CN115058119A - Self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and preparation method thereof - Google Patents
Self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and preparation method thereof Download PDFInfo
- Publication number
- CN115058119A CN115058119A CN202210778439.1A CN202210778439A CN115058119A CN 115058119 A CN115058119 A CN 115058119A CN 202210778439 A CN202210778439 A CN 202210778439A CN 115058119 A CN115058119 A CN 115058119A
- Authority
- CN
- China
- Prior art keywords
- silica
- self
- waste
- alumino
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 67
- 239000004005 microsphere Substances 0.000 title claims abstract description 65
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 238000004140 cleaning Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000000839 emulsion Substances 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 16
- 229920001843 polymethylhydrosiloxane Polymers 0.000 claims abstract description 14
- -1 fluoroalkyl silane Chemical compound 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 49
- 238000003756 stirring Methods 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000002893 slag Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 150000007529 inorganic bases Chemical class 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000010881 fly ash Substances 0.000 claims description 8
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 32
- 239000011248 coating agent Substances 0.000 abstract description 28
- 238000000576 coating method Methods 0.000 abstract description 28
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract description 3
- 239000003921 oil Substances 0.000 abstract description 3
- 230000008439 repair process Effects 0.000 abstract description 3
- 239000011538 cleaning material Substances 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 description 27
- 238000012360 testing method Methods 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 9
- 239000003344 environmental pollutant Substances 0.000 description 7
- 231100000719 pollutant Toxicity 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 239000004566 building material Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- PISDRBMXQBSCIP-UHFFFAOYSA-N trichloro(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CC[Si](Cl)(Cl)Cl PISDRBMXQBSCIP-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- AVYKQOAMZCAHRG-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AVYKQOAMZCAHRG-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/05—Polysiloxanes containing silicon bound to hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K11/00—Use of ingredients of unknown constitution, e.g. undefined reaction products
- C08K11/005—Waste materials, e.g. treated or untreated sewage sludge
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention provides a self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and a preparation method thereof, belonging to the technical field of self-cleaning materials. According to the mass percentage, the super-hydrophobic microspheres comprise the following components: and (2) component A: 70-75% of silicon-aluminum waste, 6-9% of silica fume, 6-9% of nano silicon dioxide emulsion, 6-9% of inorganic alkali and 7-10% of water; and B component: 30-50% of polymethylhydrosiloxane and 50-70% of fluoroalkyl silane; the super-hydrophobic microspheres prepared by the invention take alumino-silicate waste as a main raw material, change waste into valuable, save natural resources, and have excellent comprehensive properties of water resistance, oil resistance, dust resistance, wear resistance and the like; when the material is used as a building coating material, the repair and protection of cracked concrete can be realized; meanwhile, the coating material is more wear-resistant and has better durability.
Description
Technical Field
The invention belongs to the technical field of self-cleaning materials, and particularly relates to a self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and a preparation method thereof.
Background
The super-hydrophobic film has the important characteristics of water resistance, fog resistance, snow resistance, pollution prevention, adhesion resistance, oxidation resistance, corrosion resistance and the like, and has wide application prospects in various fields of scientific research, production, life and the like. The super-hydrophobic surface depends on the combination of a low surface energy substance and a rough surface structure, the cost of the existing super-hydrophobic coating is high, and the most critical microstructure and the low surface energy substance which form the super-hydrophobic surface are easy to damage under the action of mechanical external force such as abrasion and impact and external environment such as condensation and frosting, so that the super-hydrophobicity is reduced or fails. Therefore, the realization of the low-cost preparation of the super-hydrophobic surface and the long-term service are the international leading research subjects in the fields of material science and the like.
China is rapidly developed in urbanization and industrialization, and the annual waste amount is about 60 hundred million tons, wherein 35 hundred million tons of industry, 25-30 million tons of construction waste and 3-3.5 million tons of household waste are produced. Meanwhile, the stacking accumulation amount of the whole industrial solid waste reaches 600 hundred million tons, and meanwhile, the phenomenon of serious waste enclosing city exists. The comprehensive utilization of solid wastes is promoted, and the method has important significance for improving the utilization efficiency of resources, improving the environmental quality, promoting the development of social economy and realizing comprehensive green transformation. The green and efficient comprehensive application of the solid waste is an effective way for ecological civilization construction under new conditions in China and is also a key research direction in the fields of material science and the like.
