CN117361550A - Method for nanocrystallizing calcium silicate and peeling nanosheets - Google Patents
Method for nanocrystallizing calcium silicate and peeling nanosheets Download PDFInfo
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- 239000000378 calcium silicate Substances 0.000 title claims abstract description 225
- 229910052918 calcium silicate Inorganic materials 0.000 title claims abstract description 225
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 title claims abstract description 217
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000002135 nanosheet Substances 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 claims abstract description 95
- 239000002994 raw material Substances 0.000 claims abstract description 74
- UGGQKDBXXFIWJD-UHFFFAOYSA-N calcium;dihydroxy(oxo)silane;hydrate Chemical compound O.[Ca].O[Si](O)=O UGGQKDBXXFIWJD-UHFFFAOYSA-N 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000004964 aerogel Substances 0.000 claims abstract description 53
- 238000000498 ball milling Methods 0.000 claims abstract description 53
- 239000003607 modifier Substances 0.000 claims abstract description 41
- 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 39
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000000835 fiber Substances 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 45
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 239000012153 distilled water Substances 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 40
- 238000007709 nanocrystallization Methods 0.000 claims description 32
- 239000002064 nanoplatelet Substances 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- 239000000919 ceramic Substances 0.000 claims description 25
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 24
- 239000004917 carbon fiber Substances 0.000 claims description 24
- 229920000728 polyester Polymers 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- 238000004299 exfoliation Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 14
- 239000000920 calcium hydroxide Substances 0.000 claims description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- 239000010935 stainless steel Substances 0.000 claims description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 10
- 230000002431 foraging effect Effects 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- AZHSSKPUVBVXLK-UHFFFAOYSA-N ethane-1,1-diol Chemical compound CC(O)O AZHSSKPUVBVXLK-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 13
- 230000000975 bioactive effect Effects 0.000 abstract description 2
- 238000012377 drug delivery Methods 0.000 abstract description 2
- 238000004146 energy storage Methods 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000011232 storage material Substances 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 126
- 230000000694 effects Effects 0.000 description 25
- 230000008569 process Effects 0.000 description 13
- 238000011056 performance test Methods 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000013557 residual solvent Substances 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention discloses a method for nanocrystallizing calcium silicate and peeling a nano sheet, which comprises the following steps: preparing tobermorite slurry by adopting a calcareous raw material, a siliceous raw material, an alkaline substance and a neutral solvent; processing the tobermorite slurry by using reinforcing fibers to prepare a tobermorite material; using SiO 2 The xonotlite material is subjected to composite treatment by aerogel and absolute ethyl alcohol to prepare nano calcium silicate gel; carrying out ultrasonic modification treatment on the nano calcium silicate gel by using a modifier to obtain modified nano calcium silicate gel; and performing ball milling stripping on the modified nano calcium silicate gel to obtain the separated calcium silicate nano sheet. The nano-scale gel structure prepared by the invention has smaller particle size and larger specific surface area, and can be used for enhancing the mechanical property of materials and being used as a bioactive carrier for drug delivery or tissue engineering by effectively separating nano-sheets in calcium silicate gelAnd preparing high-performance energy storage materials and the like.
Description
Technical Field
The invention relates to the field of calcium silicate materials, in particular to a method for nanocrystallizing calcium silicate and stripping a nanosheet.
Background
Calcium silicate (CaSiO) 3 ) Is an important mineral, and is widely applied to the fields of building materials, ceramic products and medicine. However, conventional calcium silicate particles or powders have some limitations in certain applications. To overcome these limitations and achieve a wider range of applications, the preparation of nanocrystallized calcium silicate gels and nanoplatelets is a potential research area.
SiO 2 Aerogel is a novel light nano porous material and has the advantages of low density, large specific surface area, high porosity, large pore volume, low refractive index and the like. However, the alloy has high brittleness and low strength, and cannot be directly used as a heat insulation material. The xonotlite is prepared from siliceous raw materials and calcareous raw materials by dynamic hydrothermal synthesis, has high strength and high temperature resistance (the highest use temperature is 1050 ℃). In the preparation of ultra-light materials (density less than 170 kg/m) 3 ) The control of the reaction conditions in the process of the xonotlite can generate secondary xonotlite particles similar to Mao Lizhuang, the shells of the secondary xonotlite particles are compact, the interiors of the secondary xonotlite particles are hollow due to sparse crystals, and the diameters of the secondary xonotlite particles are between tens and tens of micrometers.
Conventional calcium silicate articles have some problems in certain applications. First, their larger particle size often fails to meet the requirements of nanoscale materials. Second, the binding force between the particles is strong, and it is difficult to disperse and peel effectively. In addition, the traditional method for preparing the calcium silicate nano material has complex process, involves high temperature, high pressure or chemical synthesis steps and the like, has higher cost and is not environment-friendly.
