MPa, and then the temperature and the pressure are kept for 4 hours, so that the slurry taking the xonotlite crystal as a main component is prepared.
(4) Adding 4% of polyester fiber by total mass into the tobermorite slurry obtained in the step (3), then adding 5% of oily organic silicon emulsion by total mass of the slurry, and fully stirring.
(5) And (3) extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the calcium silicate board with hydrophobicity on the whole inside and outside, namely the sample B.
Example 3
A method for manufacturing an inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing rice hull ash with the silicon dioxide content reaching 98 percent and the 400-mesh sieve residue not exceeding 5 percent; preparing slaked lime powder with calcium hydroxide content up to 90% and 325 mesh screen residue not more than 5%.
(2) Quartz powder and slaked lime powder are mixed according to the mole ratio of silicon atoms to calcium atoms of 1.1:1 are mixed in water and stirred uniformly.
(3) The evenly mixed raw materials are injected into a dynamic synthesis reaction kettle, high-temperature steam is introduced to enable the temperature in the reaction kettle to reach 200 ℃, the pressure to reach 1.6MPa, and then the temperature and the pressure are kept for 12 hours, so that the slurry taking the xonotlite crystal as a main component is prepared.
(4) Adding the tobermorite slurry obtained in the step (3) into carbon fiber accounting for 1% of the total mass, then adding oily organosilicon emulsion accounting for 5% of the total mass of the slurry, and fully stirring.
(5) And (3) extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the calcium silicate board with hydrophobicity on the whole inside and outside, namely the sample C.
Examples 4 to 6
The same components and preparation process as in example 1 were used to prepare plates having different densities, i.e., samples D to F, with densities of 170kg/m, respectively, by changing only the amount of slurry added in the mold in step (5) 3 、300kg/m 3 、400kg/m 3 。
The inside and outside hydrophobic xonotlite type calcium silicate boards prepared in examples 1 to 4 were subjected to performance test, and the test results and the test criteria are shown in Table 1 below.
TABLE 1
As shown by the detection results of the table, the inside and outside hydrophobic xonotlite type calcium silicate board prepared by the invention has the advantages of high specific strength, low heat conductivity, no water absorption and the like, has excellent fireproof performance, and has great application value for improving the building safety, especially the fireproof safety.
Example 7
A xonotlite-type calcium silicate board, comprising the following raw materials: quartz powder, slaked lime powder and distilled water;
wherein the silicon dioxide content in the quartz powder reaches 98%, and the 400-mesh sieve residue is not more than 5%; the calcium hydroxide content of the slaked lime powder reaches 90%, and the 325 mesh sieve residue is not more than 5%; the adding proportion of the quartz powder and the slaked lime powder is that the mol ratio of silicon atoms to calcium atoms is 1:1, a step of; the distilled water is added in an amount such that the water-to-solid ratio (i.e., the ratio of the mass of water to the total mass of both the quartz powder and the slaked lime powder) is 10:1.
the method for manufacturing the calcium silicate board in the embodiment 7 comprises the following specific steps:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) Injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 310 ℃, the reaction kettle starts to heat up, the heating rate is 1.5 ℃/min, the final temperature in the reaction kettle reaches 220 ℃, the pressure reaches 1.8MPa, and then, the temperature and the pressure are kept for 6 hours, and then, the temperature is reduced, so that the slurry taking the xonotlite crystal as a main component is prepared; wherein the stirring speed in the kettle is 300r/min in the heating process, the stirring speed in the heat preservation process is 100r/min, and the stirring speed in the cooling process is 100r/min;
(4) Extruding the slurry obtained in the step (3) in a die by using a hydraulic press, and drying to obtain the calcium silicate board, wherein the density is 220kg/m 3 Is a plate of (a).
Correlation test: a small amount of sample of the calcium silicate board is ground into powder for electron microscopy detection, and the result is shown in figure 1.
As can be seen from fig. 1 (a), the spherical particles Mao Lizhuang formed in this embodiment are obvious, the spherical particles are better, the surface of the spherical particles are needle-shaped tobermorite fiber crystals which are better developed, and the morphology of the fibers is clear. It can be seen from FIG. 1 (b) that the reaction product consists of xonotlite. It can be proved that the water-solid ratio of the invention is only 10: under the condition of 1, the tobermorite with better balling and clear fiber morphology and complete reaction of the reaction product can be obtained.
