CN115340339A - Inorganic decorative plate and preparation method thereof - Google Patents
Inorganic decorative plate and preparation method thereof Download PDFInfo
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- CN115340339A CN115340339A CN202211140476.6A CN202211140476A CN115340339A CN 115340339 A CN115340339 A CN 115340339A CN 202211140476 A CN202211140476 A CN 202211140476A CN 115340339 A CN115340339 A CN 115340339A
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- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 87
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- 229910010413 TiO 2 Inorganic materials 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 38
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- 238000003760 magnetic stirring Methods 0.000 claims description 14
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- 239000002344 surface layer Substances 0.000 claims description 10
- 238000012423 maintenance Methods 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 7
- 239000011707 mineral Substances 0.000 claims description 7
- 229910021487 silica fume Inorganic materials 0.000 claims description 7
- 229940088710 antibiotic agent Drugs 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 3
- 239000012466 permeate Substances 0.000 claims description 3
- 241000764238 Isis Species 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 20
- 230000015556 catabolic process Effects 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 14
- 229940043267 rhodamine b Drugs 0.000 abstract description 14
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- 239000004566 building material Substances 0.000 abstract description 2
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- 238000009395 breeding Methods 0.000 abstract 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 36
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- 230000000052 comparative effect Effects 0.000 description 16
- 230000001699 photocatalysis Effects 0.000 description 15
- 238000000576 coating method Methods 0.000 description 10
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- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 4
- 229940019931 silver phosphate Drugs 0.000 description 4
- 229910000161 silver phosphate Inorganic materials 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 239000003973 paint Substances 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 208000033809 Suppuration Diseases 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
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Images
Classifications
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- 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
- C04B28/04—Portland cements
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5049—Zinc or bismuth oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
- C04B41/67—Phosphates
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Architecture (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Civil Engineering (AREA)
- Agronomy & Crop Science (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of building materials, and particularly relates to an inorganic decorative plate and a preparation method thereof. The invention utilizes the vacuum adsorption method to prepare the inorganic decorative board with the functions of self-cleaning, antibiosis and bacteriostasis, and effectively avoids the functional material (nano TiO) caused by the internal mixing method 2 And silver-zinc composite antibacterial agent), the effective utilization rate of the functional material is improved, and the cost is reduced. Compared with common inorganic decorative boards, the inorganic decorative board has the functions of self-cleaning, antibiosis and bacteriostasis, the degradation rate of rhodamine B reaches more than 83 percent, the total antibiosis rate reaches 92-98 percent, and the inorganic decorative board effectively solves the problems thatThe problem of bacterial breeding on the surface of the decorative plate is solved, the self-cleaning function and the antifouling and stain-resistant performance are achieved, the requirements of people on environment-friendly materials are met, and the environment-friendly decorative plate has a good market prospect and an application value.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to an inorganic decorative plate and a preparation method thereof.
Background
With the vigorous development of the building industry, the demand of people for building decorative materials is rapidly increased, wherein the decorative plate becomes one of the most widely applied building decorative materials at present due to the characteristics of smooth surface, attractive appearance, durability and the like. The decorative plate is prepared from inorganic or organic materials, mainly takes decoration as a main part, has a slightly single function, and realizes the multi-functionalization of the decorative plate, which is an important development direction of the future decorative plate material. Meanwhile, the decorative plate is easily influenced by deposition of organic or other pollutants in the air in the long-term use process, so that black spots, stains and even corrosion phenomena appear on the surface of the decorative plate, and the attractiveness of the decorative plate is seriously influenced. In addition, bacteria are easy to be adsorbed on the surface of the decorative plate, so that substances are deteriorated, putrefaction and mildewed at proper temperature, and the wound is infected with suppuration, thereby seriously threatening the health of human beings.
TiO 2 The material has excellent performances of degrading pollutants, purifying air, being good in economy and the like, is widely applied to various occasions, and is a hotspot of the current functional material research. Based on this, nano TiO 2 The composite material is compounded with a decorative plate to prepare the decorative plate with photocatalytic performance, which is beneficial to the research on the functionalization of the traditional decorative material.