The technical problem to be solved urgently in China at present is to reduce the production cost and fully utilize the silicon-aluminum waste.
Disclosure of Invention
The invention aims to provide a self-cleaning super-hydrophobic microsphere prepared by using alumino-silica waste and a preparation method thereof, and aims to solve the problem that the alumino-silica waste cannot be effectively utilized at present.
In order to achieve the above purpose, the invention provides the following technical scheme:
the self-cleaning super-hydrophobic microsphere prepared from the alumino-silica waste is characterized by comprising the following components in percentage by mass:
the component A comprises: 70-75% of silicon-aluminum waste, 6-9% of silica fume, 6-9% of nano silicon dioxide emulsion, 6-9% of inorganic base and 7-10% of water;
and B component: 30-50% of polymethylhydrosiloxane and 50-70% of fluoroalkyl silane.
In the self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste, preferably, the alumino-silica waste is one or a mixture of more of fly ash, red mud and steel slag.
In the self-cleaning super-hydrophobic microspheres prepared by using the silicon-aluminum waste, preferably, the mass fraction of nano-silicon dioxide in the nano-silicon dioxide emulsion is 5-10%, and the particle size of the nano-silicon dioxide is less than 200 nm.
In the self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste as described above, the nano-silica is selected from one or more of silica sol, slag and white carbon black.
In the self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste as described above, preferably, the fluoroalkyl silane comprises triethoxy-1H, 2H-tridecafluoro-N-octyl silane or 1H, 2H-perfluorooctyltrichlorosilane.
In the self-cleaning super-hydrophobic microspheres prepared by using the silicon-aluminum waste, preferably, the inorganic alkali is one or a mixture of potassium powder, potassium hydroxide, sodium hydroxide and lithium hydroxide;
the mass fraction of silicon dioxide in the silica fume is 92-98%.
In the self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste, the mass ratio of the component A to the component B is preferably 1 (0.5-1.4).
In the self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste, preferably, the preparation method of the nano-silica emulsion comprises the following steps:
mixing the nano silicon dioxide and the deionized water in a container, and stirring the container at the temperature of 70-90 ℃ and the stirring speed of 250-350rpm for 4-6h to obtain the nano silicon dioxide emulsion.
A preparation method of self-cleaning super-hydrophobic microspheres prepared from alumino-silica waste comprises the following steps:
step one, weighing the silicon-aluminum waste and the silica fume according to the proportion into a container, uniformly stirring and mixing, then adding inorganic base and water, and stirring for 5-7h at room temperature; adding the nano silicon dioxide emulsion according to the proportion, and stirring for 1-2h to obtain a component A;
mixing polymethylhydrosiloxane and fluoroalkyl silane according to a ratio to obtain a component B;
and step three, mixing the component A and the component B, continuing stirring for 1-2 hours, then precipitating for 24 hours, extracting bottom precipitates, drying, grinding and screening to obtain the self-cleaning super-hydrophobic microspheres.
In the preparation method of the self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste, preferably, the stirring speed in the first step and the third step is 250-350 rpm;
preferably, the particle size of the self-cleaning super-hydrophobic microspheres is 15-20 μm.
Has the advantages that:
1. the super-hydrophobic microspheres prepared by the method take the silicon-aluminum waste as a main raw material, the consumption of the super-hydrophobic microspheres is over 70 percent, and the healthy and sustainable development capability of the fuel combustion industry is enhanced; changing waste into valuable, saving natural resources and having good economic benefit and long-term social benefit;
2. the self-cleaning super-hydrophobic microspheres prepared by the method have excellent comprehensive properties of water resistance, oil resistance, dust resistance, wear resistance and the like;
3. the super-hydrophobic microspheres are used as building coating materials, so that the repair and protection of cracked concrete can be realized; meanwhile, the coating material is more wear-resistant and has better durability.
