CN108083720A - A kind of nanometer modified photocatalytic self-cleaning concrete and preparation method thereof - Google Patents
A kind of nanometer modified photocatalytic self-cleaning concrete and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000002156 mixing Methods 0.000 claims abstract description 47
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims abstract description 22
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 10
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
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- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 14
- 229960000907 methylthioninium chloride Drugs 0.000 description 14
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- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 2
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B13/00—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
- B32B13/02—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material with fibres or particles being present as additives in the layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B13/00—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material
- B32B13/04—Layered products comprising a a layer of water-setting substance, e.g. concrete, plaster, asbestos cement, or like builders' material comprising such water setting substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
-
- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/04—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00017—Aspects relating to the protection of the environment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
- C04B2111/00827—Photocatalysts
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
- C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
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- Chemical & Material Sciences (AREA)
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- Structural Engineering (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- Fluid Mechanics (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to building material engineering technologies, it is desirable to provide a kind of nanometer modified photocatalytic self-cleaning concrete and preparation method thereof.The concrete is by being located at the cement slurry in middle level and being formed positioned at bilevel concrete substrate through load pressurization and after conserving drying；Wherein, cement slurry is mixed by each component of following weight parts：92.5~97.5 parts of cement, 2.5~7.5 parts of nitrating nanometer TiO2 powders, 0.5~1.5 part of water-reducing agent, 20~30 parts of water；Concrete substrate is mixed by each component of following weight parts：100 parts of cement, 100~130 parts of fine aggregate, 100~120 parts of coarse aggregate, 0.5~2.5 part of water-reducing agent, 30~40 parts of water.The present invention can effectively reduce TiO2Energy gap, improve the response wave length and photocatalysis performance to visible ray.It can effectively solve the problem that the main problem that nanoparticle agglomerates, lack of homogeneity, photocatalysis performance are bad existing for traditional photocatalysis concrete inner blending method or surface cladding process, photocatalysis performance greatly promotes.Surface roughness is minimum, improves photocatalysis continuation, possesses self-cleaning function.
Description
Technical Field
The invention relates to the technical field of building material engineering, in particular to nano modified photocatalytic self-cleaning concrete and a preparation method thereof.
Background
With the continuous development of social economy, the problem of air pollution becomes one of the main problems of close attention of human beings. Automobile exhaust is used as a main cause of air pollution, pollution control becomes increasingly severe along with continuous increase of the number of automobiles, total exhaust emission is quite large, and how to effectively control the air pollution caused by the automobile exhaust becomes a technical field which is highly valued in the industry.
Research shows that TiO is utilized2The aim of eliminating and degrading atmospheric pollutants can be effectively realized by the photocatalytic reaction principle, and the TiO with the particle size of less than 15nm2The particles have obvious surface effect and quantum effect, have extraordinary redox capability under the action of light, and have excellent photocatalytic performance. Simultaneous nano TiO 22The photocatalytic performance of the nano TiO is directly influenced by factors such as crystal structure, surface appearance, specific surface area, chemical potential and the like2The nitrogen doping treatment can greatly improve TiO2The photocatalysis efficiency can be expanded, the photoresponse wavelength can be expanded, and the photocatalysis performance can be greatly improved.
The general automobile exhaust emission interval is between 0.3m and 2m, the high-continuity photocatalysis pavement concrete is prepared by photocatalysis technology, and the cement concrete is used as nano TiO2The photocatalytic carrier of (2), using TiO2The photocatalytic activity of the photocatalyst absorbs nitrogen oxide and SO in the automobile exhaust2And the like, so that the harmful substances are converted into nitric acid, sulfuric acid and the like, and the method is an important technical means for realizing pollution-free treatment of the automobile exhaust. At present, TiO is treated at home and abroad2The application of the nano TiO material in concrete is that ① is used for introducing nano TiO into concrete by an internal doping method2② spraying on the surface of the formed concrete substrate to make the nano TiO agglomerate, resulting in high photocatalytic performance2The particles are attached to the surface of the internal gap of the concrete, the method can effectively reduce the waste of the nano particles, but the contact area of the photocatalyst on the surface of the high-density concrete material carrier and polluted air is small, the contact time is short, and the problems of low photocatalytic efficiency, poor continuity and the like of the concrete material are caused.