At present, the preparation method of the decorative plate with the photocatalytic material mainly comprises an internal doping method, a loading method and a coating method, but all have the defects that: the internal doping method is to directly mix TiO 2 The functional material is prepared by mixing the functional material with the raw material, the doping amount of the functional material is large, and TiO in the composite material 2 And the functional materials are difficult to contact with light sources and pollutants, so that the effective utilization rate of the functional materials is low. The loading method is that TiO is firstly loaded 2 When functional materials are loaded on the surface of a carrier, and then the carrier is loaded on the surface of a material (product), the bonding property of the carrier and the material (product) directly influencesThe durability of the functional material, such as the shedding of the carrier from the surface of the material (product), leads to poor durability, and the process has high requirements on the carrier, needs the porous material and the acid/alkali treatment on the surface, needs the sol-gel method to prepare the solution, has complex loading process and is limited in practical application. The coating method is to spray functional coating on the surface of the formed material (product), which can effectively improve TiO 2 But the adhesion with the matrix material is poor, and the surface coating is not scratch-resistant, so that the durability of the coating is poor.
Disclosure of Invention
The invention aims to solve the existing problems and provides an inorganic decorative plate and a preparation method thereof 2 The silver-zinc composite antibacterial agent is adsorbed on the surface layer of the inorganic decorative plate test piece, has a certain depth, and enhances TiO 2 And durability of the silver-zinc composite antibacterial agent functional layer.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an inorganic decorative plate, which comprises the following steps:
providing an inorganic decorative plate test piece;
vacuum adsorption of TiO 2 Absorbing the silver-zinc composite antibacterial agent dispersion liquid into the surface layer of an inorganic decorative plate test piece to obtain the inorganic decorative plate, wherein the TiO is 2 The-silver-zinc composite antibacterial agent dispersion comprises nano TiO 2 The composite antibacterial agent comprises silver-zinc composite antibacterial agent, surfactant and water.
Preferably, the TiO is 2 Nano TiO in-Ag-Zn composite antibiotic agent dispersion liquid 2 The mass of (b) is 0.1 to 3% of the mass of water.
Preferably, the TiO is 2 The mass of the silver-zinc composite antibacterial agent in the silver-zinc composite antibacterial agent dispersion liquid is 0.1-3% of the mass of water.
Preferably, the TiO is 2 The mass ratio of the silver-zinc composite antibacterial agent dispersion liquid to the inorganic decorative plate test piece is 1-2.
Preferably, the vacuum adsorption pressure is 10 to 15psi.
Preferably, the time of the vacuum adsorption is 1-2 min.
Preferably, the inorganic decorative plate test piece is prepared by a method comprising the following steps: and mixing inorganic powder, water and a water reducing agent, and then sequentially performing die filling, molding and maintenance to obtain the inorganic decorative plate test piece.
Preferably, the inorganic powder comprises the following components in parts by weight: 120-150 parts of cement, 5-15 parts of silica fume, 45-55 parts of mineral powder and nano SiO 2 10-15 parts.
Preferably, the TiO is 2 -the silver-zinc composite antibacterial agent dispersion is prepared by a method comprising the following steps: mixing nanometer TiO 2 Carrying out first magnetic stirring, ultrasonic treatment and second magnetic stirring on the silver-zinc composite antibacterial agent, the surfactant and water in sequence to obtain the TiO 2 -silver-zinc composite antibiotic agent dispersion.
The invention also provides the inorganic decorative plate obtained by the preparation method of the technical scheme, which comprises an inorganic decorative plate test piece and a functional material, wherein the functional material is adsorbed on the surface of the inorganic decorative plate test piece and permeates into the inorganic decorative plate test piece, and comprises nano TiO 2 And a silver-zinc composite antibacterial agent.
The invention provides a preparation method of an inorganic decorative plate, which comprises the following steps:
providing an inorganic decorative plate test piece;
vacuum adsorption of TiO 2 Absorbing the silver-zinc composite antibacterial agent dispersion liquid into the surface layer of an inorganic decorative plate test piece to obtain the inorganic decorative plate, wherein the TiO is 2 The-silver-zinc composite antibacterial agent dispersion comprises nano TiO 2 The composite antibacterial agent comprises silver-zinc composite antibacterial agent, surfactant and water.
The invention adsorbs TiO by vacuum 2 The silver-zinc composite antibacterial agent dispersion liquid is adsorbed on the surface layer of an inorganic decorative plate test piece and has a certain depth (the depth is 1-2 mm), the problem that the functional material is easy to fall off due to the fact that the functional material is sprayed on the surface of the decorative plate by a coating method and a loading method is solved, and TiO is enhanced 2 And durability, i.e. abrasion resistance, of the functional layer of the silver-zinc composite antibacterial agent(ii) a And the method is simple and easy to operate. The data of the embodiment show that after the wear resistance test, the degradation rate of the inorganic decorative plate disclosed by the invention to rhodamine B is reduced to a small extent, and the wear resistance is excellent.