Disclosure of Invention
The invention aims to provide a method for nanocrystallization and nanoplatelet peeling of calcium silicate, which is used for solving at least one technical problem, can convert a calcium silicate raw material into a nanoscale gel structure, has smaller particle size and larger specific surface area, effectively separates nanoplatelets in calcium silicate gel, has wider application range, can be used for enhancing the mechanical property of materials, can be used as a bioactive carrier for drug delivery or tissue engineering, and can be used for preparing high-performance energy storage materials and the like.
Embodiments of the present invention are implemented as follows:
a method of calcium silicate nanocrystallization and nanoplatelet exfoliation comprising:
s100, preparing tobermorite slurry by adopting a calcareous raw material, a siliceous raw material, an alkaline substance and a neutral solvent;
s200, treating the tobermorite slurry by using reinforcing fibers to prepare a tobermorite material;
s300, siO is used 2 The xonotlite material is subjected to composite treatment by aerogel and absolute ethyl alcohol to prepare nano calcium silicate gel;
s400, carrying out ultrasonic modification treatment on the nano calcium silicate gel by using a modifier to obtain modified nano calcium silicate gel;
s500, performing ball milling stripping on the modified nano calcium silicate gel to obtain separated calcium silicate nano sheets.
In a preferred embodiment of the present invention, in S100 of the above method for nanocrystallizing calcium silicate and peeling nanoplatelets, calcium hydroxide is used as the calcareous raw material, silicon dioxide is used as the siliceous raw material, potassium hydroxide is used as the alkaline material, and distilled water is used as the neutral solvent;
the mass ratio of each raw material is calcium hydroxide: silica: potassium hydroxide: distilled water= (8-12): (9-13): (0.1-0.5): (600-800).
The technical effects are as follows: by adopting calcium hydroxide, silicon dioxide, potassium hydroxide and distilled water as raw materials and proportioning according to a certain mass ratio, the characteristics of the calcium silicate nano-sheet, including shape, size, surface property and the like, can be adjusted, and the quality and performance of the prepared nano-calcium silicate gel can be improved.
In a preferred embodiment of the present invention, in S100 of the above method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the step of preparing the tobermorite slurry includes:
s101, taking the raw materials according to the mass ratio of the raw materials, and uniformly mixing to obtain the tobermorite slurry.
The technical effects are as follows: ensures that various raw materials in the tobermorite slurry of the calcium silicate are fully mixed, and is favorable for forming a uniform system, thereby improving the consistency and stability of the preparation.
In a preferred embodiment of the present invention, in S200 of the above method for nanocrystallizing and nanoplatelets peeling, the reinforcing fibers include polyester fibers, carbon fibers and ceramic fibers;
the mass ratio of the raw materials is as follows: polyester fiber: carbon fiber: ceramic fiber= (80-100): (1-5): (3-5): (3-5).
The technical effects are as follows: the mechanical properties of the xonotlite material can be remarkably improved by using the polyester fiber, the carbon fiber and the ceramic fiber as the reinforcing fiber, the toughness of the material can be generally improved by using the polyester fiber, the strength can be increased by using the carbon fiber, and better wear resistance and high-temperature performance can be provided by using the ceramic fiber. Through reasonable selection and matching of different types of reinforcing fibers, the reinforcing fibers fully play a role through reasonable proportioning, and the overall performance of the calcium silicate material is improved.
In a preferred embodiment of the present invention, in S200 of the above method for nanocrystallizing calcium silicate and exfoliating nanosheets, the step of preparing the xonotlite material includes:
s201, mixing and uniformly stirring the tobermorite slurry, the polyester fiber, the carbon fiber and the ceramic fiber according to the mass ratio of the raw materials;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
and S203, drying the formed wet blank to prepare the tobermorite material.
The technical effects are as follows: the method is favorable for forming the xonotlite material with a certain shape and density by press filtration, so that the material has higher compactness. And drying the formed wet blank to prepare the xonotlite material, removing residual moisture, and improving the stability and durability of the calcium silicate material.
In a preferred embodiment of the present invention, in S300 of the method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the mass ratio of the raw materials is SiO 2 Aerogel: absolute ethyl alcohol: xonotlite material = 1: (3-5): (5-10).
The technical effects are as follows: siO (SiO) 2 The aerogel has a larger specific surface area, and the surface of the calcium silicate material can be uniformly covered by the composite treatment, so that a nanoscale structure is formed, the specific surface area of the calcium silicate material is increased, the active surface area of the material can be increased, and the reactivity and the adsorption performance of the material are improved. Absolute ethyl alcohol as solvent, capable of SiO 2 The aerogel and the xonotlite material are fully mixed, and the reaction rate is improved, so that uniform nano calcium silicate gel is formed.
In a preferred embodiment of the present invention, in S300 of the above method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the step of preparing the nano calcium silicate gel includes:
s301, taking SiO according to the mass ratio of the raw materials 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 Feeding the aerogel into a vacuum impregnation apparatus, and then mixing the xonotlite material with the SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 3-6 hours to ensure that the SiO is prepared 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 18-36 h to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at the temperature of 40-60 ℃ under the pressure of 10-20 MPa for 5-12 hours to obtain the nano calcium silicate gel.