Example 8
A xonotlite-type calcium silicate board, comprising the following raw materials: quartz powder, slaked lime powder, distilled water, glass fiber and hydrophobic long-chain alkyl modified polysiloxane;
wherein the silicon dioxide content in the quartz powder reaches 98%, and the 400-mesh sieve residue is not more than 5%; the calcium hydroxide content of the slaked lime powder reaches 90%, and the 325 mesh sieve residue is not more than 5%; the adding proportion of the quartz powder and the slaked lime powder is that the mol ratio of silicon atoms to calcium atoms is 1:1, a step of; the distilled water is added in an amount such that the water-to-solid ratio (i.e., the ratio of the mass of water to the total mass of both the quartz powder and the slaked lime powder) is 10:1, a step of; the mass of the glass fiber is 3% of the total mass of the quartz powder and the slaked lime powder; the mass of the long-chain alkyl modified polysiloxane is 0.3% of the total mass of the quartz powder and the slaked lime powder.
The long-chain alkyl modified polysiloxane was subjected to nuclear magnetic resonance test, and the results are shown in FIG. 2. The nuclear magnetic resonance spectrometer is AVANCE III 600M type manufactured by BRUKER company, deuterated chloroform is used as solvent, and the 1H-NMR and 13C-NMR spectra of FIG. 2a and FIG. 2b can be seen, wherein the sample is polysiloxane with long chain alkyl.
The manufacturing method of the inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) And (3) injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 310 ℃, the reaction kettle starts to heat up, the heating rate is 1.5 ℃/min, the final temperature in the reaction kettle reaches 220 ℃, the pressure reaches 1.8MPa, and then, the temperature and the pressure are kept for 6 hours, and then, the temperature is reduced, so that the slurry taking the xonotlite crystal as a main component is prepared. Wherein the stirring speed in the kettle is 300r/min in the heating process, the stirring speed in the heat preservation process is 100r/min, and the stirring speed in the cooling process is 100r/min;
(4) Adding glass fibers and long-chain alkyl modified polysiloxane into the tobermorite slurry obtained in the step (3) and fully stirring, wherein the stirring speed is 80r/min, and the stirring time is 15min until the glass fibers and the long-chain alkyl modified polysiloxane are fully and uniformly mixed with the slurry.
(5) Extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the product with the density of 220kg/m 3 The inside and outside of the (C) are provided with hydrophobic calcium silicate plates.
The entire calcium silicate board of this example was subjected to a hydrophobicity test, the hydrophobicity of which was 99.4%, and the specific report results are shown in fig. 3.
Example 9
A xonotlite-type calcium silicate board, comprising the following raw materials: quartz powder, slaked lime powder, distilled water, glass fiber and hydrophobic hydrogen-containing silicone oil;
wherein the silicon dioxide content in the quartz powder reaches 98%, and the 400-mesh sieve residue is not more than 5%; the calcium hydroxide content of the slaked lime powder reaches 90%, and the 325 mesh sieve residue is not more than 5%; the adding proportion of the quartz powder and the slaked lime powder is that the mol ratio of silicon atoms to calcium atoms is 1:0.8; the distilled water is added in an amount such that the water-to-solid ratio (i.e., the ratio of the mass of water to the total mass of both the quartz powder and the slaked lime powder) is 12:1, a step of; the mass of the glass fiber is 8% of the total mass of the quartz powder and the slaked lime powder; the mass of the hydrogen-containing silicone oil is 0.8 percent of the total mass of the quartz powder and the slaked lime powder.
The hydrogen-containing silicone oil used in this example is hydrophobic and its infrared spectrum is shown in fig. 4.
The manufacturing method of the inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) And (3) injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 320 ℃, the reaction kettle starts to heat up, the heating rate is 1.8 ℃/min, the final temperature in the reaction kettle reaches 230 ℃, the pressure reaches 2.3MPa, and then, the temperature and the pressure are maintained for 5.5 hours, and then, the temperature is reduced, so that the slurry taking the tobermorite crystal as a main component is prepared. Wherein the stirring speed in the kettle is 280r/min in the heating process, 110r/min in the heat preservation process and 90r/min in the cooling process;
(4) Adding glass fiber and hydrogen-containing silicone oil into the tobermorite slurry obtained in the step (3) and fully stirring for 20min until the glass fiber and the hydrogen-containing silicone oil are fully and uniformly mixed with the slurry.