Furthermore, compared with the internal doping method, the preparation method of the invention has the advantages of small using amount of functional materials and reduced TiO 2 The dosage of the-silver-zinc composite antibacterial agent dispersion liquid is increased, and the TiO content is increased 2 And the utilization rate of the silver-zinc composite antibacterial agent. Moreover, the preparation method is simple, complex carrier materials are not needed, the preparation mode of the functional material dispersion liquid is simple, the functional material dispersion liquid can be directly applied to production, and the preparation method is low in energy consumption, high in efficiency and good in economy.
The invention also provides the inorganic decorative plate and TiO prepared by the preparation method in the technical scheme 2 Has self-cleaning function, the silver-zinc composite antibacterial agent has antibacterial and bacteriostatic functions, and the inorganic decorative plate test piece adsorbs TiO in vacuum 2 After the silver-zinc composite antibacterial agent dispersion liquid is obtained, excellent self-cleaning effect and antibacterial and bacteriostatic functions are obtained. The data of the embodiment shows that the degradation rate of the inorganic decorative board of the invention to rhodamine B solution reaches more than 83%; the degradation rate of the soy sauce pollutants is more than 48 percent; the degradation rate of NO pollution gas reaches over 84 percent; the total antibacterial rate is 92-98%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram of an inorganic decorative plate prepared by vacuum adsorption in the example, in which 1 is a sealed barrel, 2 is an inorganic decorative plate test piece, and 3 is TiO 2 -silver zinc composite antibacterial agent dispersion, 4 is air pipe, 5 is vacuum air pump.
Detailed Description
The invention provides a preparation method of an inorganic decorative plate, which comprises the following steps:
providing an inorganic decorative plate test piece;
vacuum adsorption of TiO 2 Absorbing the silver-zinc composite antibacterial agent dispersion liquid into the surface layer of an inorganic decorative plate test piece to obtain the inorganic decorative plate, wherein the TiO is 2 The-silver-zinc composite antibacterial agent dispersion liquid comprises nano TiO 2 The silver-zinc composite antibacterial agent comprises silver-zinc composite antibacterial agent, surfactant and water.
In the present invention, unless otherwise specified, all the raw materials used are commercially available in the art.
In the present invention, the inorganic decorative panel test piece is preferably produced by a method comprising the steps of: and mixing inorganic powder, water and a water reducing agent, and then sequentially performing die filling, molding and maintenance to obtain the inorganic decorative plate test piece.
In the invention, the inorganic powder preferably comprises the following components in parts by weight: 120 to 150 portions of cement, 5 to 15 portions of silica fume, 45 to 55 portions of mineral powder and nano SiO 2 10-15 parts; more preferably comprises the following components in parts by weight: 130 parts of cement, 10 parts of silica fume, 50 parts of mineral powder and nano SiO 2 10 parts.
In the present invention, the cement is preferably P · O52.5 white cement.
In the invention, the silica fume is preferably SiO 2 The content is more than or equal to 95 percent, and the specific surface area value is more than or equal to 15000m 2 /kg。
In the invention, the ore powder is preferably S95 grade, and the specific surface area value is more than or equal to 450m 2 The strength and activity index per kg in 28 days is more than or equal to 95.
In the invention, the nano SiO 2 The particle diameter of (3) is preferably 15nm.
In the invention, the inorganic powder comprises an active mineral material which is a main raw material of the inorganic decorative plate, and the cement, the silica fume and the mineral powder are gelled materials, can be quickly hydrated to generate strength, and ensure that the inorganic decorative plate has certain mechanical properties; nano SiO 2 Can promote the hydration of cement, fill the inner pores of the inorganic decorative plate and improve the strength.
In the present invention, the mass of the water is preferably 6.3 to 6.5%, more preferably 6.4% of the mass of the inorganic powder.
In the present invention, the mass of the water reducing agent is preferably 1 to 1.5%, more preferably 1.2% of the mass of the inorganic powder.
In the invention, the water reducing agent is preferably a polycarboxylic acid high-efficiency water reducing agent.
In the invention, the water reducing agent can reduce water consumption, promote cement hydration and improve strength.
In the invention, the mixing mode is preferably stirring, and the rotating speed of the stirring is preferably 350-400 r/min, and more preferably 380r/min; the time is preferably 30 to 50 seconds, more preferably 30 seconds. The invention has no special requirements on the stirring equipment, such as a stirrer.