The technical effects are as follows: siO under vacuum condition 2 Aerogel can completely infiltrate the xonotlite material to ensure SiO 2 The aerogel is uniformly distributed in the xonotlite material and aids in the formation of the calcium silicate gel and stabilization of the structure. The calcium silicate gel is put into absolute ethyl alcohol for aging, so that the calcium silicate gel is gelled and crystallized, and the structural adjustment and the particle size control of the calcium silicate gel are facilitated. Drying with supercritical carbon dioxide can remove residual solvent more effectively without causing collapse of the gel structure, while the use of supercritical carbon dioxide can promote the formation of nano-sized particles of calcium silicate gel.
In the preferred embodiment of the present invention, in S400 of the method for nanocrystallization and nanoplatelet peeling of calcium silicate, the modifier is a mixed solution of absolute ethyl alcohol and distilled water, and the mass ratio of the absolute ethyl alcohol is: distilled water = 2.4:1.
the technical effects are as follows: the mixed solution of absolute ethyl alcohol and distilled water is used as a modifier, so that the dispersing effect of an organic solvent is provided in the modifying process, and the effect of a surfactant is provided by the distilled water, so that the calcium silicate gel can be effectively modified while organic residues are not introduced.
In a preferred embodiment of the present invention, in S400 of the above method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the step of performing ultrasonic modification treatment on the nano calcium silicate gel using a modifier to obtain a modified nano calcium silicate gel includes:
s401, mixing absolute ethyl alcohol and distilled water together according to the mass ratio of the raw materials to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1 (8-10) adding the modifier to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 50-160W, and the time range is 9-20 min, so as to obtain the modified nano calcium silicate gel.
The technical effects are as follows: the ultrasonic wave can generate high-frequency vibration in the solution, so that the penetration of the solvent and the movement of molecules are promoted, and the nano particles are effectively ultrasonically dispersed and surface-modified. By modifying the calcium silicate gel with ultrasound, finer dispersion and uniform surface modification are achieved. By adjusting the power, time and frequency of the ultrasonic wave, the effective modification of the calcium silicate gel can be realized, the uniform dispersion and adsorption of the modifier are promoted, and the full effect of the modifier can be realized under the condition that the structural damage of the calcium silicate gel is not caused.
In a preferred embodiment of the present invention, in S500 of the method for nanocrystallization and nanoplatelet exfoliation, the step of ball-milling and exfoliating the modified nano-calcium silicate gel includes:
s501, bearing stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 6-12 mm, and the density of the ball milling balls is 7.8-8.0 g/cm 3 ；
S502, starting ball milling equipment for 8-13 hours, and stripping and dispersing the nano calcium silicate gel to obtain the calcium silicate nano sheet.
The technical effects are as follows: the ball milling equipment is used for bearing the stainless steel ball grinding balls, ball milling stripping is carried out on the modified nano calcium silicate gel, and during the ball milling process, the calcium silicate gel can be mechanically stripped under the intense movement and collision action of the steel balls, so that the calcium silicate nano sheet is formed. Stainless steel ball grinding balls with the diameter of 6-12 mm and the density of 7.8-8.0 g/cm < 3 > are selected, and sufficient mechanical energy is provided in the ball milling process, so that the calcium silicate gel is effectively stripped and dispersed. The morphology and the size of the calcium silicate nano-sheets are adjusted by controlling the ball milling process, so that the stripping process is ensured to be carried out fully and orderly, the modified nano-calcium silicate gel is stripped and dispersed, and the calcium silicate nano-sheets are finally obtained. The prepared nano-sheet has larger specific surface area and more uniform size distribution, and provides excellent raw materials for the application of calcium silicate materials.
The embodiment of the invention has the beneficial effects that:
according to the method for nanocrystallizing the calcium silicate and stripping the nano sheets, the nanocrystallization and the nano sheets stripping of the calcium silicate material are realized by reasonably selecting raw materials, controlling the mass ratio, adopting the steps of reinforcing fibers, nanocrystallization treatment, ultrasonic modification, ball milling stripping and the like, and the performance and the application potential of the material are improved.
The invention adopts the raw materials of calcium hydroxide, silicon dioxide, potassium hydroxide, distilled water and the like to mix according to a certain mass ratio, and can adjust the characteristics of the calcium silicate nano-sheet, including shape, size, surface property and the like, thereby improving the quality and performance of the prepared nano-calcium silicate gel.
In the process of preparing the tobermorite slurry, the method ensures that various raw materials in the tobermorite slurry of calcium silicate are fully mixed, is beneficial to forming a uniform system, and improves the consistency and stability of preparation.