(5) Extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the product with the density of 220kg/m 3 The inside and outside of the (C) are provided with hydrophobic calcium silicate plates.
Comparative example 1
The hydrophilic hydrogen-containing silicone oil emulsion prepared from the hydrogen-containing silicone oil of example 9 is used for replacing the preparation of the tobermorite plate, and other raw materials, proportions, reaction steps and conditions are the same as those of example 9.
The appearance of the hydrogen-containing silicone oil emulsion is milky white water-like liquid and hydrophilic. The infrared spectrum chart is shown in figure 5, and the spectrum chart shows that besides the absorption peak of hydrogen-containing silicone oil, a large amount of water absorption peak exists.
The prepared xonotlite type calcium silicate board is subjected to waterproof performance test, the inside of the calcium silicate board is opened, water is respectively splashed on the outer surface of the board and the internal section of the opened board, and the phenomenon is that: whether the outer surface of the board and the open inner section are substantially waterproof, water penetrates the board to varying degrees, forming a wet watermark.
Comparative example 2
The amount of the emulsion added was increased from 0.8% by mass of the total mass of both the quartz powder and the hydrated lime powder in comparative example 1 to 15%, and other raw materials, proportions, and reaction steps and conditions were the same as those in comparative example 1, to prepare a xonotlite-type calcium silicate board.
The prepared xonotlite type calcium silicate board is subjected to a waterproof performance test, the inside of the calcium silicate board is opened, water is respectively splashed on the outer surface of the board and the opened inner section, and as a result, the original six outer surfaces of the board have no obvious water absorption phenomenon, the outer surface of the board can be proved to be basically hydrophobic, water absorption points with different degrees appear on the surface of the inner section of the board, and the surface of the section presents irregularly distributed wet watermarks. This phenomenon indicates that the surface of the sheet is substantially hydrophobic and the internal hydrophobic effect is poor.
The phenomena of comparative examples 1 and 2 were analyzed, one of the reasons being that since the silicone oil of comparative example 1 was added little and was hydrophilic, most of the silicone oil was extruded with water, and as a result, the surface and the inside were not substantially waterproof, whereas comparative example 2 was that since a large amount of silicone oil emulsion was added, although the slurry was extruded with most of the water in the slurry during the extrusion molding in the mold, and most of the hydrophilic silicone oil emulsion was carried out, a small portion was remained in the interior of the sheet, and therefore, the water-repellent phenomenon was formed in the place where the interior of the sheet was waterproof, while the surface of the sheet was always in contact with water during the extrusion, and by the continuous extrusion, a relatively large amount of silicone oil component was accumulated or deposited on the surface, and a silicone oil enrichment process was formed, so that a water-repellent layer was formed on the surface after drying.
The calcium silicate boards of example 8 and comparative example 2 were each broken into small pieces, and electron microscopic observation was performed at the cross section, and specific results are shown in fig. 6 and 7, wherein fig. 6 is the internal microstructure of the calcium silicate board of comparative example 2, and fig. 7 is the internal microstructure of the calcium silicate board of example 8. The cylindrical objects on the two pictures are glass fibers, and as can be seen from the pictures, the glass fiber surface of the picture 6 is smooth, and few fibrous objects are attached on the glass fiber surface; whereas the glass fibers of fig. 7 are covered with a large amount of fibers, the main component of which should be tobermorite, it can be seen from fig. 7 that the polysiloxane of example 8 is sufficiently reactive with both tobermorite fibers and glass fibers, respectively.
Comparative example 3
The hydrophilic polyether modified amino alkyl long-chain alkyl modified silicone oil of the long-chain alkyl modified polysiloxane of the example 8 is used for replacing the calcium silicate board for preparing the xonotlite, and other raw materials, proportions, reaction steps and conditions are the same as those of the example 8.
The waterproof performance test was carried out on the produced xonotlite-type calcium silicate board, and the phenomenon was the same as in comparative example 1, and the surface and the inside of the board were not substantially waterproof.