In the invention, the mixed slurry obtained after mixing is preferably filled into a mold.
In the invention, the temperature of the mold is preferably 25-30 ℃, and the mold is preferably a pouring mold.
In the present invention, the molding is preferably press molding, the press molding pressure is preferably 280 to 300KN, more preferably 300KN, the press molding press rate is preferably 2.4 ± 0.2KN/s, the press molding dwell time is preferably 30s, and the present invention does not require a special apparatus for press molding, such as a compression tester.
In the invention, the maintenance preferably comprises natural environment maintenance and constant temperature maintenance in sequence, the temperature of the natural environment maintenance is preferably 10-30 ℃, the time is preferably 24 hours, the temperature of the constant temperature maintenance is preferably 75-85 ℃, more preferably 85 ℃, and the time is preferably 2 d.
After the inorganic decorative plate test piece is obtained, the invention adopts vacuum adsorption to adsorb TiO 2 Absorbing the silver-zinc composite antibacterial agent dispersion liquid into the surface layer of an inorganic decorative plate test piece to obtain the inorganic decorative plate, wherein the TiO is 2 The-silver-zinc composite antibacterial agent dispersion liquid comprises nano TiO 2 The composite antibacterial agent comprises silver-zinc composite antibacterial agent, surfactant and water.
In the present invention, the TiO is 2 The silver-zinc composite antibacterial agent dispersion is preferably prepared by a method comprising the following steps: mixing nanometer TiO 2 Carrying out first magnetic stirring, ultrasonic treatment and second magnetic stirring on the silver-zinc composite antibacterial agent, the surfactant and water in sequence to obtain the TiO 2 -silver zinc composite antimicrobial agent dispersion.
In the present invention, the TiO is 2 Nano TiO in-Ag-Zn composite antibiotic agent dispersion liquid 2 The mass of (b) is preferably 0.1 to 3%, more preferably 0.5 to 2% of the mass of water.
In the present invention, the nano TiO is 2 The particle diameter of (A) is preferably 25 to 60nm. The nano TiO 2 The photocatalytic activity of (2) is inversely related to the particle size, such as nano TiO 2 The particle size is too large, and the photocatalytic activity is reduced when the particle size is more than 100 nm; such as nano TiO 2 Although the particle size is too small, the nano powder having a smaller particle size tends to be agglomerated, and the photocatalytic activity is rather lowered. Therefore, the invention selects the nano TiO with the grain diameter of 25-60 nm according to the self-cleaning effect 2 。
In the present invention, the nano TiO 2 Preferably hydrophilic anatase TiO 2 . The nano TiO 2 According to the crystal structure, anatase type, rutile type and brookite type can be classified. Wherein the brookite type TiO 2 No photocatalytic activity exists; and rutile type TiO 2 Has high refractive index, and is suitable for being used as a heat reflection material. Anatase type TiO 2 Has better photocatalytic performance, and can remove H in the air under the irradiation of sunlight (especially ultraviolet light) 2 O、O 2 The polarized hydrogen oxygen radical has strong oxidizing power, can oxidize most organic matters and inorganic pollutants in water and mineralize the organic matters and the inorganic pollutants into inorganic micromolecules and CO 2 And H 2 O and other harmless substances.
In the present invention, the nano TiO is 2 Adsorbing the nano TiO as a functional material 2 The obtained inorganic decorative board has self-cleaning function.
In the present invention, theTiO 2 The mass of the silver-zinc composite antibacterial agent in the silver-zinc composite antibacterial agent dispersion liquid is preferably 0.1 to 3%, more preferably 0.5 to 1.5% of the mass of water.
In the invention, the particle size of the silver-zinc composite antibacterial agent is preferably 0.8-2.5 μm, and the invention has no special requirement on the density of the silver-zinc composite antibacterial agent. In the specific embodiment of the invention, the density of the silver-zinc composite antibacterial agent is 2-3 g/mL.
In the invention, the silver-zinc composite antibacterial agent is a functional material, and the inorganic decorative plate obtained after adsorbing the silver-zinc composite antibacterial agent has antibacterial and bacteriostatic functions.
The silver-zinc composite antibacterial agent mainly comprises nano ZnO and silver phosphate, the mass ratio of the silver phosphate to the nano ZnO is preferably 2-7, the silver-series antibacterial agent (silver phosphate) and the zinc-series antibacterial agent (nano ZnO) are compounded, and anatase TiO is added at the same time 2 Not only has the function of silver ion contact reaction, but also exerts the functions of nano ZnO and nano TiO 2 The photocatalytic activity function of the three materials is fully exerted, and the price is greatly reduced compared with that of a silver antibacterial agent used alone.