Polyester fiber, carbon fiber and ceramic fiber are used as reinforcing fibers, and the mass ratio is controlled, so that the mechanical properties of the tobermorite material, including toughness, strength, wear resistance and the like, are improved.
The invention adopts SiO 2 The aerogel and the absolute ethyl alcohol are used for carrying out composite treatment on the xonotlite material, and then supercritical carbon dioxide is used for drying, so that the nano calcium silicate gel is prepared, the nano calcium silicate gel with a nano-scale structure is formed, and the active surface area of the material and the effectiveness of modification are improved.
According to the invention, the mixed solution of absolute ethyl alcohol and distilled water is used as a modifier, and the nano calcium silicate gel is modified by ultrasonic treatment equipment, so that the effective modification of the calcium silicate gel is realized without introducing organic residues, and the uniformity and effect of modification are improved.
According to the invention, through ball milling stripping in ball milling equipment, proper stainless steel ball grinding balls are selected, and the ball milling time range is controlled, so that the calcium silicate nano-sheets are separated, and the calcium silicate nano-sheets with larger specific surface area and uniform size distribution are obtained.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a method for nanocrystallization of calcium silicate and exfoliation of nanosheets according to the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. The components of the embodiments of the present invention generally described and illustrated in the figures herein can be arranged and designed in a wide variety of different configurations.
Referring to fig. 1, the present invention provides a method for nanocrystallization of calcium silicate and peeling of nanoplatelets, comprising:
s100, preparing tobermorite slurry by adopting a calcareous raw material, a siliceous raw material, an alkaline substance and a neutral solvent;
s200, treating the tobermorite slurry by using reinforcing fibers to prepare a tobermorite material;
s300, siO is used 2 The xonotlite material is subjected to composite treatment by aerogel and absolute ethyl alcohol to prepare nano calcium silicate gel;
s400, carrying out ultrasonic modification treatment on the nano calcium silicate gel by using a modifier to obtain modified nano calcium silicate gel;
s500, performing ball milling stripping on the modified nano calcium silicate gel to obtain separated calcium silicate nano sheets.
In a preferred embodiment of the present invention, in S100 of the above method for nanocrystallizing calcium silicate and peeling nanoplatelets, calcium hydroxide is used as the calcareous raw material, silicon dioxide is used as the siliceous raw material, potassium hydroxide is used as the alkaline material, and distilled water is used as the neutral solvent;
the mass ratio of each raw material is calcium hydroxide: silica: potassium hydroxide: distilled water= (8-12): (9-13): (0.1-0.5): (600-800).
The technical effects are as follows: by adopting calcium hydroxide, silicon dioxide, potassium hydroxide and distilled water as raw materials and proportioning according to a certain mass ratio, the characteristics of the calcium silicate nano-sheet, including shape, size, surface property and the like, can be adjusted, and the quality and performance of the prepared nano-calcium silicate gel can be improved.
In a preferred embodiment of the present invention, in S100 of the above method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the step of preparing the tobermorite slurry includes:
s101, taking the raw materials according to the mass ratio of the raw materials, and uniformly mixing to obtain the tobermorite slurry.
The technical effects are as follows: ensures that various raw materials in the tobermorite slurry of the calcium silicate are fully mixed, and is favorable for forming a uniform system, thereby improving the consistency and stability of the preparation.
In a preferred embodiment of the present invention, in S200 of the above method for nanocrystallizing and nanoplatelets peeling, the reinforcing fibers include polyester fibers, carbon fibers and ceramic fibers;
the mass ratio of the raw materials is as follows: polyester fiber: carbon fiber: ceramic fiber= (80-100): (1-5): (3-5): (3-5).
The technical effects are as follows: the mechanical properties of the xonotlite material can be remarkably improved by using the polyester fiber, the carbon fiber and the ceramic fiber as the reinforcing fiber, the toughness of the material can be generally improved by using the polyester fiber, the strength can be increased by using the carbon fiber, and better wear resistance and high-temperature performance can be provided by using the ceramic fiber. Through reasonable selection and matching of different types of reinforcing fibers, the reinforcing fibers fully play a role through reasonable proportioning, and the overall performance of the calcium silicate material is improved.
In a preferred embodiment of the present invention, in S200 of the above method for nanocrystallizing calcium silicate and exfoliating nanosheets, the step of preparing the xonotlite material includes:
s201, mixing and uniformly stirring the tobermorite slurry, the polyester fiber, the carbon fiber and the ceramic fiber according to the mass ratio of the raw materials;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
and S203, drying the formed wet blank to prepare the tobermorite material.
The technical effects are as follows: the method is favorable for forming the xonotlite material with a certain shape and density by press filtration, so that the material has higher compactness. And drying the formed wet blank to prepare the xonotlite material, removing residual moisture, and improving the stability and durability of the calcium silicate material.
In a preferred embodiment of the present invention, in S300 of the method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the mass ratio of the raw materials is SiO 2 Aerogel: absolute ethyl alcohol: xonotlite material = 1: (3-5): (5-10).