Example 10
The addition amount of the long-chain alkyl-modified polysiloxane of example 8 was increased from 0.3% by mass of the long-chain alkyl-modified polysiloxane to 10% by mass of the long-chain alkyl-modified polysiloxane, based on the total mass of both the quartz powder and the slaked lime powder, and other raw materials, proportions, reaction steps and conditions were the same as those of example 8, to prepare a tobermorite sheet.
The calcium silicate board of this example was subjected to a hydrophobicity test with a hydrophobicity of 99.5%, and after the production wastewater of this example was left to stand, there was a layer of a significantly thin white oil on the surface of the wastewater, and the main component thereof was tested to be a long-chain alkyl polysiloxane. It can be seen that the amount of the modified polysiloxane of example 8 added has satisfied the waterproof requirement, and that most of the modified polysiloxane added in example 10 did not participate in the reaction, and a part thereof was discharged with water.
Example 11
A xonotlite-type calcium silicate board, comprising the following raw materials: rice hull ash, slaked lime powder, distilled water, carbon fiber and amino modified silicone oil;
wherein the silicon dioxide content in the rice hull ash reaches 98%, and the 400-mesh sieve residue is not more than 5%; the calcium hydroxide content of the slaked lime powder reaches 90%, and the 325 mesh sieve residue is not more than 5%; the adding proportion of the rice hull ash and the slaked lime powder is that the mol ratio of silicon atoms to calcium atoms is 1:1.2; the distilled water was added in an amount such that the water-to-solid ratio (i.e., the ratio of the mass of water to the total mass of both rice hull ash and slaked lime powder) was 9:1, a step of; the mass of the carbon fiber is 6% of the total mass of the rice hull ash and the slaked lime powder; the mass of the amino modified silicone oil is 0.5 percent of the total mass of the rice hull ash and the slaked lime powder.
The amino-modified silicone oil used in this example is hydrophobic and its infrared spectrum is shown in fig. 8.
The manufacturing method of the inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing rice hull ash and slaked lime powder;
(2) Adding rice hull ash and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) And (3) injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 280 ℃, the reaction kettle starts to heat, the heating rate is 1.2 ℃/min, the final temperature in the reaction kettle reaches 220 ℃, the pressure reaches 2.1MPa, and then, after heat preservation and pressure maintaining are carried out for 6 hours, cooling is carried out, so that the slurry taking the xonotlite crystal as a main component is prepared. Wherein the stirring speed in the kettle is 250r/min in the heating process, 90r/min in the heat preservation process and 110r/min in the cooling process;
(4) Adding the tobermorite slurry obtained in the step (3) into carbon fibers, adding amino modified silicone oil, and fully stirring for 20min at the stirring speed of 100r/min until the carbon fibers, the amino modified silicone oil and the slurry are fully and uniformly mixed.
(5) Extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the product with the overall hydrophobicity and the density of 220kg/m 3 Is a calcium silicate board of (2).
Example 12
A xonotlite-type calcium silicate board, comprising the following raw materials: quartz powder, slaked lime powder, distilled water, glass fiber, hydrophobic long-chain alkyl polysiloxane and fly ash;
wherein the silicon dioxide content in the quartz powder reaches 98%, and the 400-mesh sieve residue is not more than 5%; the calcium hydroxide content of the slaked lime powder reaches 90%, and the 325 mesh sieve residue is not more than 5%; the adding proportion of the quartz powder and the slaked lime powder is that the mol ratio of silicon atoms to calcium atoms is 1:0.9; the distilled water is added in an amount such that the water-to-solid ratio (i.e., the ratio of the mass of water to the total mass of both the quartz powder and the slaked lime powder) is 10:1, a step of; the mass of the glass fiber is 3% of the total mass of the quartz powder and the slaked lime powder; the mass of the long-chain alkyl modified polysiloxane is 0.4% of the total mass of the quartz powder and the slaked lime powder, and the mass of the fly ash is 10% of the total mass of the quartz powder and the slaked lime powder.
