CN116283041B - Building composite material and preparation method and application thereof - Google Patents
Building composite material and preparation method and application thereof Download PDFInfo
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- CN116283041B CN116283041B CN202310587210.4A CN202310587210A CN116283041B CN 116283041 B CN116283041 B CN 116283041B CN 202310587210 A CN202310587210 A CN 202310587210A CN 116283041 B CN116283041 B CN 116283041B
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000004568 cement Substances 0.000 claims abstract description 50
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000002086 nanomaterial Substances 0.000 claims abstract description 35
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 18
- 239000011707 mineral Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 12
- TVUBDAUPRIFHFN-UHFFFAOYSA-N dioxosilane;oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4].O=[Si]=O TVUBDAUPRIFHFN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011258 core-shell material Substances 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 19
- KRXBVZUTZPDWQI-UHFFFAOYSA-N ethane-1,2-diol;titanium Chemical compound [Ti].OCCO KRXBVZUTZPDWQI-UHFFFAOYSA-N 0.000 claims description 18
- 239000005543 nano-size silicon particle Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 239000000413 hydrolysate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000012798 spherical particle Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 239000004567 concrete Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011378 shotcrete Substances 0.000 description 4
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000003469 silicate cement Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 239000010457 zeolite 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
- 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
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B28/02—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 hydraulic cements other than calcium sulfates
-
- 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
Abstract
Disclosed is a building composite selected from the group consisting of silica-titania composite nanomaterial; the silicon dioxide-titanium dioxide composite nano material is of a core-shell structure. In addition, a method for the production thereof and the use thereof as mineral admixture are disclosed. The building composite material can better improve the early compressive strength and the flexural strength of the cement paste, thereby obviously improving the mechanical property of the cement paste.
Description
Technical Field
The invention belongs to the field of novel building materials; relates to a building composite material, a preparation method and application thereof.
Background
The cement concrete material is widely applied to building structures and is a large building material with the largest use amount in modern civil engineering. The cement concrete material has the advantages of being castable, good in fire resistance, good in economical efficiency, high in energy efficiency, rich in source, simple in construction and the like. However, the cement concrete material has the characteristics of high compressive strength, low tensile strength, high brittleness and easy cracking, and is easily influenced by mechanical and environmental factors. The formation and development of cracks have great negative influence on the durability of the concrete structure, and the service life of the concrete material is seriously shortened. Meanwhile, the consumption of various raw materials to natural resources and the pollution to the environment are also very serious social problems.
With the development of society, modern engineering structures are gradually developed to be high-rise, large-sized and multifunctional. According to the actual requirements of engineering, researchers continuously explore, from the proposal of high-strength concrete to the development of high-performance concrete, the bearing capacity of the cement concrete material is effectively improved, and the performance of the concrete material is improved. In particular, green concrete is a mainstream development direction of the development of cement concrete materials.
The mineral admixture is an important component of green concrete, and the scientific and reasonable use of the mineral admixture not only can reduce the cement dosage in the cement concrete, but also can improve certain properties of the cement concrete.
In recent years, nanotechnology and technology are continuously developed, and with the improvement of the mastery degree of nanotechnology, nanomaterials are widely focused in various fields. Due to the nano size, the nano-size material has special performances such as volume effect, surface effect, quantum size effect, macroscopic quantum tunneling effect and the like. In view of the unique characteristics of the nano materials, the research of the nano materials in various industries is still in progress, and the nano materials are favored by people in the aspect of building engineering materials, so that the nano materials have favorable development prospect.
The Nanjing water conservancy science institute discloses a nano-scale sprayed concrete modified admixture in Chinese patent application CN102826774A, which comprises the following components in parts by mass: nano SiO 2 60-95; 5-40 parts of superfine mineral admixture; 0 to 10 percent of surfactant; wherein, nano SiO 2 Is SiO 2 High-activity nano particle material with content more than or equal to 95%; the volume average diameter of the nano-scale sprayed concrete modified admixture powder particles is less than or equal to 150nm. The superfine mineral admixture consists of one or more of fly ash, zeolite powder, metakaolin and slag powder; the surfactant is composed of one of organic powders such as polycarboxylic acids, naphthalene, aliphatic, sulfamate, etc. The admixture is mixed into the sprayed concrete mixture according to the mass of 5-15% of cement, so that the rebound rate of wet sprayed concrete is less than or equal to 8%, the setting time is less than or equal to 2min, and the thickness of a primary spraying layer is more than or equal to 35cm.