The technical effects are as follows: siO (SiO) 2 The aerogel has a larger specific surface area, and the surface of the calcium silicate material can be uniformly covered by the composite treatment, so that a nanoscale structure is formed, the specific surface area of the calcium silicate material is increased, the active surface area of the material can be increased, and the reactivity and the adsorption performance of the material are improved. Absolute ethyl alcohol as solvent, capable of SiO 2 The aerogel and the xonotlite material are fully mixed, and the reaction rate is improved, so that uniform nano calcium silicate gel is formed.
In a preferred embodiment of the present invention, in S300 of the above method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the step of preparing the nano calcium silicate gel includes:
s301, taking SiO according to the mass ratio of the raw materials 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 Feeding the aerogel into a vacuum impregnation apparatus, and then mixing the xonotlite material with the SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 3-6 hours to ensure that the SiO is prepared 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 18-36 h to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at the temperature of 40-60 ℃ under the pressure of 10-20 MPa for 5-12 hours to obtain the nano calcium silicate gel.
The technical effects are as follows: siO under vacuum condition 2 Aerogel can completely infiltrate the xonotlite material to ensure SiO 2 The aerogel is uniformly distributed in the xonotlite material and aids in the formation of the calcium silicate gel and stabilization of the structure. The calcium silicate gel is put into absolute ethyl alcohol for aging, so that the calcium silicate gel is gelled and crystallized, and the structural adjustment and the particle size control of the calcium silicate gel are facilitated. Drying with supercritical carbon dioxide can remove residual solvent more effectively without causing collapse of the gel structure, while the use of supercritical carbon dioxide can promote the formation of nano-sized particles of calcium silicate gel.
In the preferred embodiment of the present invention, in S400 of the method for nanocrystallization and nanoplatelet peeling of calcium silicate, the modifier is a mixed solution of absolute ethyl alcohol and distilled water, and the mass ratio of the absolute ethyl alcohol is: distilled water = 2.4:1.
the technical effects are as follows: the mixed solution of absolute ethyl alcohol and distilled water is used as a modifier, so that the dispersing effect of an organic solvent is provided in the modifying process, and the effect of a surfactant is provided by the distilled water, so that the calcium silicate gel can be effectively modified while organic residues are not introduced.
In a preferred embodiment of the present invention, in S400 of the above method for nanocrystallization and nanoplatelet exfoliation of calcium silicate, the step of performing ultrasonic modification treatment on the nano calcium silicate gel using a modifier to obtain a modified nano calcium silicate gel includes:
s401, mixing absolute ethyl alcohol and distilled water together according to the mass ratio of the raw materials to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1 (8-10) adding the modifier to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 50-160W, and the time range is 9-20 min, so as to obtain the modified nano calcium silicate gel.
The technical effects are as follows: the ultrasonic wave can generate high-frequency vibration in the solution, so that the penetration of the solvent and the movement of molecules are promoted, and the nano particles are effectively ultrasonically dispersed and surface-modified. By modifying the calcium silicate gel with ultrasound, finer dispersion and uniform surface modification are achieved. By adjusting the power, time and frequency of the ultrasonic wave, the effective modification of the calcium silicate gel can be realized, the uniform dispersion and adsorption of the modifier are promoted, and the full effect of the modifier can be realized under the condition that the structural damage of the calcium silicate gel is not caused.
In a preferred embodiment of the present invention, in S500 of the method for nanocrystallization and nanoplatelet exfoliation, the step of ball-milling and exfoliating the modified nano-calcium silicate gel includes:
s501, bearing stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 6-12 mm, and the density of the ball milling balls is 7.8-8.0 g/cm 3 ；
S502, starting ball milling equipment for 8-13 hours, and stripping and dispersing the nano calcium silicate gel to obtain the calcium silicate nano sheet.