4. The super-hydrophobic microsphere has low preparation cost and simple synthesis, and the byproduct is H 2 And H 2 And O meets the aims of green chemistry and carbon neutralization, not only has high utilization rate, but also has the outstanding characteristics of energy conservation, consumption reduction and the like without high-temperature calcination in the preparation process, and has very wide application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. Wherein:
FIG. 1 is a scanning electron microscope image of a self-cleaning super-hydrophobic microsphere prepared in example 1 of the present invention;
FIG. 2 shows the change rule of the contact angle and the rolling angle of the self-cleaning super-hydrophobic microsphere prepared in example 1 of the present invention during the process of wear resistance test.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The invention provides a technical approach for solving the problem of environmental pollution caused by discharge and accumulation of solid waste and fly ash, and can produce a self-cleaning hydrophobic material with excellent performance to meet the requirement of the market on novel building materials.
The invention adopts inorganic alkali to etch the silicon-aluminum waste and the nano silicon dioxide (NS) to prepare the self-cleaning super-hydrophobic microspheres (SMs) with micron to nano scale. The low surface energy and wear resistant surface of the self-cleaning super-hydrophobic microspheres (SMs) is constructed by using Fluoroalkylsilane (FAS) and Polymethylhydrosiloxane (PMHS). The method provides a new idea and a new technology for recycling the silicon-aluminum waste and the silica fume generated by fuel combustion, can promote the development of building materials, has important theoretical significance and obvious engineering application value, and has very wide market prospect.
The invention provides a self-cleaning super-hydrophobic microsphere prepared by using alumino-silicon waste, which comprises the following components in percentage by mass:
the component A comprises: 70-75% of alumino-silica waste (such as 71%, 72%, 73%, 74%), 6-9% of silica fume (such as 6.5%, 7%, 7.5%, 8%, 8.5%, 9%), 6-9% of nano-silica emulsion (such as 6.5%, 7%, 7.5%, 8%, 8.5%, 9%), 6-9% of inorganic base (such as 6.5%, 7%, 7.5%, 8%, 8.5%, 9%), and 7-10% of water (such as 7%, 7.5%, 8%, 8.5%, 9%, 9.5%);
and B component: 30-50% (such as 35%, 40%, 45%, 50%) of polymethylhydrosiloxane, and 50-70% (such as 55%, 60%, 65%, 70%) of fluoroalkylsilane.
In a specific embodiment of the invention, the mass ratio of the component A to the component B is 1 (0.5-1.4) (such as 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1.0, 1:1.1, 1:1.2, 1: 1.3). Too low or too high content of the component B can cause the hydrophobic property of the microspheres to be poor, and the low content of the component B has larger influence on the hydrophobic property of the microspheres.
In the specific embodiment of the invention, the alumino-silicate waste is one or a mixture of more of fly ash, red mud and steel slag.
The grain size of the fly ash is 3-5 mu m, and the grain size of the steel slag is not more than 10 mu m.
In one embodiment of the present invention, the silica content of the silica fume is 92-98% (e.g., 93%, 94%, 95%, 96%, 97%, 98%).
In an embodiment of the present invention, the mass fraction of the nano-silica in the nano-silica emulsion is 5-10% (e.g. 6%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%), and the particle size of the nano-silica is less than 200 nm. Too low or too high a content of nanosilica in the nanosilica emulsion may deteriorate the hydrophobic properties of the microspheres.
In a specific embodiment of the present invention, the nano-silica is selected from one or more of silica sol, slag and silica white. The nano silicon dioxide is amorphous phase silicon dioxide.
The main chemical component of the slag is SiO 2 、Al 2 O 3 And CaO; the slag in the invention is superfine slag, and the grain diameter of the slag is 2-3 mu m.