The university of Chengdu Congress discloses a low temperature nanocomposite cement in chinese patent application CN108751884A, comprising: portland cement, sulphoaluminate cement, calcium chloride and SiO 2 Lithium carbonate Li 2 CO 3 And a water reducing agent JSS; silicate-sulphoaluminate composite cement composed of ordinary silicate cement and sulphoaluminate cement according to the proportion of 4:6; calcium chloride: the addition amount is 2-5% of silicate-sulphoaluminate composite cement; mixing silicate-sulphoaluminate composite cement and calcium chloride to obtain composite cement base solution; siO (SiO) 2 : the addition amount is 0.1-0.4% of the composite cement base solution; lithium carbonate Li 2 CO 3 : the addition amount is the composite cement base solution: 0.03-0.05%; water reducer JSS: the addition amount is 0.5-0.7% of the composite cement base solution; the water-cement ratio of the composite cement base solution is 0.5-0.6. The nano composite cement has the advantages of freezing resistance, low initial viscosity and good fluidity; the pump period is adjustable, and the initial and final setting interval time is short; low costEnvironmental protection; the cement slurry has good stability and high calculus rate.
The university of eastern and south China patent application CN106431042A discloses a method for dispersing and surface treating nano-sized mineral admixture, which comprises the following steps: (1) Fully dispersing the nano-sized mineral admixture to be treated in water to obtain a dispersion liquid; (2) Adding aminosilane into the dispersion liquid in the step (1) to enable the aminosilane to be combined with hydroxyl groups on the surfaces of nano particles of the nano-sized mineral admixture after being hydrolyzed; (3) Then adding a polycarboxylic acid polymer containing carboxyl branched chains to combine the hydrolyzed organic group with the amino group on the surface of the aminosilane; (4) And (3) extracting the nano-sized mineral admixture in the dispersion liquid in the step (3), cleaning the unreacted aminosilane and polycarboxylic acid polymer on the surface, and drying to obtain the nano-sized mineral admixture after surface treatment. The nano-sized mineral admixture treated by the method has the advantages of stable dispersing effect, capability of fully contacting with aqueous solution and small obstruction to the pozzolan reaction of particles.
The nano material is used as mineral admixture and added into cement concrete material, so that the nano filling effect of the nano material can be exerted, the microstructure of cement stone is improved, meanwhile, nano material particles can be used as nucleation sites of hydration products, the formation of the hydration products is promoted, and the hydration reaction process of cement is promoted. The nano material improves the microstructure of cement, so that the mechanical property of the cement concrete material is improved.
However, the existing mineral admixture is not ideal for improving the mechanical properties of cement paste, especially the early compressive strength and flexural strength of cement paste.
Disclosure of Invention
The invention aims to provide a building composite material, a preparation method and application thereof. Compared with the prior art, the building composite material can better improve the early compressive strength and the flexural strength of the cement paste, thereby obviously improving the mechanical property of the cement paste.
In order to achieve the above object, on the one hand, the technical scheme adopted by the invention is as follows: a building composite selected from the group consisting of silica-titania composite nanomaterial; the silica-titania composite nano material is characterized by being of a core-shell structure.
The building composite material according to the present invention, wherein the silica-titania composite nanomaterial has an average particle diameter of 100 to 800nm.
Preferably, the average particle size of the silica-titania composite nanomaterial is 300-400nm.
The building composite according to the present invention, wherein the silica-titania composite nanomaterial is composed of silica spherical particles as an inner core and a titania layer as an outer shell.
The building composite according to the present invention, wherein the ratio of the particle diameter of the spherical silica particles to the thickness of the titania layer is (4-8): 1.
Preferably, the ratio of the particle diameter of the spherical silica particles to the thickness of the titania layer is (5-7): 1.
The building composite material of the invention, wherein the titanium dioxide layer is of a porous structure.
The building composite according to the present invention, wherein the titanium dioxide layer has an average pore size of two BJHs of 10nm or less.
The building composite material according to the invention, wherein the average pore diameters of the two BJH are respectively 3-5nm and 6-8nm.
Preferably, the average pore diameters of the two BJHs are 3.5-4.5nm and 6.5-7.5nm, respectively.