Although the photocatalytic concrete is concerned by more and more researchers, many problems which are difficult to solve still exist in the actual preparation process, the most important is that the photocatalytic activity duration is short, so that the utilization value of the photocatalytic concrete is low, good economic benefits are difficult to form, and the technical popularization of the photocatalytic concrete is seriously restricted.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provides nano modified photocatalytic self-cleaning concrete and a preparation method thereof. The invention can effectively decompose substances, viruses, bacteria and the like with malodor on the surface of the concrete, absorb atmospheric pollutants in the air, particularly discharged by automobiles, and greatly improve the photocatalytic efficiency and photocatalytic persistence of the concrete.
In order to solve the technical problem, the solution of the invention is as follows:
providing nano modified photocatalysis self-cleaning concrete, wherein the concrete is formed by loading, pressurizing, maintaining and drying cement slurry positioned in a middle layer and concrete base materials positioned in an upper layer and a lower layer; wherein,
the cement paste is prepared by mixing the following components in parts by weight: 92.5-97.5 parts of cement and nitrogen-doped nano TiO22.5-7.5 parts of powder, 0.5-1.5 parts of water reducing agent and 20-30 parts of water;
the concrete base material is prepared by mixing the following components in parts by weight: 100 parts of cement, 100-130 parts of fine aggregate, 100-120 parts of coarse aggregate, 0.5-2.5 parts of water reducing agent and 30-40 parts of water.
In the invention, the nitrogen-doped nano TiO2The powder is prepared by the following steps: mixing sulfur or ammonium sulfate with nano TiO2Mixing the powder evenly, sulfurizing nitrogen in ammonium sulfate and nano TiO2The mass ratio of titanium in the powder is 1: 4-12; ball milling at a rotating speed of 300-900 r/min for 0.5-4 h, calcining at 400-1200 ℃ for 1-8 h, and cooling to obtain the nitrogen-doped nano TiO2Powder;
in the invention, the cement is commercially available P.O 42.5R ordinary portland cement, and meets GB/T175-2007 execution standard; the nano TiO2Is anatase type nano TiO2The diameter is 10-40 nm; the fine aggregate is natural sand or quartz sand, meets GB/T14684-2011 execution standard, and has a mud content of less than 1%; the coarse aggregate is crushed stone with the particle size of 2.36-4.76 mm, meets GB/T14685-2011 execution standard, and has the needle sheet content of less than 10%, the porosity of less than 47% and the mud content of less than 0.5%; the water reducing agent is a polycarboxylic acid water reducing agent, meets GB/T8076-2008 execution standard, and has a water reducing rate of more than 20%.
In the invention, the thickness of the cement paste positioned in the middle layer after curing and drying is 0.5 mm-1 mm; the thickness of the concrete base material on the upper layer after curing and drying is 2 mm-3 mm.
The invention further provides a preparation method of the nano modified photocatalytic self-cleaning concrete, which comprises the following steps:
(1) weighing the raw material components according to the proportion;
(2) mixing cement with newly prepared nitrogen-doped nano TiO2Mixing the powder in a ball mill for 0.5-1 h, adding a water reducing agent and water, and continuously mixing for 2-3 min to prepare cement slurry for later use;
(3) mixing cement, fine aggregate, coarse aggregate, a water reducing agent and water, and preparing fresh concrete according to concrete production specifications for later use;
(4) firstly, paving a concrete base material of a bottom layer with fresh concrete, paving a cement slurry layer on the surface of the concrete base material after the surface is trowelled, and completely covering the surface of the concrete base material of the bottom layer with cement slurry by using vibration equipment; after standing for 1-1.5 h, paving a layer of fresh concrete on the surface of the cement paste, and using vibration equipment to enable the fresh concrete to completely cover the surface of the cement paste, so as to form an upper-layer concrete base material;
(5) covering the concrete base material on the upper layer with a film, and keeping pressurizing at a load of 0.2-0.3 kPa during the curing process of the concrete; and after the curing is finished, removing the load and the film to obtain the nano modified photocatalytic self-cleaning concrete.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention is to nano TiO2The nitrogen doping treatment is carried out, and the difference of N-O in the aspects of ionic radius, electronegativity and the like is utilized to effectively reduce TiO2The forbidden band width of the nano TiO is improved2The response wavelength to visible light can be greatly improved2The photocatalytic performance of (a).