In the specific embodiment of the invention, the inorganic alkali is one or a mixture of potassium powder, potassium hydroxide, sodium hydroxide and lithium hydroxide;
in particular embodiments of the invention, the fluoroalkylsilane comprises triethoxy-1H, 1H,2H, 2H-tridecafluoro-N-octylsilane or 1H,1H,2H, 2H-perfluorooctyltrichlorosilane.
In the specific embodiment of the invention, the preparation method of the nano silicon dioxide emulsion comprises the following steps:
mixing the nano-silica and the deionized water in a container, and stirring the container for 4-6h (such as 4.5h, 5h and 5.5h) at the stirring speed of 70-90 ℃ (such as 75 ℃, 80 ℃ and 85 ℃) and 250-350rpm (such as 260rpm, 280rpm, 300rpm, 320rpm and 340rpm) to obtain the nano-silica emulsion.
The invention also provides a preparation method of the self-cleaning super-hydrophobic microspheres prepared from the silicon and aluminum waste, and the preparation method comprises the following steps:
step one, weighing the silicon-aluminum waste and the silica fume according to the proportion into a container, uniformly stirring and mixing, then adding inorganic base and water, and stirring for 5-7h at room temperature; adding the nano silicon dioxide emulsion according to the proportion, and stirring for 1-2h to obtain a component A;
mixing polymethylhydrosiloxane and fluoroalkyl silane according to a ratio to obtain a component B;
and step three, mixing the component A and the component B, continuing stirring for 1-2 hours, then precipitating for 24 hours, extracting bottom precipitates, drying, grinding and screening to obtain the self-cleaning super-hydrophobic microspheres.
In the specific embodiment of the invention, the stirring speed in the first step and the third step is 250-350 rpm; the particle size of the self-cleaning super-hydrophobic microspheres is 15-20 μm.
The principle of the invention is that the surface of the alumino-silica waste and the silica fume is etched by alkali to form a rough surface substance, the polymethylhydrosiloxane is used as a cross-linking agent, the etched alumino-silica waste, the silica fume and the nano-silica emulsion are bonded together to form a rough structure substance, and meanwhile, the fluoroalkylsilane is bonded on the rough structure substance to provide low surface energy, so that the self-cleaning superhydrophobic microsphere is formed and used as a coating material of a building material, and has higher wear resistance and self-cleaning function.
Example 1
The self-cleaning super-hydrophobic microsphere prepared by using the silicon-aluminum waste comprises the following components;
the component A comprises:
the waste silica-alumina (comprising 40% of fly ash, 20% of red mud and 11% of steel slag), 7% of silica fume, 8% of nano silicon dioxide emulsion, 7% of water and 7% of inorganic base (sodium hydroxide);
and B component:
30% of polymethylhydrosiloxane;
fluoroalkylsilane (triethoxy-1H, 2H-tridecafluoro-N-octylsilane) 70%;
the mass ratio of the component A to the component B is 1:1.
The mass fraction of silicon dioxide in the silica fume is 92%.
The preparation method of the self-cleaning super-hydrophobic microsphere provided in the embodiment comprises the following steps:
step one, weighing the silicon-aluminum waste and the silica fume according to the proportion into a container, uniformly stirring and mixing, then adding inorganic base and water, and stirring at room temperature for 5 hours at the stirring speed of 300 rpm; adding the nano silicon dioxide emulsion according to the proportion, stirring for 1h at the stirring speed of 300rpm to obtain a component A;
mixing polymethylhydrosiloxane and fluoroalkyl silane according to a ratio to obtain a component B;
and step three, mixing the component A and the component B, continuing stirring for 1h at the stirring speed of 300rpm, then precipitating, extracting bottom precipitates, drying for 24h at 80 ℃, grinding and screening, and passing through a 30-mesh screen to obtain the self-cleaning super-hydrophobic microspheres.
Wherein, the preparation process of the nano silicon dioxide emulsion comprises the following steps:
mixing silica sol and deionized water in a container, and stirring the container at the temperature of 80 ℃ and the stirring speed of 300rpm for 5 hours to obtain the nano silicon dioxide emulsion.