The technical effects are as follows: the ball milling equipment is used for bearing the stainless steel ball grinding balls, ball milling stripping is carried out on the modified nano calcium silicate gel, and during the ball milling process, the calcium silicate gel can be mechanically stripped under the intense movement and collision action of the steel balls, so that the calcium silicate nano sheet is formed. Stainless steel ball grinding balls with the diameter of 6-12 mm and the density of 7.8-8.0 g/cm < 3 > are selected, and sufficient mechanical energy is provided in the ball milling process, so that the calcium silicate gel is effectively stripped and dispersed. The morphology and the size of the calcium silicate nano-sheets are adjusted by controlling the ball milling process, so that the stripping process is ensured to be carried out fully and orderly, the modified nano-calcium silicate gel is stripped and dispersed, and the calcium silicate nano-sheets are finally obtained. The prepared nano-sheet has larger specific surface area and more uniform size distribution, and provides excellent raw materials for the application of calcium silicate materials.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
(one) example 1:
a method for nanocrystallization of calcium silicate and peeling of nanosheets, comprising:
s101, calcium hydroxide is used as the raw materials according to the mass ratio: silica: potassium hydroxide: distilled water = 10:11:0.3:700, uniformly mixing all the raw materials to obtain tobermorite slurry;
s201, the mass ratio of each raw material is as follows: polyester fiber: carbon fiber: ceramic fiber = 90:3:4:3, mixing and uniformly stirring the xonotlite slurry, the polyester fiber, the carbon fiber and the ceramic fiber;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
s203, drying the formed wet blank to prepare a tobermorite material;
s301, according to each originalThe mass ratio of the materials is SiO 2 Aerogel: absolute ethyl alcohol: xonotlite material = 1:4:7 SiO is taken out 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 Feeding the aerogel into a vacuum impregnation apparatus, and then mixing the xonotlite material with the SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 5 hours to ensure that the SiO is prepared 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 24 hours to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at 50 ℃, under 15MPa for 8 hours to obtain nano calcium silicate gel;
s401, the mass ratio of the raw materials is absolute ethyl alcohol: distilled water = 2.4:1, mixing absolute ethyl alcohol and distilled water together to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1:9 the modifier is added to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 100W, and the time is 13min, so as to obtain modified nano calcium silicate gel;
s501, carrying stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 9mm, and the density of the ball milling balls is 7.9g/cm 3 ；
S502, starting ball milling equipment, wherein the time range is 11 hours, and stripping and dispersing the nano calcium silicate gel to obtain the calcium silicate nano sheet.
(II) example 2:
a method for nanocrystallization of calcium silicate and peeling of nanosheets, comprising:
s101, calcium hydroxide is used as the raw materials according to the mass ratio: silica: potassium hydroxide: distilled water = 8:9:0.1:600, uniformly mixing the raw materials to obtain tobermorite slurry;
s201, the mass ratio of each raw material is as follows: polyester fiber: carbon fiber: ceramic fiber = 80:1:3:3, mixing and uniformly stirring the xonotlite slurry, the polyester fiber, the carbon fiber and the ceramic fiber;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
s203, drying the formed wet blank to prepare a tobermorite material;
s301, the mass ratio of each raw material is SiO 2 Aerogel: absolute ethyl alcohol: xonotlite material = 1:3:5 SiO is taken out 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 Feeding the aerogel into a vacuum impregnation apparatus, and then mixing the xonotlite material with the SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 3 hours to ensure that the SiO is prepared 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 18 hours to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at the temperature of 40 ℃, the pressure of 10MPa and the time of 5 hours to obtain nano calcium silicate gel;
s401, the mass ratio of the raw materials is absolute ethyl alcohol: distilled water = 2.4:1, mixing absolute ethyl alcohol and distilled water together to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1:8 the modifier is added to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 50W, and the time range is 9min, so as to obtain modified nano calcium silicate gel;
s501, carrying stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 6mm, and the density of the ball milling balls is 7.8g/cm 3 ；
S502, starting ball milling equipment for 8 hours to strip and disperse the nano calcium silicate gel to obtain the calcium silicate nano sheet.
(III) example 3:
a method for nanocrystallization of calcium silicate and peeling of nanosheets, comprising:
s101, calcium hydroxide is used as the raw materials according to the mass ratio: silica: potassium hydroxide: distilled water = 12:13:0.5:800, taking all raw materials, and uniformly mixing to obtain tobermorite slurry;
s201, the mass ratio of each raw material is as follows: polyester fiber: carbon fiber: ceramic fiber = 100:5:5:5, mixing and uniformly stirring the xonotlite slurry, the polyester fiber, the carbon fiber and the ceramic fiber;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
s203, drying the formed wet blank to prepare a tobermorite material;
s301, the mass ratio of each raw material is SiO 2 Aerogel: absolute ethyl alcohol: xonotlite material = 1:5:10 SiO is taken out 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 Feeding the aerogel into a vacuum impregnation apparatus, and then mixing the xonotlite material with the SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 6 hours to ensure that the SiO is prepared 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 36h to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at the temperature of 60 ℃, the pressure of 20MPa and the time of 12 hours to obtain nano calcium silicate gel;
s401, the mass ratio of the raw materials is absolute ethyl alcohol: distilled water = 2.4:1, mixing absolute ethyl alcohol and distilled water together to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1:10 the modifier is added to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 160W, and the time range is 20min, so as to obtain modified nano calcium silicate gel;
s501, carrying stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 12mm, and the density of the ball milling balls is 8.0g/cm 3 ；
S502, starting ball milling equipment, wherein the time range is 13 hours, and stripping and dispersing the nano calcium silicate gel to obtain the calcium silicate nano sheet.