The manufacturing method of the inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into water according to a required molar ratio, mixing and uniformly stirring;
(3) And (3) injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 300 ℃, the reaction kettle starts to heat, the heating rate is 2.5 ℃/min, the final temperature in the reaction kettle reaches 230 ℃, the pressure reaches 1.8MPa, and then, the temperature and the pressure are maintained for 6 hours, and then, the temperature is reduced, so that the slurry taking the xonotlite crystal as a main component is prepared. Wherein the stirring speed in the kettle is 250r/min in the heating process, the stirring speed in the heat preservation process is 80r/min, and the stirring speed in the cooling process is 100r/min;
(4) Adding glass fibers, long-chain alkyl polysiloxane and fly ash into the tobermorite slurry obtained in the step (3) and fully stirring, wherein the stirring speed is 80r/min, and the stirring time is 15min until the glass fibers, the long-chain alkyl polysiloxane and the slurry are fully and uniformly mixed.
(5) Extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the product with the density of 220kg/m 3 The inside and outside of the (C) are provided with hydrophobic calcium silicate plates.
Example 13
A xonotlite-type calcium silicate board, comprising the following raw materials: quartz powder, slaked lime powder, distilled water, glass fiber, hydrophobic amino alkyl long-chain alkyl modified silicone oil and fly ash;
wherein the silicon dioxide content in the quartz powder reaches 98%, and the 400-mesh sieve residue is not more than 5%; the calcium hydroxide content of the slaked lime powder reaches 90%, and the 325 mesh sieve residue is not more than 5%; the adding proportion of the quartz powder and the slaked lime powder is that the mol ratio of silicon atoms to calcium atoms is 1:0.8; the distilled water is added in an amount such that the water-to-solid ratio (i.e., the ratio of the mass of water to the total mass of both the quartz powder and the slaked lime powder) is 12:1, a step of; the mass of the glass fiber is 8% of the total mass of the quartz powder and the slaked lime powder; the mass of the amino alkyl long-chain alkyl modified silicone oil is 1% of the total mass of the quartz powder and the slaked lime powder, and the mass of the fly ash is 20% of the total mass of the quartz powder and the slaked lime powder.
The manufacturing method of the inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) And (3) injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 320 ℃, the reaction kettle starts to heat up, the heating rate is 1.8 ℃/min, the final temperature in the reaction kettle reaches 230 ℃, the pressure reaches 2.3MPa, and then, the temperature and the pressure are maintained for 5.5 hours, and then, the temperature is reduced, so that the slurry taking the tobermorite crystal as a main component is prepared. Wherein the stirring speed in the kettle is 280r/min in the heating process, 110r/min in the heat preservation process and 90r/min in the cooling process;
(4) Adding glass fiber, amino long-chain alkyl modified silicone oil and fly ash into the tobermorite slurry obtained in the step (3) and fully stirring for 20min until the glass fiber, the amino long-chain alkyl modified silicone oil and the slurry are fully and uniformly mixed.
(5) Extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the product with the density of 220kg/m 3 The inside and outside of the (C) are provided with hydrophobic calcium silicate plates.
Example 14
The amount of the fly ash of example 13 was increased from 20% by mass to 40% by mass based on the total mass of both the quartz powder and the slaked lime powder, and the other raw materials, the proportions, the reaction steps and the conditions were the same as those of example 13, thereby preparing a xonotlite-type calcium silicate board.
Example 15
A xonotlite-type calcium silicate board, comprising the following raw materials: quartz powder, slaked lime powder, distilled water, glass fiber, hydrophobic long-chain alkyl polysiloxane, fly ash and carboxymethyl cellulose;
wherein the silicon dioxide content in the quartz powder reaches 98%, and the 400-mesh sieve residue is not more than 5%; the calcium hydroxide content of the slaked lime powder reaches 90%, and the 325 mesh sieve residue is not more than 5%; the adding proportion of the quartz powder and the slaked lime powder is that the mol ratio of silicon atoms to calcium atoms is 1:1, a step of; the distilled water is added in an amount such that the water-to-solid ratio (i.e., the ratio of the mass of water to the total mass of both the quartz powder and the slaked lime powder) is 10:1, a step of; the mass of the glass fiber is 3% of the total mass of the quartz powder and the slaked lime powder; the mass of the long-chain alkyl modified polysiloxane is 0.3% of the total mass of the quartz powder and the slaked lime powder, the mass of the fly ash is 10% of the total mass of the quartz powder and the slaked lime powder, and the mass of the carboxymethyl cellulose is 0.3% of the total mass of the quartz powder and the slaked lime powder.