Wherein the mass fraction of the nano silicon dioxide in the nano silicon dioxide emulsion is 8 percent, and the particle size of the nano silicon dioxide is 100-190 nm.
The self-cleaning superhydrophobic microspheres prepared in this example were subjected to hydrophobicity and abrasion resistance tests as shown in fig. 1.
Vulcanized rubber which is in a liquid state at room temperature and the self-cleaning super-hydrophobic microspheres are mixed according to the ratio of 19: mixed and coated on the surface of a building material at a mass ratio of 1 to form a coating material (namely a sample).
The surface layer is abraded by 800-mesh abrasive paper under the pressure of 800Pa, a sample is subjected to a friction experiment test by dragging a coating material at a constant speed, the surfaces of the coating material before and after the friction experiment are coated by adopting clean water, and the contact angle and the rolling angle of the surfaces are tested.
Before a friction experiment, the contact angle of a coating material coated by clean water is 153.6 degrees, and the rolling angle is 16.5 degrees; after the rubbing test, the contact angle of the coating material was 150 °, and the rolling angle was 15.5 °.
Domestic sewage is sucked, the domestic sewage is dripped on the surface of the coating material, the contact angle is 151 degrees and the rolling angle is 15.4 degrees after the domestic sewage is dripped.
The surface layer was abraded with 800-mesh sandpaper under a pressure of 800Pa, and the contact angle and the sliding angle were monitored along a cumulative abrasion distance of 0 to 20 m. Fig. 2 shows the change rule of the contact angle and the rolling angle of the self-cleaning super-hydrophobic microsphere prepared in example 1 of the present invention during the abrasion resistance test. The contact angle of the sample increased to 153.2 ° when the initial rubbing distance was 2m, and the contact angle tended to level off above 150 ° when the abrasion distance was 20 m. When the rubbing distance was 16m, the roll angle continued to increase to 10 ° or more.
The surface of the coating material also had a retention of 99% area after 20m rubbing (1% reduction in coating material).
The self-cleaning super-hydrophobic microsphere prepared in the embodiment has good wear resistance, large contact angle and good hydrophobicity.
Example 2
The difference between this example and example 1 is that the raw material components of component A and component B are different, and the other method steps are the same as example 1 and are not described again.
The component A comprises:
the waste of silicon and aluminum (comprising 30 percent of fly ash, 10 percent of red mud and 32 percent of steel slag), 6 percent of silicon ash, 6 percent of nano silicon dioxide emulsion, 10 percent of water and 6 percent of inorganic alkali (potassium hydroxide);
and B component:
40% of polymethylhydrosiloxane;
60% of fluoroalkylsilane (1H,1H,2H, 2H-perfluorooctyltrichlorosilane);
the mass ratio of the component A to the component B is 1: 1.2.
The self-cleaning superhydrophobic microspheres prepared in this example were subjected to the same hydrophobicity and abrasion resistance tests as in example 1.
The contact angle before the surface friction test of the sample is 151.3 degrees, and the rolling angle is 15.5 degrees; after the rubbing test, the contact angle was 149.2 ° and the rolling angle was 15.9 °.
After the pollutants are coated, the contact angle is 147 degrees, and the rolling angle is 16 degrees.
Example 3
The difference between this example and example 1 is that the raw materials of component A and component B are different, and the other method steps are the same as example 1, and are not described again here.
In the component A, the alumino-silica waste (including 71% of fly ash) was otherwise the same as the component A of example 1.
And B component:
35% of polymethylhydrosiloxane;
fluoroalkylsilane (triethoxy-1H, 2H-tridecafluoro-N-octylsilane) 65%.
The same performance test as in example 1 was performed on the self-cleaning superhydrophobic microspheres prepared in this example.
Before a friction experiment, the contact angle of a coating material is 151.5 degrees, and the rolling angle is 15.1 degrees; after the rubbing test, the contact angle of the coating material was 149.5 ° and the rolling angle was 15.9 °.
After the pollutants are coated, the contact angle is 148 degrees, and the rolling angle is 16.5 degrees.