The building composite according to the present invention, wherein the titanium dioxide layer is an amorphous phase.
The building composite according to the present invention, wherein the BET surface area of the silica-titania composite nanomaterial is 100 to 140m 2 /g。
Preferably, the BET surface area of the silica-titania composite nanomaterial is 110-130m 2 /g。
On the other hand, the invention also provides a preparation method of the building composite material, which comprises the following steps:
(1) Respectively preparing nano silicon dioxide dispersion liquid and ethylene glycol titanium hydrolysate with pH=5-7;
(2) Under the irradiation of 200-600W ultraviolet light, dripping the ethylene glycol titanium hydrolysate into the nano silicon dioxide dispersion liquid at the dripping speed of 1-3mL/min, wherein the volume ratio of the ethylene glycol titanium hydrolysate to the nano silicon dioxide dispersion liquid is 1 (4-6), and stirring while dripping; filtering, washing and drying;
(3) Calcining the dried product at 300-400 ℃ for 2-10h.
In yet another aspect, the present invention also provides the use of the building composite as a mineral admixture.
The use according to the invention, wherein the mineral admixture is added in an amount of 0.1-4wt%.
The use according to the invention, wherein the use is further to increase the early compressive and flexural strength of the cement paste.
The use according to the invention, wherein the cement paste has a water to ash ratio of 0.3-0.4.
Compared with the prior art, the building composite material can better improve the early compressive strength and the flexural strength of the cement paste, thereby obviously improving the mechanical property of the cement paste.
Drawings
Fig. 1 (a) and 1 (B) are SEM pictures of untreated nano-silica particles and finally obtained silica-titania composite nano-material, respectively.
Fig. 2 is a TEM photograph of the silica-titania composite nanomaterial.
FIG. 3 is a BJH curve of an isothermal adsorption line of a silica-titania composite nanomaterial.
Detailed Description
It must be noted that, as used in this specification and the appended claims, the singular forms "a," "an," and "the" include both a reference and a plurality of references (i.e., more than two, including two) unless the context clearly dictates otherwise.
Unless otherwise indicated, the numerical ranges in the present invention are approximate, and thus values outside the ranges may be included. The numerical ranges may be expressed herein as from "about" one particular value, and/or to "about" another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about," it will be understood that the particular value forms another aspect. It will also be understood that the endpoints of each of the numerical ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
References in the specification and the claims to parts by weight of a particular element or component in a composition or article refer to the relationship by weight between that element or component and any other element or component in the composition or article.
In the present invention, unless specifically indicated to the contrary, or implied by the context of the context or conventional means in the art, the solutions referred to in the present invention are aqueous solutions; when the solute of the aqueous solution is a liquid, all fractions and percentages are by volume, and the volume percent of the component is based on the total volume of the composition or product comprising the component; when the solute of the aqueous solution is a solid, all fractions and percentages are by weight, and the weight percentages of the components are based on the total weight of the composition or product comprising the components.
References to "comprising," "including," "having," and similar terms in this invention are not intended to exclude the presence of any optional components, steps or procedures, whether or not any optional components, steps or procedures are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all methods claimed through use of the term "comprising" may include one or more additional steps, apparatus parts or components and/or materials. In contrast, the term "consisting of … …" excludes any component, step or procedure not specifically recited or enumerated. The term "or" refers to members recited individually as well as in any combination unless otherwise specified.
Furthermore, the contents of any of the referenced patent documents or non-patent documents in the present invention are incorporated by reference in their entirety, especially with respect to the definitions and general knowledge disclosed in the art (in case of not inconsistent with any definitions specifically provided by the present invention).
In the present invention, parts are parts by weight unless otherwise indicated, temperatures are expressed in degrees celsius or at ambient temperature, and pressures are at or near atmospheric. Room temperature represents 20-30 ℃. The particle size of the spherical particles is the diameter, and the particle size of the non-spherical particles adopts the equivalent particle size. There are numerous variations and combinations of reaction conditions (e.g., component concentrations, solvents needed, solvent mixtures, temperatures, pressures, and other reaction ranges) and conditions that can be used to optimize the purity and yield of the product obtained by the process. Only reasonable routine experimentation will be required to optimize such process conditions.