The manufacturing method of the inside and outside hydrophobic xonotlite type calcium silicate board comprises the following specific steps:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) And (3) injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 310 ℃, the reaction kettle starts to heat up, the heating rate is 1.5 ℃/min, the final temperature in the reaction kettle reaches 220 ℃, the pressure reaches 1.8MPa, and then, the temperature and the pressure are kept for 6 hours, and then, the temperature is reduced, so that the slurry taking the xonotlite crystal as a main component is prepared. Wherein the stirring speed in the kettle is 300r/min in the heating process, the stirring speed in the heat preservation process is 100r/min, and the stirring speed in the cooling process is 100r/min;
(4) Adding glass fibers, long-chain alkyl polysiloxane, fly ash and carboxymethyl cellulose into the tobermorite slurry obtained in the step (3), fully stirring, wherein the stirring speed is 80r/min, the slurry gradually layering phenomenon occurs in the stirring process, the upper layer is water, the lower layer is solid components except water, and the stirring time is shortened to 8 min.
(5) Extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the product with the density of 220kg/m 3 The inside and outside of the (C) are provided with hydrophobic calcium silicate plates.
The relevant performance tests were carried out for examples 8 to 15 and the relevant comparative examples, the specific results being given in table 2 below:
TABLE 2
From the above data, it can be seen that the compressive strength, flexural strength, etc. of example 8 are significantly improved as compared with comparative example 2. For analysis reasons, since the polysiloxane added plays a promoting role in several properties, it can be seen from the electron microscope photographs of fig. 6 and 7 that the polysiloxane of example 8 is sufficiently reacted and combined with both xonotlite fiber and glass fiber, respectively, so that the xonotlite fiber and the glass fiber are also closely combined together by it, so that it greatly improves the adhesion between these materials, not only improves the mechanical properties of the materials, but also prevents moisture from invading the interface between the glass fiber and the calcium silicate fiber. On the other hand, because it is also closely combined on the surface of the glass fiber, a layer of film is formed, so that the integrity of the surface of the fiber can be improved, the film also plays a role in protecting the fiber, the tensile strength of the fiber can be improved, and the fiber is prevented from being damaged in wiredrawing.
From the test data of example 10, it can be seen that the added amount of the modified silicone oil is increased to 10% of the total mass of the siliceous material and the calcareous material, the hydrophobicity is not improved basically, and other properties are not changed obviously, and from this, it can be seen that the added amount of the modified silicone oil is 0.3-0.8% which meets the requirements of hydrophobicity and mechanical property improvement. The amount of modified silicone oil added during the preparation process may be more than 0.8% and up to 15%, 20% or even more, based on the total mass of siliceous material and calcareous material, all being within the scope of the present application.
The above examples are merely illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solution of the present invention should fall within the scope of protection defined by the claims of the present invention as long as the inside and outside hydrophobic calcium silicate material mainly comprising xonotlite, including the material added with fly ash and the like, is maintained.
Claims (10)
1. The internal and external hydrophobic xonotlite type calcium silicate board is characterized in that the raw materials comprise siliceous materials, calcareous materials, water and organic silicon waterproof agents, wherein the organic silicon waterproof agents are hydrophobic modified silicone oil or oily organic silicon emulsion, and the organic silicon waterproof agents are added into slurry after the reaction of the siliceous materials and the calcareous materials for mixed use when the calcium silicate board is prepared.
2. An internal and external hydrophobic xonotlite-type calcium silicate board as claimed in claim 1, wherein said organosilicon waterproofing agent is added in an amount of 0.1 to 10% by mass of the total mass of both the siliceous material and the calcareous material.
3. An inside and outside hydrophobic xonotlite-type calcium silicate board as claimed in claim 1, wherein when the water repellent agent is a hydrophobic modified silicone oil, the amount added is 0.1% to 0.8% of the total mass of both siliceous material and calcareous material; the hydrophobic modified silicone oil comprises any one or a combination of several of the following components: hydrophobic amino long-chain alkyl modified silicone oil, hydrophobic hydrogen-containing silicone oil, hydrophobic long-chain alkyl polysiloxane and hydrophobic amino silicone oil; when the organic silicon waterproof agent is oily organic silicon emulsion, the oily organic silicon emulsion is changed into oily emulsion after one or more times of modification, and the addition amount of the oily organic silicon emulsion is 1-10% of the total mass of the siliceous material and the calcareous material.