2. The invention carries out layer-by-layer treatment on the concrete, applies load in the curing process to ensure that the cement paste layer is completely attached to the concrete base materials of the upper layer and the bottom layer, and forms self-cleaning concrete with excellent surface appearance after demoulding and curing. The main problems of nano-particle agglomeration, poor uniformity and poor photocatalytic performance existing in the traditional photocatalytic concrete internal doping method or surface coating method can be effectively solved, and the photocatalytic performance is greatly improved.
3. The nano modified photocatalysis self-cleaning concrete prepared by the invention fully combines fluid cement paste with a concrete base material to form C-S-H gel with the grain size and the grain diameter of nano TiO2The method has the advantages that the concrete surface roughness is extremely low, the problem that the photocatalysis persistence of the traditional photocatalysis concrete is reduced due to the covering and accumulation of surface impurities caused by roughness is solved, the photocatalysis persistence of the concrete is greatly improved, and the method has an excellent self-cleaning function.
Drawings
FIG. 1 shows a schematic view of 5X 104The surface morphology of the nano modified photocatalysis self-cleaning concrete under multiple.
Detailed Description
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The cement used in each embodiment of the invention is commercial P.O 42.5R ordinary portland cement, and conforms to GB/T175-2007 execution standard; the nano TiO2Is anatase type nano TiO2The diameter is 10-40 nm; the fine aggregate is natural sand or quartz sand, meets GB/T14684-2011 execution standard, and has a mud content of less than 1%; the coarse aggregate is crushed stone with the particle size of 2.36-4.76 mm, meets GB/T14685-2011 execution standard, and has the needle sheet content of less than 10%, the porosity of less than 47% and the mud content of less than 0.5%; the water reducing agent is a polycarboxylic acid water reducing agent, meets GB/T8076-2008 execution standard, and has a water reducing rate of more than 20%.
Example 1
(1) Nitrogen doped nano TiO2Preparation of powder:
mixing sulfur or ammonium sulfate with nano TiO2Mixing the powder evenly, sulfurizing nitrogen in ammonium sulfate and nano TiO2The mass ratio of titanium in the powder is 1: 4; ball milling at 300r/min for 0.5 hr, calcining at 400 deg.c for 1 hr, and cooling to obtain nitrogen doped nanometer TiO2And (3) powder.
(2) Preparing cement paste:
the cement paste is prepared by mixing the following components in parts by weight: 92.5 parts of cement and nitrogen-doped nano TiO22.5 parts of powder, 0.5 part of water reducing agent and 20 parts of water;
weighing the raw material components according to the proportion; mixing cement with newly prepared nitrogen-doped nano TiO2And mixing the powder in a ball mill for 0.5h, adding a water reducing agent and water, and continuously mixing for 2min to prepare cement slurry for later use.
(3) Preparing nano modified photocatalytic self-cleaning concrete:
the nano modified photocatalysis self-cleaning concrete is formed by loading, pressurizing, maintaining and drying cement slurry positioned in the middle layer and concrete base materials positioned in the upper layer and the lower layer; the thickness of the cement paste positioned in the middle layer after curing and drying is 0.5 mm; the thickness of the concrete base material on the upper layer after curing and drying is 2 mm.
The concrete base material is prepared by mixing the following components in parts by weight: 100 parts of cement, 100 parts of fine aggregate, 100 parts of coarse aggregate, 0.5 part of water reducing agent and 30 parts of water.
(3.1) mixing cement, fine aggregate, coarse aggregate, a water reducing agent and water, and preparing fresh concrete according to concrete production specifications for later use;
(3.2) paving the concrete base material of the bottom layer with fresh concrete, paving a cement slurry layer on the surface of the concrete base material after the surface is leveled, and completely covering the surface of the concrete base material of the bottom layer with the cement slurry by using vibration equipment; after standing for 1h, paving a layer of fresh concrete on the surface of the cement paste, and using vibration equipment to enable the fresh concrete to completely cover the surface of the cement paste, thereby forming an upper concrete base material;
(3.3) covering the concrete base material of the upper layer with a film, and keeping the pressure at the load of 0.2kPa during the curing process of the concrete; and after the curing is finished, removing the load and the film to obtain the nano modified photocatalytic self-cleaning concrete.