Example 4
In this embodiment, the mass fraction of the nano-silica in the nano-silica emulsion is changed, and other steps of the method are the same as those in embodiment 1, and are not repeated herein.
The mass fraction of the nano silicon dioxide in the nano silicon dioxide emulsion is 5 percent, and the particle size of the nano silicon dioxide is 100-190 nm.
The same performance test as in example 1 was performed on the self-cleaning superhydrophobic microspheres prepared in this example.
Before a friction experiment, the contact angle of a coating material is 151.8 degrees, and the rolling angle is 15.2 degrees; after the rubbing test, the contact angle of the coating material was 149.9 °, and the rolling angle was 16.2 °.
After the pollutants are dripped, the contact angle is 147.2 degrees, and the rolling angle is 17.1 degrees.
Example 5
The difference between this example and example 1 is that the mass ratio between the component a and the component B is changed, and the other method steps are the same as example 1 and will not be described again.
The mass ratio of the component A to the component B is 1: 0.6.
The same performance test as in example 1 was performed on the self-cleaning superhydrophobic microspheres prepared in this example.
Before a friction experiment, the contact angle of a coating material is 145 degrees, and the rolling angle is 10 degrees; after the rubbing test, the contact angle of the coating material was 142 °, and the rolling angle was 12 °.
After the pollutants are dripped, the contact angle is 140 degrees, and the rolling angle is 11 degrees.
Example 6
The difference between the embodiment and the embodiment 1 is that the raw material selected in the preparation process of the nano-silica emulsion is ultrafine slag with the particle size of 2-3 μm, and the other method steps are the same as the embodiment 1 and are not repeated herein.
The same performance test as in example 1 was performed on the self-cleaning superhydrophobic microspheres prepared in this example.
Before a friction experiment, the contact angle of a coating material coated by clean water is 152.8 degrees, and the rolling angle is 15.4 degrees; after the rubbing test, the contact angle of the coating material was 150.2 °, and the rolling angle was 16.2 °.
After the pollutants are dripped, the contact angle is 148.3 degrees, and the rolling angle is 16.5 degrees.
Comparative example 1
The comparative example differs from example 1 in that: the procedure of example 1 was repeated except that no silica sol, i.e., no nanosilica emulsion was added.
The same performance test as in example 1 was performed on the self-cleaning superhydrophobic microspheres prepared in this comparative example.
Before a friction experiment, the contact angle of a coating material coated by clean water is 106 degrees, and the rolling angle is 7 degrees; after the rubbing test, the contact angle of the coating material was 95 ° and the rolling angle was 22 °.
After the pollutants are dripped, the contact angle is 100 degrees, and the rolling angle is 23 degrees.
Comparative example 2
The comparative example differs from example 2 in that: the procedure of example 1 was repeated except that no inorganic base was added.
The same performance test as in example 1 was performed on the self-cleaning superhydrophobic microspheres prepared in this comparative example.
Before a friction experiment, the contact angle of a coating material coated by clean water is 92 degrees, and the rolling angle is 28 degrees; after the rubbing test, the contact angle of the coating material was 84 ° and the rolling angle was 31 °.
After the pollutants are dripped, the contact angle is 87 degrees, and the rolling angle is 30 degrees.
In conclusion: the super-hydrophobic microspheres prepared by the method take the silicon-aluminum waste as a main raw material, the consumption of the super-hydrophobic microspheres is over 70 percent, and the healthy and sustainable development capability of the fuel combustion industry is enhanced; changing waste into valuable, saving natural resources and having good economic benefit and long-term social benefit;
the self-cleaning super-hydrophobic microspheres have excellent comprehensive properties of water resistance, oil resistance, dust resistance, wear resistance and the like; when the material is used as a building coating material, the repair and protection of cracked concrete can be realized; meanwhile, the coating material is more wear-resistant and has better durability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The self-cleaning super-hydrophobic microsphere prepared from the alumino-silica waste is characterized by comprising the following components in percentage by mass:
the component A comprises: 70-75% of silicon-aluminum waste, 6-9% of silica fume, 6-9% of nano silicon dioxide emulsion, 6-9% of inorganic base and 7-10% of water;
and B component: 30-50% of polymethylhydrosiloxane and 50-70% of fluoroalkyl silane.