In the present invention, the TiO is 2 The mass of the surfactant in the silver-zinc composite antibacterial agent dispersion liquid is preferably 0.1 to 0.6%, more preferably 0.5%, of the mass of water.
In the present invention, the surfactant is preferably Sodium Dodecyl Sulfate (SDS), which in a specific embodiment of the present invention has a density of 0.37g/cm 3 The melting point is 204-207 ℃.
In the present invention, the surfactant may be nano TiO 2 The silver-zinc composite antibacterial agent is uniformly dispersed in water without agglomeration and precipitation, and the obtained TiO 2 The dispersion liquid of the-silver-zinc composite antibacterial agent has good dispersion effect.
In the present invention, the time of the first magnetic stirring, the ultrasonic and the second magnetic stirring is independently preferably 10 to 25min.
In the present invention, the rotation speeds of the first magnetic stirring and the second magnetic stirring are independently preferably 300 to 400r/min, and more preferably 350r/min; the time is independently preferably 15 to 25min, more preferably 20min. The invention has no special requirements on the equipment for the first magnetic stirring and the second magnetic stirring, such as a magnetic stirrer.
In the present invention, the frequency of the ultrasound is preferably 50 to 60Hz, more preferably 55Hz, and the time of the ultrasound is preferably 10 to 15min, more preferably 15min.
In the invention, the first magnetic stirring, the ultrasonic and the second magnetic stirring are used for obtaining TiO 2 The silver-zinc composite antibacterial agent dispersion liquid has good stability, and can keep good dispersion effect without agglomeration and precipitation.
To obtain the TiO 2 After the-silver-zinc composite antibacterial agent dispersion liquid and the inorganic decorative plate test piece are treated by vacuum adsorption, the invention adopts the vacuum adsorption to remove TiO 2 And (4) absorbing the silver-zinc composite antibacterial agent dispersion liquid into the surface layer of the inorganic decorative plate test piece to obtain the inorganic decorative plate.
In the present invention, the TiO is 2 The mass ratio of the silver-zinc composite antibacterial agent dispersion to the inorganic decorative plate test piece is preferably 1-2.
The invention adopts vacuum adsorption to adsorb TiO 2 Absorbing the-silver-zinc composite antibacterial agent dispersion liquid into the surface layer of the inorganic decorative plate test piece, and absorbing TiO 2 Immersing the inorganic decorative plate test piece to 1/3-3/4 of the plate thickness by the silver-zinc composite antibacterial agent dispersion liquid without completely soaking the whole inorganic decorative plate test piece, wherein the used TiO is 2 The dispersion liquid of the silver-zinc composite antibacterial agent is less. In a specific embodiment of the invention, the thickness of the inorganic decorative plate test piece is 7mm, and the TiO 2 The-silver-zinc composite antibacterial agent dispersion liquid only needs to immerse the inorganic decorative plate test piece by 3-5 mm in depth.
In the present invention, the TiO is 2 The ratio of the weight parts of water in the silver-zinc composite antibacterial agent dispersion liquid to the total weight parts of the inorganic powder in the inorganic decorative board test piece is preferably 150-250.
In the present invention, the pressure of the vacuum adsorption is preferably 10 to 15psi, more preferably 10psi.
In the present invention, the time for the vacuum adsorption is preferably 1 to 2min, more preferably 1min.
In the invention, the pressure (vacuum degree) and time of vacuum adsorption can influence the depth and the loading capacity of the dispersion liquid adsorbed to the interior of the inorganic decorative plate test piece, the pressure of vacuum adsorption is too small or the time of vacuum adsorption is too short, and TiO adsorbed to the interior of the inorganic decorative plate 2 The dispersion liquid of the silver-zinc composite antibacterial agent is less, the adsorption depth is small, and the self-cleaning, antibacterial and bacteriostatic functions of the inorganic decorative board can be weakened. In the pressure and time range of vacuum adsorption, the inorganic decorative plate test piece and TiO are subjected to vacuum adsorption 2 Under the condition of the same components of the silver-zinc composite antibacterial agent dispersion liquid, the pressure and time of vacuum adsorption are changed, and the self-cleaning performance and the antibacterial performance of the inorganic decorative plate are not greatly influenced.