Example 2
(1) Nitrogen doped nano TiO2Preparation of powder:
mixing sulfur or ammonium sulfate with nano TiO2Mixing the powder evenly, sulfurizing nitrogen in ammonium sulfate and nano TiO2The mass ratio of titanium in the powder is 1: 12; ball-milling at 900r/min for 4h, calcining at 1200 deg.C for 8h, and cooling to obtain nitrogen-doped nanometer TiO2And (3) powder.
(2) Preparing cement paste:
the cement paste is prepared by mixing the following components in parts by weight: 97.5 portions of cement and nitrogen-doped nano TiO27.5 parts of powder, 1.5 parts of water reducing agent and 30 parts of water;
weighing the raw material components according to the proportion; mixing cement with newly prepared nitrogen-doped nano TiO2And mixing the powder in a ball mill for 1h, adding a water reducing agent and water, and continuously mixing for 3min to prepare cement slurry for later use.
(3) Preparing nano modified photocatalytic self-cleaning concrete:
the nano modified photocatalysis self-cleaning concrete is formed by loading, pressurizing, maintaining and drying cement slurry positioned in the middle layer and concrete base materials positioned in the upper layer and the lower layer; the thickness of the cement paste positioned in the middle layer after curing and drying is 1 mm; the thickness of the concrete base material on the upper layer after curing and drying is 4 mm.
The concrete base material is prepared by mixing the following components in parts by weight: 100 parts of cement, 130 parts of fine aggregate, 120 parts of coarse aggregate, 2.5 parts of water reducing agent and 40 parts of water.
(3.1) mixing cement, fine aggregate, coarse aggregate, a water reducing agent and water, and preparing fresh concrete according to concrete production specifications for later use;
(3.2) paving the concrete base material of the bottom layer with fresh concrete, paving a cement slurry layer on the surface of the concrete base material after the surface is leveled, and completely covering the surface of the concrete base material of the bottom layer with the cement slurry by using vibration equipment; after standing for 1.5h, paving a layer of fresh concrete on the surface of the cement paste, and using vibration equipment to enable the fresh concrete to completely cover the surface of the cement paste, thereby forming an upper concrete base material;
(3.3) covering the concrete base material of the upper layer with a film, and keeping the pressure at the load of 0.3kPa during the curing process of the concrete; and after the curing is finished, removing the load and the film to obtain the nano modified photocatalytic self-cleaning concrete.
Example 3
(1) Nitrogen doped nano TiO2Preparation of powder:
mixing sulfur or ammonium sulfate with nano TiO2Mixing the powder evenly, sulfurizing nitrogen in ammonium sulfate and nano TiO2The mass ratio of titanium in the powder is 1: 7; ball-milling at 600r/min for 2h, calcining at 800 deg.C for 5h, and cooling to obtain nitrogen-doped nanometer TiO2And (3) powder.
(2) Preparing cement paste:
the cement paste is prepared by mixing the following components in parts by weight: 95 parts of cement and nitrogen-doped nano TiO24 parts of powder, 1 part of water reducing agent and 25 parts of water;
weighing the raw material components according to the proportion; mixing cement with newly prepared nitrogen-doped nano TiO2And mixing the powder in a ball mill for 40min, adding a water reducing agent and water, and continuously mixing for 2.5min to prepare cement slurry for later use.
(3) Preparing nano modified photocatalytic self-cleaning concrete:
the nano modified photocatalysis self-cleaning concrete is formed by loading, pressurizing, maintaining and drying cement slurry positioned in the middle layer and concrete base materials positioned in the upper layer and the lower layer; the thickness of the cement paste positioned in the middle layer after curing and drying is 0.7 mm; the thickness of the concrete base material on the upper layer after curing and drying is 2.5 mm.
The concrete base material is prepared by mixing the following components in parts by weight: 100 parts of cement, 120 parts of fine aggregate, 110 parts of coarse aggregate, 1.5 parts of water reducing agent and 35 parts of water.