Example 1
(1) The preparation method of the nano silicon dioxide dispersion liquid comprises the following specific steps: 2 parts of nano silicon dioxide with the average particle size of 300nm, 4 parts of sodium dodecyl sulfate, 6 parts of n-tetradecanol and 88 parts of water are weighed, uniformly mixed and stirred for 1h at 60 ℃ to obtain nano silicon dioxide dispersion liquid.
(2) The preparation method of the ethylene glycol titanium hydrolysate comprises the following specific steps: 2 parts of ethylene glycol titanium, 18 parts of ethylene glycol and 80 parts of water are weighed, and the pH=6.2 is adjusted to obtain an ethylene glycol titanium hydrolysate.
(3) Under the irradiation of 400W ultraviolet light, the ethylene glycol titanium hydrolysate is dripped into the nano silicon dioxide dispersion liquid at the dripping speed of 2mL/min, the volume ratio of the ethylene glycol titanium hydrolysate to the nano silicon dioxide dispersion liquid is 1:5, and the stirring is carried out while the dripping speed is 300rpm, and the reaction is continued for 2h after the dripping. Filtering, washing with water and ethanol for 2 times, and vacuum drying.
(4) And calcining the dried product at a high temperature of 350 ℃ for 6 hours to obtain the silicon dioxide-titanium dioxide composite nano material with the core-shell structure.
FIGS. 1 (A) and 1 (B) are untreated nanosilica particles and, respectivelyFinally, the silica-titania composite nano material is obtained. Fig. 2 shows that the silica-titania composite nanomaterial is a core-shell structure, and the average thickness of the titania layer is 24nm. FIG. 3 shows that the titanium dioxide layer has a porous structure, and the average pore diameters of BJH are 2, 4.2nm and 7.0nm respectively; BET surface area of 116m 2 And/g. Powder XRD patterns showed that the titania layer was amorphous and that no anatase and rutile phases were present.
Comparative example 1
(1) The preparation method of the nano silicon dioxide dispersion liquid comprises the following specific steps: 2 parts of nano silicon dioxide with the average particle size of 300nm, 4 parts of sodium dodecyl sulfate, 6 parts of n-tetradecanol and 88 parts of water are weighed, uniformly mixed and stirred for 1h at 60 ℃ to obtain nano silicon dioxide dispersion liquid.
(2) The preparation method of the ethylene glycol titanium hydrolysate comprises the following specific steps: 2 parts of ethylene glycol titanium, 18 parts of ethylene glycol and 80 parts of water are weighed, and the pH=6.2 is adjusted to obtain an ethylene glycol titanium hydrolysate.
(3) And (3) dropwise adding the ethylene glycol titanium hydrolysate into the nano silicon dioxide dispersion liquid at a dropwise adding speed of 2mL/min, wherein the volume ratio of the ethylene glycol titanium hydrolysate to the nano silicon dioxide dispersion liquid is 1:5, stirring is carried out while dropwise adding, the stirring speed is 300rpm, and the reaction is continued for 2h after the dropwise adding is finished. Filtering, washing with water and ethanol for 2 times, and vacuum drying.
(4) And calcining the dried product at a high temperature of 350 ℃ for 6 hours to obtain the silicon dioxide-titanium dioxide composite nano material with the core-shell structure.
TEM shows that the silicon dioxide-titanium dioxide composite nano material has a core-shell structure, the titanium dioxide layer has a porous structure, and the average aperture of BJH is 8.7; BET surface area of 59.1m 2 And/g. Powder XRD patterns showed that the titania layer was anatase phase.
Application examples
The composite nanomaterial of example 1, the composite nanomaterial of comparative example 1, and untreated nanosilica particles (comparative example 2) were all added to cement in an amount of 2% as mineral admixtures, with a water-cement ratio of 0.35; the reference cement was used as a control group. The specification of the test block of the cement paste is 4cm multiplied by 4cm; the test block is molded and cured in the early age according to GB/T17671-2021.
The cement adopts standard cement. The main chemical composition of the standard cement is CaO 63.62 percent and SiO 2 20.83%、Al 2 O 3 4.97%、Fe 2 O 3 3.21%、MgO 2.26%、SO 3 2.09%、Na 2 O0.61%; 190 mesh screen residue 0.5%, specific surface area 358m 2 Per kg, density of 3.10g/cm 3 。
The results are shown in Table 1.