The vacuum adsorption method of the invention is to soak the formed inorganic decorative plate test piece in TiO 2 In the-silver-zinc composite antibacterial agent dispersion liquid, adopting a vacuum pumping mode to make TiO 2 The silver-zinc composite antibacterial agent dispersion liquid is adsorbed to the surface layer of the inorganic decorative plate test piece to a certain depth, so that the inorganic decorative plate has the functions of self-cleaning, antibiosis and bacteriostasis. The invention has no special requirements for the vacuum adsorption equipment, and in the specific embodiment of the invention, for example, tiO is used 2 And respectively placing the silver-zinc composite antibacterial agent dispersion liquid and the inorganic decorative plate test piece in an open container, placing the open container in vacuum pumping equipment, and controlling the pressure and time of vacuum adsorption to obtain the inorganic decorative plate with self-cleaning, antibacterial and bacteriostatic functions.
The schematic diagram of the preparation of the inorganic decorative plate by the vacuum adsorption method is shown in figure 1, wherein 1 is a sealing barrel, 2 is an inorganic decorative plate test piece, and 3 is TiO 2 -silver zinc composite antibacterial agent dispersion, 4 is air pipe, 5 is vacuum air pump. The inorganic decorative board prepared by the invention has the functions of self-cleaning, antibiosis and bacteriostasis.
In the present invention, the vacuum adsorption is preferably followed by drying to obtain the inorganic decorative board, the drying temperature is preferably room temperature, i.e. no additional heating or cooling is required, and the drying time is preferably 6 to 24 hours, and more preferably 12 hours.
The invention also provides the inorganic decorative plate obtained by the preparation method of the technical scheme, which comprises an inorganic decorative plate test piece and a functional material, wherein the functional material is adsorbed on the surface of the inorganic decorative plate test piece and permeates into the inorganic decorative plate test piece, and comprises nano TiO 2 And a silver-zinc complex antimicrobial agent.
In the present invention, the depth of the penetration is preferably 1 to 2mm.
Compared with the existing coating method for spraying the functional material on the surface of a decorative plate test piece, the inorganic decorative plate has the advantages that the self-cleaning function and the antibacterial and bacteriostatic functions are not greatly changed before and after a wear test.
For further illustration of the present invention, the inorganic decorative sheet and the method for manufacturing the same according to the present invention will be described in detail with reference to the drawings and examples, which should not be construed as limiting the scope of the present invention.
Example 1
1) Weighing 200 parts of inorganic powder (130 parts of cement, 10 parts of silica fume, 50 parts of mineral powder and nano SiO) 2 10 parts of water (6.4 percent of the mass of the inorganic powder) and a polycarboxylic acid high-efficiency water reducing agent (1.2 percent of the mass of the inorganic powder) are put into a stirrer and stirred for 30 seconds at 380r/min to obtain mixed slurry; pouring the mixed slurry into a mold, placing the mold under a pressure tester for compression molding, wherein the loading load of the mold is 300KN, the pressurizing rate is 2.4 +/-0.2 KN/s, standing the mold for 24h in a natural environment at 25 ℃ after the mold is subjected to constant pressure for 30s, and then placing the mold in a water bath box at 85 ℃ for maintenance for 2d to obtain an inorganic decorative plate test piece.
2) Weighing 200 parts of water and nano TiO 2 Adding (0.5% of water mass), sodium dodecyl sulfate (0.5% of water mass) and silver-zinc composite antibacterial agent (1.5% of water mass, and the mass ratio of silver phosphate to nano ZnO is 2: 1) into a magnetic stirrer, stirring at 350r/min for 20min to obtain mixed solution, continuously putting the mixed solution into an ultrasonic instrument, performing ultrasonic treatment at the ultrasonic frequency of 55Hz for 15min, putting the mixed solution after ultrasonic treatment into the magnetic stirrer again,continuously stirring for 20min at 350r/min to obtain TiO 2 -silver-zinc composite antibiotic agent dispersion.
3) TiO obtained in the step 2) 2 Putting the silver-zinc composite antibacterial agent dispersion liquid and the inorganic decorative plate test piece obtained in the step 1) into vacuum adsorption equipment in sequence, performing negative pressure adsorption through a vacuum pump, and stably adsorbing for 1min when the vacuum degree is 10psi. And after the adsorption is finished, waiting for the vacuum degree to slowly return to zero, taking out the test piece, placing the test piece in an environment with the natural temperature of 25 ℃, and drying for 12 hours to obtain the inorganic decorative plate with the functions of antibiosis, bacteriostasis and self-cleaning.