(3.1) mixing cement, fine aggregate, coarse aggregate, a water reducing agent and water, and preparing fresh concrete according to concrete production specifications for later use;
(3.2) paving the concrete base material of the bottom layer with fresh concrete, paving a cement slurry layer on the surface of the concrete base material after the surface is leveled, and completely covering the surface of the concrete base material of the bottom layer with the cement slurry by using vibration equipment; after standing for 70min, paving a layer of fresh concrete on the surface of the cement paste, and using vibration equipment to enable the fresh concrete to completely cover the surface of the cement paste, thereby forming an upper concrete base material;
(3.3) covering the concrete base material of the upper layer with a film, and keeping the pressure at the load of 0.25kPa during the curing process of the concrete; and after the curing is finished, removing the load and the film to obtain the nano modified photocatalytic self-cleaning concrete.
Comparative example 1
The nano photocatalytic concrete is prepared by a coating method, and a concrete base material is prepared by mixing 100 parts of cement, 130 parts of fine aggregate, 100 parts of coarse aggregate, 2.5 parts of a water reducing agent and 30 parts of water in proportion and is formed by mechanical pressing.
With commercially available nano-TiO2Is a photocatalyst, a polycarboxylic acid high-efficiency water reducing agent is a dispersant, and the mixing amount of the dispersant is nano TiO21 percent of the doping amount, measured nano TiO2Adding the nano TiO into water together with a dispersant, uniformly stirring, and ball-milling by adopting a planetary ball mill to obtain nano TiO with the mass fraction of 5%2And (3) dispersing the mixture.
And (3) after the base material concrete is molded for 3d, the large surface layer of the concrete product is subjected to dipping treatment by using the nano dispersion liquid, the dipping height is 12mm, the dipping time is 3min, and the dipped concrete sample is continuously cured to 28d and then is subjected to testing and application treatment.
Comparative example 2
The nano photocatalytic concrete is prepared by a coating method, and a concrete base material is prepared by mixing 100 parts of cement, 130 parts of fine aggregate, 100 parts of coarse aggregate, 2.5 parts of a water reducing agent and 30 parts of water in proportion and is formed by mechanical pressing.
Nitrogen doping of nano TiO2Is a photocatalyst, a polycarboxylic acid high-efficiency water reducing agent is a dispersant, and the mixing amount of the dispersant is nano TiO21 percent of the mixing amountMeasured amount of nano TiO2Adding the nano TiO into water together with a dispersant, uniformly stirring, and ball-milling by adopting a planetary ball mill to obtain nano TiO with the mass fraction of 5%2And (3) dispersing the mixture.
And (3) after the base material concrete is molded for 3d, the large surface layer of the concrete product is subjected to dipping treatment by using the nano dispersion liquid, the dipping height is 12mm, the dipping time is 3min, and the dipped concrete sample is continuously cured to 28d and then is subjected to testing and application treatment.
Test example 1: test method for photocatalytic degradation of methylene blue
The test procedure for photocatalytic degradation of methylene blue was as follows:
(1) preparing 10mg/L methylene blue solution, diluting respectively to obtain 8mg/L, 6mg/L, 4mg/L and 2mg/L methylene blue solution, measuring the linear relation between the concentration of the methylene blue and the absorbance at the wavelength of 664nm by using an ultraviolet spectrophotometer, and obtaining a standard curve;
(2) cutting the nano modified photocatalytic self-cleaning concrete into small test pieces with the size of 30 multiplied by 50 multiplied by 100mm, cleaning the test pieces after the cutting is finished, and naturally drying the test pieces for 24 hours;
(3) adding 10mg/L methylene blue solution into a container, putting a sample to be tested, and turning on an ultraviolet lamp to perform a photocatalytic test;
(4) measuring the absorbance of the solution by using an ultraviolet-visible spectrophotometer after the photocatalysis is carried out for a certain time, and calculating the concentration of the methylene blue solution according to a standard curve;
(5) according to the concentration characterization of methylene blue, the catalytic efficiency of the nano modified photocatalytic self-cleaning concrete is as follows: (initial concentration-concentration after a certain time of photocatalysis)/initial concentration
Test example 2: photocatalytic degradation of NOxTest method (2)
Photocatalytic degradation of NOxThe test instrument comprises a photocatalytic reaction container, the top of which is provided with a simulated sunlight light source. One end of the photocatalytic reaction container is connected withThe other end of the gas flow controller is connected with a gas output device. In the test, a sample (the size of the sample is 30X 50X 100mm) is placed in a photocatalytic reaction vessel, and a sunlight light source is turned on for irradiation. Gas input device for providing dry air and NO2A mixture of standard gases.