(IV) example 4:
a method for nanocrystallization of calcium silicate and peeling of nanosheets, comprising:
s101, calcium hydroxide is used as the raw materials according to the mass ratio: silica: potassium hydroxide: distilled water = 9:10:0.2:650 taking all the raw materials, and uniformly mixing to obtain tobermorite slurry;
s201, the mass ratio of each raw material is as follows: polyester fiber: carbon fiber: ceramic fiber = 90:2:4:4, mixing and uniformly stirring the xonotlite slurry, the polyester fiber, the carbon fiber and the ceramic fiber;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
s203, drying the formed wet blank to prepare a tobermorite material;
s301, the mass ratio of each raw material is SiO 2 Aerogel: absolute ethyl alcohol: xonotlite material = 1:3.5:6 SiO is taken out 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 AerogelFeeding into a vacuum impregnation apparatus, and then mixing said xonotlite material with said SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 4 hours to enable the SiO to be mixed 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 20 hours to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at the temperature of 45 ℃ and the pressure of 12MPa for 6 hours to obtain nano calcium silicate gel;
s401, the mass ratio of the raw materials is absolute ethyl alcohol: distilled water = 2.4:1, mixing absolute ethyl alcohol and distilled water together to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1:8.5 the modifier is added to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 80W, and the time is 12min, so as to obtain modified nano calcium silicate gel;
s501, carrying stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 8mm, and the density of the ball milling balls is 7.8g/cm 3 ；
S502, starting ball milling equipment for 9 hours to strip and disperse the nano calcium silicate gel to obtain the calcium silicate nano sheet.
(fifth) example 5:
a method for nanocrystallization of calcium silicate and peeling of nanosheets, comprising:
s101, calcium hydroxide is used as the raw materials according to the mass ratio: silica: potassium hydroxide: distilled water = 11:0.4:750, taking and uniformly mixing the raw materials to obtain tobermorite slurry;
s201, the mass ratio of each raw material is as follows: polyester fiber: carbon fiber: ceramic fiber = 95:4:4.5:4.5 mixing and uniformly stirring the xonotlite slurry, the polyester fiber, the carbon fiber and the ceramic fiber;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
s203, drying the formed wet blank to prepare a tobermorite material;
s301, the mass ratio of each raw material is SiO 2 Aerogel: absolute ethyl alcohol: xonotlite material = 1:4.5:9 SiO is taken out 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 Feeding the aerogel into a vacuum impregnation apparatus, and then mixing the xonotlite material with the SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 5.5 hours to ensure that the SiO is prepared 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 30 hours to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at the temperature of 55 ℃, the pressure of 18MPa and the time range of 10 hours to obtain nano calcium silicate gel;
s401, the mass ratio of the raw materials is absolute ethyl alcohol: distilled water = 2.4:1, mixing absolute ethyl alcohol and distilled water together to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1:9.5 the modifier is added to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 130W, and the time is 16min, so as to obtain modified nano calcium silicate gel;
s501, carrying stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 11mm, and the density of the ball milling balls is 7.9g/cm 3 ；
S502, starting ball milling equipment, and enabling the time range to be 12 hours, so that the nano calcium silicate gel is stripped and dispersed, and the calcium silicate nano sheet is obtained.
(six) Performance test
And respectively performing basic performance test, stability test and engineering performance test on the finished product of the calcium silicate nano sheet prepared in the embodiment.
The results of the basic performance test are shown in table 1.
Table 1: basic performance test results
The method for testing the stability comprises the following steps: grinding the calcium silicate nano sheet, adding distilled water to prepare a suspension emulsion, dripping 3mL of the suspension emulsion into a 15mL test tube with scales, adding 12mL of deionized water into the suspension tube, shaking and standing the suspension tube, observing the existence of delamination and precipitation after 24 hours and 48 hours, and evaluating the dispersion stability of the suspension emulsion. 200mL of the emulsion filtered by a 120 mesh screen was added to a 1000mL jar, and after stirring for 30 minutes, the emulsion was observed for breaking or flocculation, and the mechanical stability of the coating emulsion was determined. The results are shown in Table 2.
Table 2: stability test results
As shown in the table, the calcium silicate nano-sheet prepared by the invention has better dilution stability and mechanical stability, does not have the phenomena of delamination damage, flocculation generation and the like, and has excellent performance.
Grinding the calcium silicate nano-sheets, adding distilled water, preparing into emulsion, and performing engineering performance test. The experimental temperature of engineering performance test is 20 ℃, and the experimental temperature mainly comprises the influence on the working performance such as fluidity, water loss and the like. The results are shown in Table 3.
Table 3: engineering performance test results
| Material | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Water to ash ratio | 0.40 | 0.40 | 0.40 | 0.40 | 0.40 |
| Fluidity/cm | 20 | 21 | 22.5 | 21.5 | 20.5 |
| Water loss per mL | 79 | 78 | 78.5 | 79 | 78 |
| Free water/mL | 0 | 0 | 0 | 0 | 0 |
As shown in the table above, the calcium silicate nano sheet prepared by the method has good engineering performance and can meet the construction requirements.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (10)
1. A method for nanocrystallization and nanoplatelet peeling of calcium silicate, comprising:
s100, preparing tobermorite slurry by adopting a calcareous raw material, a siliceous raw material, an alkaline substance and a neutral solvent;
s200, treating the tobermorite slurry by using reinforcing fibers to prepare a tobermorite material;
s300, siO is used 2 The xonotlite material is subjected to composite treatment by aerogel and absolute ethyl alcohol to prepare nano calcium silicate gel;
s400, carrying out ultrasonic modification treatment on the nano calcium silicate gel by using a modifier to obtain modified nano calcium silicate gel;
s500, performing ball milling stripping on the modified nano calcium silicate gel to obtain separated calcium silicate nano sheets.