Example 2
The difference between this example and example 1 is that in step 2), nano TiO is present 2 And the quality of the silver-zinc composite antibacterial agent, the vacuum degree and the stable adsorption time in the step 3), and the nano TiO in the step 2) of the embodiment 2 The weight of the silver-zinc composite antibacterial agent is 1.0 percent of the weight of water, and the weight of the silver-zinc composite antibacterial agent is 1.0 percent of the weight of water; in the step 3), the vacuum degree is 15psi, and the stable adsorption is 1min.
Example 3
The difference between this example and example 1 is that in step 2), nano TiO is present 2 And the quality of the silver-zinc composite antibacterial agent, the vacuum degree and the stable adsorption time in the step 3), and the nano TiO in the step 2) of the embodiment 2 2.0 percent of the mass of water, and 0.5 percent of the mass of the silver-zinc composite antibacterial agent; in the step 3), the vacuum degree is 15psi, and the stable adsorption is 2min.
Comparative example 1
This comparative example is different from example 1 only in that steps 2) and 3) were not performed to obtain an inorganic decorative panel test piece (ordinary decorative panel).
Comparative example 2
Preparation of inorganic decorative board by coating method
This comparative example differs from example 1 only in step 3), step 3) being changed to:
the obtained TiO is 2 The-silver-zinc composite antibacterial agent dispersion liquid is uniformly sprayed on the surface of the inorganic decorative plate test piece, and the spraying amount is 10g/m 2 And (6) counting.
Test example 1
1. Self-cleaning performance test
The change of the chromaticity on the surface of the sample was detected by a color difference meter, the photocatalytic performance of the inorganic decorative plate of examples 1 to 3, the inorganic decorative plate test piece of comparative example 1, and the photocatalytic performance of the inorganic decorative plate of comparative example 2 were evaluated by the degradation performance of rhodamine B (RhB) and soy sauce contaminants, and 5mL of rhodamine B solution and soy sauce sample were dropped onto the surface of the decorative plate, respectively, and the results are shown in table 1. Wherein the concentration of the rhodamine B solution is 80mg/L, and the soy sauce is commercial edible soy sauce without dilution.
NO degradation Rate test
And (3) setting up photocatalytic reaction equipment according to GB/T23761-2009 performance test method for photocatalytic air purification materials, thereby carrying out photocatalytic degradation test. In the experiment, the inorganic decorative boards of examples 1 to 3, the inorganic decorative board test piece of comparative example 1 and the inorganic decorative board test piece of comparative example 2 were placed in an NO reactor with a concentration of 5mg/L, respectively, and the NO concentration of the inorganic decorative boards after being irradiated by an ultraviolet lamp with a lambda of 254nm for 1 hour was measured to evaluate the photocatalytic performance of the inorganic decorative board test pieces of examples 1 to 3 and comparative example 1 and the inorganic decorative board test piece of comparative example 2, and the results are shown in Table 1.
3. Test for antibacterial Properties
The total antibacterial rate of the decorative plate is tested by referring to GB/T30706-2014 antibacterial property test method and evaluation of photocatalytic antibacterial materials and products under visible light irradiation and GB 4789.2-2016 colony total number determination of food hygiene microbiology inspection, and the results are shown in Table 1.
4. Abrasion resistance test
According to GB/T6739-2006 determination of paint film hardness by color paint and varnish pencil method, the inorganic decorative sheet test pieces of comparative example 1 and the inorganic decorative sheet test piece of comparative example 2 of examples 1 to 3 were cut into test pieces having a size of 50mm × 100mm × 7mm, respectively, and then placed on an abrasion resistance tester to perform an abrasion resistance test under test conditions: the rotating speed is 100r/min, the test counterweight is 100g, and the test time is 1min. After the wear resistance test, rhodamine B (RhB) is degraded to be a photocatalytic performance index, and the self-cleaning performance of the decorative plate is tested, and the result is shown in Table 1.