4. An inside and outside hydrophobic xonotlite-type calcium silicate board as claimed in claim 1, wherein said siliceous material comprises quartz powder, silica fume or rice hull ash; the calcareous material comprises slaked lime slurry or slaked lime powder; the silicon atom and calcium atom mole ratio in the siliceous material and the calcareous material is 1:0.8 to 1.2; the water content in the raw materials is 5-40 times of the total mass of the siliceous material and the calcareous material.
5. An inside and outside hydrophobic xonotlite type calcium silicate board as claimed in claim 4, wherein the water in the raw material is distilled water added in an amount of 8 to 12 times by mass of the total mass of the siliceous material and the calcareous material.
6. An internally and externally hydrophobic xonotlite-type calcium silicate board as claimed in claim 1, wherein said raw material further comprises reinforcing fiber, said reinforcing fiber being at least one of glass fiber, carbon fiber, pulp, cotton linter, polyester fiber and polyacrylonitrile fiber; the addition amount of the reinforcing fiber is 1-8% of the total mass of the siliceous material and the calcareous material; the raw materials also comprise fly ash, and the addition amount of the fly ash is 0-40% of the total mass of the siliceous material and the calcareous material.
7. A method for producing an inside and outside hydrophobic xonotlite type calcium silicate board as claimed in claim 1 to 6, comprising the steps of:
(1) Preparing a siliceous material and a calcareous material;
(2) Mixing and uniformly stirring the siliceous material and the calcareous material in water according to a required proportion;
(3) Injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 200-380 ℃, and starting to heat the reaction kettle to ensure that the temperature in the reaction kettle reaches 200-250 ℃ and the pressure is 1.5-3MPa, and preserving heat and pressure for 2-12 hours at the temperature and the pressure to obtain tobermorite slurry;
(4) Adding reinforcing fibers and an organosilicon waterproofing agent into the tobermorite slurry obtained in the step (3), and then fully stirring to fully contact and mix all substances in the slurry, wherein the organosilicon waterproofing agent is hydrophobic modified silicone oil or oily organosilicon emulsion;
(5) And (3) extruding the slurry prepared in the step (4) in a die by using a hydraulic press, and drying to obtain the inside and outside hydrophobic xonotlite type calcium silicate board.
8. The method for manufacturing the inside and outside hydrophobic xonotlite type calcium silicate board as claimed in claim 7, wherein the method comprises the following specific steps:
(1) Preparing quartz powder and slaked lime powder;
(2) Adding quartz powder and slaked lime powder into distilled water according to a required molar ratio, mixing and uniformly stirring;
(3) Injecting the uniformly mixed raw material slurry into a dynamic synthesis reaction kettle, introducing high-temperature steam, wherein the temperature of the steam is 300-350 ℃, the reaction kettle starts to heat up, the heating rate is 1-2.5 ℃/min, the final temperature in the reaction kettle reaches 200-230 ℃, the pressure reaches 1.5-2.0MPa, and then, the slurry taking tobermorite crystals as main components is prepared after heat preservation and pressure maintaining for 6 hours; wherein the stirring speed in the kettle is 250-320r/min in the heating process, the stirring speed in the heat preservation process is 80-120r/min, and the stirring speed in the cooling process is 80-120r/min;
(4) Adding the xonotlite slurry obtained in the step (3) into the reinforcing fiber and the hydrophobic modified silicone oil and fully stirring for 10-20min until the reinforcing fiber and the hydrophobic modified silicone oil are fully and uniformly mixed with the slurry;
(5) And (3) extruding the slurry obtained in the step (4) in a die by using a hydraulic press, and drying to obtain the calcium silicate board with hydrophobicity on the whole inside and outside.
9. The method for producing an inside and outside hydrophobic xonotlite type calcium silicate board as claimed in claim 7, wherein in said step (4), fly ash is added in addition to the reinforcing fiber and the organosilicon waterproofing agent.
10. The xonotlite-type calcium silicate board as an energy-saving heat-insulating material or a multifunctional composite heat-insulating material prepared by compounding with heat-insulating, fireproof and decorative materials.
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