The test steps are as follows:
(1) mixing dry air with NO2Standard gas (NO)2Gas concentration about 60ppm) as 4: 1 proportion to prepare mixed gas, and the prepared mixed gas NO2The concentration was about 12 ppm.
(2) The sample was placed in a sealed photocatalytic container.
(3) And (3) inputting a certain amount of reaction gas into the reaction container, wherein the flow rate of the mixed gas is 80L/h, and starting the sunlight light source after ventilating for 30 min.
After a certain time of photocatalytic reaction, sampling and measuring input and output NO2The gas concentration.
Calculating NO according to the input and output gas concentration2Efficiency of photocatalytic reaction of degradation (initial NO)2concentration-NO after photocatalytic reaction2Concentration)/initial NO2And (4) concentration.
Test example 3: concrete surface morphology testing method
And (3) preparing samples according to SEM observation sample preparation standards, observing the surface of the concrete structure by adopting an TESCAN VEGA 2LMU electron microscope, and strictly cleaning the surface of the sample before observation to prevent the observation from being interfered.
Table 1 shows the photocatalytic degradation effect of the photocatalytic concrete prepared in examples 1 to 3 and comparative examples 1 to 2 on methylene blue. As can be seen from Table 1, the photocatalytic efficiency of the photocatalytic concrete of comparative example 1 prepared by the conventional coating method for 24 hours is only 25.6%, and TiO content is only 25.6%2The nitrogen doping treatment has little influence on the degradation effect of methylene blue; examples of Nano-modified self-cleaning photocatalytic concrete prepared by novel ProcessThe photocatalytic efficiency of 24h methylene blue of 1 to example 3 can be improved to more than 50 percent along with the nano TiO2The addition amount is increased, and compared with the traditional coated photocatalytic concrete, the degradation efficiency of the methylene blue is obviously improved.
TABLE 1 photocatalytic degradation efficiency of nano modified photocatalytic self-cleaning concrete for methylene blue
| Test specimen | Initial concentration of methylene blue/mg/L | 24h photocatalytic efficiency/%) |
| Example 1 | 10 | 59.3 |
| Example 2 | 10 | 51.5 |
| Example 3 | 10 | 56.2 |
| Comparative example 1 | 10 | 25.6 |
| Comparative example 2 | 10 | 28.7 |
Table 2 shows the photocatalytic degradation effect of the photocatalytic concrete obtained in examples 1 to 3 and comparative examples 1 to 2 on NOx. The results in table 2 show that under the conditions of the comparative example 1, the 24hNOx photocatalytic efficiency is only 28.7%, the 5d continuous photocatalytic efficiency is reduced to 16.4%, the photocatalytic efficiency of the comparative example 2 after nitrogen doping treatment is obviously improved, the photocatalytic efficiency of the comparative example 224hNOx is 38.4%, and the improvement amplitude is 33.8%; after the nano photocatalytic self-cleaning concrete is prepared, the 24hNOx photocatalytic efficiency is further improved along with nano TiO2Increased by increasing the doping amount, 7.5 percent of nitrogen-doped TiO2When the amount is added, the photocatalytic efficiency reaches 54.4 percent, and the photocatalytic efficiency in the compact concrete is relatively high. In addition, nano TiO2The nitrogen doping treatment has a remarkable effect on improving the continuity of the photocatalytic concrete, the 5d continuous photocatalytic efficiency of the examples 1-3 can reach more than 35% and is far higher than that of the comparative examples 1-2, and the results in the table 2 show that the nano modified photocatalytic self-cleaning concrete has excellent photocatalytic performance compared with the common photocatalytic concrete and can remarkably improve the photocatalytic continuity of the concrete.
TABLE 2 nanometer modified photocatalytic self-cleaning concrete to NOxEfficiency of photocatalytic degradation
| Test specimen | Flow rate of mixed gas/L/h | 24h photocatalytic efficiency/%) | 5d sustained photocatalytic efficiency% |
| Example 1 | 80 | 54.4 | 41.1 |
| Example 2 | 80 | 46.6 | 35.6 |
| Example 3 | 80 | 49.3 | 36.7 |
| Comparative example 1 | 80 | 28.7 | 16.4 |
| Comparative example 2 | 80 | 38.4 | 23.2 |
Fig. 3 is an SEM image of the concrete surface morphology of example 1, and the result shows that the nano-modified photocatalytic concrete has a good mirror effect, the particle size of the C-S-H gel is very small, the concrete surface roughness is very small, the covering and accumulation of surface impurities caused by roughness of the conventional photocatalytic concrete can be effectively avoided, the concrete flatness can completely satisfy the functional requirement of self-cleaning, and the concrete photocatalytic persistence is greatly improved.