2. The self-cleaning superhydrophobic microsphere prepared by using the alumino-silica waste as claimed in claim 1, wherein the alumino-silica waste is one or a mixture of more of fly ash, red mud and steel slag.
3. The self-cleaning superhydrophobic microsphere prepared by using the alumino-silica waste as claimed in claim 1, wherein the mass fraction of nano-silica in the nano-silica emulsion is 5-10%, and the particle size of the nano-silica is less than 200 nm.
4. The self-cleaning superhydrophobic microsphere prepared by using the alumino-silica waste as claimed in claim 3, wherein the nano silica is selected from one or more of silica sol, slag and white carbon black.
5. The self-cleaning superhydrophobic microspheres made of alumino-silicate waste according to claim 1, wherein the fluoroalkylsilane comprises triethoxy-1H, 2H-tridecafluoro-N-octylsilane or 1H, 2H-perfluorooctyltrichlorosilane.
6. The self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste as claimed in claim 1, wherein the inorganic alkali is one or a mixture of potassium powder, potassium hydroxide, sodium hydroxide and lithium hydroxide;
the mass fraction of silicon dioxide in the silica fume is 92-98%.
7. The self-cleaning super-hydrophobic microspheres prepared by using the alumino-silica waste as claimed in claim 1, wherein the mass ratio of the component A to the component B is 1 (0.5-1.4).
8. The self-cleaning super-hydrophobic microsphere prepared by using the alumino-silica waste as claimed in claim 1, wherein the preparation method of the nano-silica emulsion comprises the following steps:
mixing the nano silicon dioxide and the deionized water in a container, and stirring the container at the temperature of 70-90 ℃ and the stirring speed of 250-350rpm for 4-6h to obtain the nano silicon dioxide emulsion.
9. The preparation method of the self-cleaning super-hydrophobic microspheres prepared from the alumino-silica waste as set forth in any one of claims 1 to 8, wherein the preparation method comprises the following steps:
step one, weighing the silicon-aluminum waste and the silica fume according to the proportion into a container, uniformly stirring and mixing, then adding inorganic base and water, and stirring for 5-7h at room temperature; adding the nano silicon dioxide emulsion according to the proportion, and stirring for 1-2h to obtain a component A;
mixing polymethylhydrosiloxane and fluoroalkyl silane according to a ratio to obtain a component B;
and step three, mixing the component A and the component B, continuing stirring for 1-2 hours, then precipitating for 24 hours, extracting bottom precipitates, drying, grinding and screening to obtain the self-cleaning super-hydrophobic microspheres.
10. The method for preparing self-cleaning super-hydrophobic microspheres from alumino-silica waste as claimed in claim 9, wherein the stirring speed in the first step and the third step is 250-350 rpm;
the particle size of the self-cleaning super-hydrophobic microspheres is 15-20 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210778439.1A CN115058119A (en) | 2022-07-04 | 2022-07-04 | Self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210778439.1A CN115058119A (en) | 2022-07-04 | 2022-07-04 | Self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115058119A true CN115058119A (en) | 2022-09-16 |
Family
ID=83203698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210778439.1A Pending CN115058119A (en) | 2022-07-04 | 2022-07-04 | Self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115058119A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116904058A (en) * | 2023-06-16 | 2023-10-20 | 青岛理工大学 | Super-hydrophobic powder prepared by utilizing hole slag micro powder as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973559A (en) * | 2017-11-22 | 2018-05-01 | 广西大学 | The preparation method and applications of porous geological polymer microballoon |
| CN112321297A (en) * | 2020-10-20 | 2021-02-05 | 广西大学 | Method for preparing porous oxide microspheres by using geopolymer as binder |
| CN112608119A (en) * | 2020-12-23 | 2021-04-06 | 武汉理工大学 | Foam concrete doped with light silica microspheres through 3D printing and preparation method thereof |