Table 1 test results of performance test of the inorganic decorative boards of examples 1 to 3, the inorganic decorative board test piece of comparative example 1, and the inorganic decorative board of comparative example 2
As can be seen from Table 1, the inorganic decorative board prepared by the vacuum adsorption method has the functions of antibiosis, bacteriostasis and self-cleaning, the degradation rate of rhodamine B solution is more than 83%, the degradation rate of soy sauce pollutants is more than 48%, the degradation rate of NO gas is more than 84%, and the total antibacterial rate is more than 92%. The common decorative board of comparative example 1 has a degradation rate of only 28% for RhB, 22% for soy sauce, 24% for NO gas, and 35% for total antibacterial rate. Therefore, compared with the common decorative board, the inorganic decorative board provided by the invention has the advantages that the photocatalytic performance (including antibacterial, bacteriostatic and self-cleaning performances) is obviously improved, the degradation effect on organic dye (RhB), soy sauce and NO gas is obvious, and meanwhile, the antibacterial and bacteriostatic effects are higher.
After the abrasion resistance test, the degradation rate of the inorganic decorative plate (coating method) of the comparative example 2 to RhB is reduced to 36%; compared with the numerical value before abrasion resistance, the reduction amplitude is as high as 44%; after the wear-resistant test, the degradation rate of the inorganic decorative plate provided by the invention on RhB is still up to over 64%, and the maximum reduction amplitude is only 19%. After a wear-resisting test, the inorganic decorative plate with the antibacterial, bacteriostatic and self-cleaning functions, which is prepared by adopting the vacuum adsorption method, still maintains the higher self-cleaning function and has good durability compared with the conventional coating method.
Although the present invention has been described in detail with reference to the above embodiments, it is to be understood that the present invention is not limited to the details of the embodiments, and that other embodiments may be devised without departing from the spirit and scope of the present invention.
Claims (10)
1. The preparation method of the inorganic decorative plate is characterized by comprising the following steps:
providing an inorganic decorative plate test piece;
vacuum adsorption of TiO 2 Absorbing the silver-zinc composite antibacterial agent dispersion liquid into the surface layer of an inorganic decorative plate test piece to obtain the inorganic decorative plate, wherein the TiO is 2 The-silver-zinc composite antibacterial agent dispersion comprises nano TiO 2 The composite antibacterial agent comprises silver-zinc composite antibacterial agent, surfactant and water.
2. The method of claim 1, wherein the TiO is selected from the group consisting of 2 Nano TiO in-Ag-Zn composite antibiotic agent dispersion liquid 2 The mass of (b) is 0.1 to 3% of the mass of water.
3. The method of claim 1, wherein the TiO is selected from the group consisting of 2 The mass of the silver-zinc composite antibacterial agent in the silver-zinc composite antibacterial agent dispersion liquid is 0.1-3% of the mass of water.
4. A method for preparing in accordance with claim 2 or 3, wherein said TiO is in the form of a powder 2 The mass ratio of the silver-zinc composite antibacterial agent dispersion liquid to the inorganic decorative plate test piece is 1-2.
5. The method of claim 1, wherein the vacuum adsorption is performed at a pressure of 10 to 15psi.
6. The production method according to claim 1 or 5, wherein the time for the vacuum adsorption is 1 to 2min.
7. The manufacturing method according to claim 1, wherein the inorganic decorative plate test piece is manufactured by a method comprising the steps of: and mixing inorganic powder, water and a water reducing agent, and then sequentially performing die filling, molding and maintenance to obtain the inorganic decorative plate test piece.
8. The method for producing according to claim 7, which isIs characterized in that the inorganic powder comprises the following components in parts by weight: 120-150 parts of cement, 5-15 parts of silica fume, 45-55 parts of mineral powder and nano SiO 2 10-15 parts.
9. The method of claim 1, wherein the TiO is selected from the group consisting of 2 -the silver-zinc composite antibacterial agent dispersion is prepared by a method comprising the following steps: mixing nanometer TiO 2 Carrying out first magnetic stirring, ultrasonic treatment and second magnetic stirring on the silver-zinc composite antibacterial agent, the surfactant and water in sequence to obtain the TiO 2 -silver-zinc composite antibiotic agent dispersion.
10. The inorganic decorative board obtained by the preparation method according to any one of claims 1 to 9, comprising an inorganic decorative board test piece and a functional material, wherein the functional material is adsorbed on the surface of the inorganic decorative board test piece and permeates into the inorganic decorative board test piece, and the functional material comprises nano TiO 2 And a silver-zinc composite antibacterial agent.
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| CN112841220A (en) * | 2021-01-11 | 2021-05-28 | 同曦集团有限公司 | Silver-zinc nano composite antibacterial agent and preparation method and application thereof |
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| CN106273825A (en) * | 2016-08-05 | 2017-01-04 | 贺州市恒达板业有限公司 | A kind of manufacture method of antibacterial decorative panel |
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