Based on the foregoing description, the actual scope of the invention encompasses not only the disclosed embodiments, but also all equivalent ways of practicing or implementing the invention under the claims.
Claims (5)
1. The nano modified photocatalytic self-cleaning concrete is characterized in that the concrete is formed by loading, pressurizing, maintaining and drying cement slurry positioned in a middle layer and concrete base materials positioned in an upper layer and a lower layer; wherein,
the cement paste is prepared by mixing the following components in parts by weight: 92.5-97.5 parts of cement and nitrogen-doped nano TiO22.5-7.5 parts of powder, 0.5-1.5 parts of water reducing agent and 20-30 parts of water;
the concrete base material is prepared by mixing the following components in parts by weight: 100 parts of cement, 100-130 parts of fine aggregate, 100-120 parts of coarse aggregate, 0.5-2.5 parts of water reducing agent and 30-40 parts of water.
2. The concrete of claim 1, wherein the nitrogen-doped nano TiO2The powder is prepared by the following steps: mixing sulfur or ammonium sulfate with nano TiO2Mixing the powder evenly, sulfurizing nitrogen in ammonium sulfate and nano TiO2The mass ratio of titanium in the powder is 1: 4-12; ball milling at a rotating speed of 300-900 r/min for 0.5-4 h, calcining at 400-1200 ℃ for 1-8 h, and cooling to obtain the nitrogen-doped nano TiO2And (3) powder.
3. The concrete according to claim 1, wherein the cement is a commercially available P-O42.5R portland cement, complying with GB/T175-2007 standards; the nano TiO2Is anatase type nano TiO2The diameter is 10-40 nm; the fine aggregate is natural sand or quartz sand, meets GB/T14684-2011 execution standard, and has a mud content of less than 1%; the coarse aggregate is crushed stone with the particle size of 2.36-4.76 mm, meets GB/T14685-2011 execution standard, and has the needle sheet content of less than 10%, the porosity of less than 47% and the mud content of less than 0.5%; the water reducing agent is a polycarboxylic acid water reducing agent, meets GB/T8076-2008 execution standard, and has a water reducing rate of more than 20%.
4. The concrete as claimed in claim 1, wherein the thickness of the cement paste at the middle layer after curing and drying is 0.5mm to 1 mm; the thickness of the concrete base material on the upper layer after curing and drying is 2 mm-3 mm.
5. The preparation method of the nano-modified photocatalytic self-cleaning concrete as claimed in claims 1 to 4, characterized by comprising the following steps:
(1) weighing the raw material components according to the proportion;
(2) mixing cement with newly prepared nitrogen-doped nano TiO2Mixing the powder in a ball millAfter 0.5-1 h, adding a water reducing agent and water, and continuously mixing for 2-3 min to prepare cement slurry for later use;
(3) mixing cement, fine aggregate, coarse aggregate, a water reducing agent and water, and preparing fresh concrete according to concrete production specifications for later use;
(4) firstly, paving a concrete base material of a bottom layer with fresh concrete, paving a cement slurry layer on the surface of the concrete base material after the surface is trowelled, and completely covering the surface of the concrete base material of the bottom layer with cement slurry by using vibration equipment; after standing for 1-1.5 h, paving a layer of fresh concrete on the surface of the cement paste, and using vibration equipment to enable the fresh concrete to completely cover the surface of the cement paste, so as to form an upper-layer concrete base material;
(5) covering the concrete base material on the upper layer with a film, and keeping pressurizing at a load of 0.2-0.3 kPa during the curing process of the concrete; and after the curing is finished, removing the load and the film to obtain the nano modified photocatalytic self-cleaning concrete.
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| CN112624709A (en) * | 2021-01-15 | 2021-04-09 | 福州大学 | Antibacterial cement concrete and preparation method thereof |
| CN116425568A (en) * | 2023-04-11 | 2023-07-14 | 同济大学 | Preparation method of concrete with oxygen release function |
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