| CN113060956A (en) * | 2021-05-17 | 2021-07-02 | 西南石油大学 | Geopolymer microspheres and preparation method thereof |
-
2022
- 2022-07-04 CN CN202210778439.1A patent/CN115058119A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973559A (en) * | 2017-11-22 | 2018-05-01 | 广西大学 | The preparation method and applications of porous geological polymer microballoon |
| CN112321297A (en) * | 2020-10-20 | 2021-02-05 | 广西大学 | Method for preparing porous oxide microspheres by using geopolymer as binder |
| CN112608119A (en) * | 2020-12-23 | 2021-04-06 | 武汉理工大学 | Foam concrete doped with light silica microspheres through 3D printing and preparation method thereof |
| CN113060956A (en) * | 2021-05-17 | 2021-07-02 | 西南石油大学 | Geopolymer microspheres and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| PANG, B等: ""Interface Properties of Nanosilica-Modified Waterborne Epoxy Cement Repairing System"" * |
| PANG; BO等: ""5S Multifunctional Intelligent Coating with Superdurable, Superhydrophobic, Self-Monitoring, Self-Heating, and Self-Healing Properties for Existing Construction Application"" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116904058A (en) * | 2023-06-16 | 2023-10-20 | 青岛理工大学 | Super-hydrophobic powder prepared by utilizing hole slag micro powder as well as preparation method and application thereof |
| CN116904058B (en) * | 2023-06-16 | 2024-01-30 | 青岛理工大学 | Super-hydrophobic powder prepared by utilizing hole slag micro powder as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110218504B (en) | Steel structure anticorrosive paint | |
| CN115058119A (en) | Self-cleaning super-hydrophobic microsphere prepared from silicon-aluminum waste and preparation method thereof | |
| CN114752278B (en) | Solvent-free high-temperature-resistant heavy-duty anticorrosive paint and preparation method thereof | |
| CN102690586A (en) | Heavy-duty anticorrosive coating for flue gas desulphurization equipment and preparation technology thereof | |
| CN105621907A (en) | Calcium-base geopolymer and preparation method thereof | |
| CN111718144B (en) | Preparation method and application of cement-based material additive | |
| CN109437710A (en) | A kind of high water-cement ratio low cost low-density well cementing cement mortar and preparation method thereof | |
| CN109575769A (en) | Super-hydrophobic and super oleophobic coating of one kind and preparation method thereof | |
| CN113061358B (en) | Anti-permeation long-acting anticorrosive coating and preparation method and application thereof | |
| CN109516707A (en) | A kind of preparation method for the recycled aggregate inhibiting alkali-aggregate reaction | |
| CN104293329A (en) | High-temperature well-cementing material system and composition thereof | |
| CN103214893A (en) | Phase-change thermal insulation putty | |
| CN110550916A (en) | Corrosion-resistant PHC pipe pile and preparation method thereof | |
| CN113511870A (en) | Solid waste base marine repair material and preparation method thereof | |
| CN113388275A (en) | Modified lithium-based concrete sealing curing agent and preparation method thereof | |
| CN113292901A (en) | Anticorrosive paint for blast furnace gas generator blade and preparation method and application thereof | |
| CN112321297B (en) | Method for preparing porous oxide microspheres by using geopolymer as binder | |
| CN109082151B (en) | Water-based super-amphiphobic silica sol and preparation method and application thereof | |
| Zhuang et al. | Influence of the moisture state of recycled fine aggregate on the impermeability of concrete | |
| CN112225478A (en) | Limestone machine-made sand concrete modifier and concrete containing same | |
| CN115558416B (en) | High-temperature-resistant anti-coking coating and preparation method thereof | |
| CN109467328B (en) | Gypsum-based quasi-round aggregate for self-leveling ground and preparation method thereof | |
| CN115612400A (en) | Wear-resistant and anti-scouring coating and preparation method thereof | |
| CN102219470A (en) | Energy-saving environment-friendly adhesive | |
| WO2021092985A1 (en) | Self-cleaning artificial stone slab for outdoor use and method for fabrication thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220916 |