2. The method for nanocrystallizing and peeling a nano sheet according to claim 1, wherein in S100, calcium hydroxide is used as the calcareous raw material, silicon dioxide is used as the siliceous raw material, potassium hydroxide is used as the alkaline substance, and distilled water is used as the neutral solvent;
the mass ratio of each raw material is calcium hydroxide: silica: potassium hydroxide: distilled water= (8-12): (9-13): (0.1-0.5): (600-800).
3. The method of calcium silicate nanocrystallization and nanoplatelet exfoliation according to claim 2, wherein in S100, the step of preparing the tobermorite slurry comprises:
s101, taking the raw materials according to the mass ratio of the raw materials, and uniformly mixing to obtain the tobermorite slurry.
4. The method of calcium silicate nanocrystallization and nanoplatelet exfoliation according to claim 1, wherein in S200, the reinforcing fibers comprise polyester fibers, carbon fibers, and ceramic fibers;
the mass ratio of the raw materials is as follows: polyester fiber: carbon fiber: ceramic fiber= (80-100): (1-5): (3-5): (3-5).
5. The method of calcium silicate nanocrystallization and nanoplatelet exfoliation according to claim 4, wherein in S200, the step of preparing the xonotlite material comprises:
s201, mixing and uniformly stirring the tobermorite slurry, the polyester fiber, the carbon fiber and the ceramic fiber according to the mass ratio of the raw materials;
s202, uniformly stirring, then sending into a filter press, and press-filtering and forming;
and S203, drying the formed wet blank to prepare the tobermorite material.
6. The method for nanocrystallization and nanoplatelet peeling according to claim 1, wherein,
in S300, the mass ratio of each raw material is SiO 2 Aerogel: anhydrous ethanolAlcohol: xonotlite material = 1: (3-5): (5-10).
7. The method of nanocrystallization and nanoplatelet exfoliation according to claim 6, wherein in S300, the step of preparing the nanosilicate gel comprises:
s301, taking SiO according to the mass ratio of the raw materials 2 Aerogel, absolute ethanol and xonotlite materials for standby;
s302, the SiO is processed 2 Feeding the aerogel into a vacuum impregnation apparatus, and then mixing the xonotlite material with the SiO 2 Mixing aerogel, starting the vacuum impregnation equipment for 3-6 hours to ensure that the SiO is prepared 2 Completely infiltrating the xonotlite material with aerogel;
s303, standing for 18-36 h to form calcium silicate gel;
s304, placing the calcium silicate gel into the absolute ethyl alcohol for aging for 3-6 days to gel and crystallize the calcium silicate;
s305, conveying the gelled and crystallized calcium silicate gel into an autoclave, and drying by using supercritical carbon dioxide at the temperature of 40-60 ℃ under the pressure of 10-20 MPa for 5-12 hours to obtain the nano calcium silicate gel.
8. The method for nanocrystallization and nanoplatelet peeling according to claim 1, wherein in S400, the modifier is a mixed solution of absolute ethyl alcohol and distilled water, and the mass ratio of the absolute ethyl alcohol is: distilled water = 2.4:1.
9. the method of nanocrystallization of calcium silicate and exfoliation of nanoplatelets according to claim 8, wherein in S400, the step of performing ultrasonic modification treatment on the nanosilicate gel using a modifier to obtain a modified nanosilicate gel comprises:
s401, mixing absolute ethyl alcohol and distilled water together according to the mass ratio of the raw materials to prepare a modifier for later use;
s402, modifying agent according to mass ratio: calcium silicate gel = 1 (8-10) adding the modifier to the calcium silicate gel;
s403, sending the mixed solution of the modifier and the calcium silicate gel into ultrasonic treatment equipment, wherein the power is 50-160W, and the time range is 9-20 min, so as to obtain the modified nano calcium silicate gel.
10. The method of calcium silicate nanocrystallization and nanoplatelet exfoliation according to claim 1, wherein in S500, the step of ball-milling the modified nano-calcium silicate gel comprises:
s501, bearing stainless steel ball grinding balls in ball milling equipment, wherein the diameter of the ball milling balls is 6-12 mm, and the density of the ball milling balls is 7.8-8.0 g/cm 3 ；
S502, starting ball milling equipment for 8-13 hours, and stripping and dispersing the nano calcium silicate gel to obtain the calcium silicate nano sheet.
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