As can be seen from Table 1, the composite nanomaterial of example 1 of the present invention can better improve early compressive strength and flexural strength compared with comparative examples 1-2 and a control group (reference cement), thereby remarkably improving mechanical properties of cement paste.
Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present invention may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present invention as defined in the appended claims.
Claims (4)
1. A building composite selected from the group consisting of silica-titania composite nanomaterial; the silicon dioxide-titanium dioxide composite nano material is of a core-shell structure; the average grain diameter of the silicon dioxide-titanium dioxide composite nano material is 100-800nm; the silicon dioxide-titanium dioxide composite nano material consists of silicon dioxide spherical particles serving as a core and a titanium dioxide layer serving as a shell; the ratio of the particle diameter of the spherical silica particles to the thickness of the titanium dioxide layer is (4-8): 1;
it is characterized in that the method comprises the steps of,
the titanium dioxide layer is of a porous structure; the titanium dioxide layer has two BJH average pore diameters below 10 nm; the average pore diameters of the two BJH are respectively 3-5nm and 6-8nm; the titanium dioxide layer is an amorphous phase;
wherein the method comprises the steps ofThe BET surface area of the silicon dioxide-titanium dioxide composite nano material is 100-140m 2 /g；
The preparation method of the building composite material comprises the following steps:
(1) The preparation method of the nano silicon dioxide dispersion liquid comprises the following specific steps: 2 parts of nano silicon dioxide with the average particle size of 300nm, 4 parts of sodium dodecyl sulfate, 6 parts of n-tetradecanol and 88 parts of water are weighed, uniformly mixed and stirred for 1 hour at 60 ℃ to obtain nano silicon dioxide dispersion liquid;
(2) The preparation method of the ethylene glycol titanium hydrolysate comprises the following specific steps: weighing 2 parts of ethylene glycol titanium, 18 parts of ethylene glycol and 80 parts of water, and adjusting the pH value to be 6.2 to obtain an ethylene glycol titanium hydrolysate;
(3) Under the irradiation of 400W ultraviolet light, dropwise adding the ethylene glycol titanium hydrolysate into the nano silicon dioxide dispersion liquid at a dropwise adding speed of 2mL/min, wherein the volume ratio of the ethylene glycol titanium hydrolysate to the nano silicon dioxide dispersion liquid is 1:5, stirring is carried out while dropwise adding, the stirring speed is 300rpm, and the reaction is continued for 2 hours after the dropwise adding is finished; filtering, washing with water and ethanol for 2 times, and vacuum drying;
(4) And calcining the dried product at a high temperature of 350 ℃ for 6 hours to obtain the silicon dioxide-titanium dioxide composite nano material with the core-shell structure.
2. Use of the building composite according to claim 1 as mineral admixture in cement.
3. Use according to claim 2, wherein the mineral admixture is added in an amount of 0.1-4wt%.
4. Use according to claim 2, wherein the use is further to increase the early compressive and flexural strength of the cement paste, wherein the cement paste has a water to ash ratio of 0.3-0.4.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102762498A (en) * | 2010-02-19 | 2012-10-31 | 株式会社德山 | Method for producing inorganic oxide particles |
| CN115368055A (en) * | 2022-08-10 | 2022-11-22 | 佛山市鲸砼科技有限公司 | Antibacterial agent for building, antibacterial mortar and application thereof |
| CN116063025A (en) * | 2023-03-30 | 2023-05-05 | 中国标准化研究院 | Composite mineral admixture for building and preparation method thereof |
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| WO2001042140A1 (en) * | 1999-12-13 | 2001-06-14 | Jonathan Sherman | Nanoparticulate titanium dioxide coatings, and processes for the production and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102762498A (en) * | 2010-02-19 | 2012-10-31 | 株式会社德山 | Method for producing inorganic oxide particles |
| CN115368055A (en) * | 2022-08-10 | 2022-11-22 | 佛山市鲸砼科技有限公司 | Antibacterial agent for building, antibacterial mortar and application thereof |
| CN116063025A (en) * | 2023-03-30 | 2023-05-05 | 中国标准化研究院 | Composite mineral admixture for building and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 王丹.纳米SiO2对水泥基材料表面改性研究.《中国博士学位论文全文数据库（电子期刊）》.2019,第35-104页. * |
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