CN108129096A - For the cement slurry and preparation method of nanometer modified photocatalytic self-cleaning concrete - Google Patents
For the cement slurry and preparation method of nanometer modified photocatalytic self-cleaning concrete Download PDFInfo
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- CN108129096A CN108129096A CN201711208281.XA CN201711208281A CN108129096A CN 108129096 A CN108129096 A CN 108129096A CN 201711208281 A CN201711208281 A CN 201711208281A CN 108129096 A CN108129096 A CN 108129096A
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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
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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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/30—Oxides other than silica
- C04B14/305—Titanium oxide, e.g. titanates
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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
- C04B2111/00474—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
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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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- Ceramic Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The present invention relates to building material engineering technologies, it is desirable to provide a kind of cement slurry and preparation method for nanometer modified photocatalytic self-cleaning concrete.The cement slurry is mixed by each component of following weight parts：92.5~97.5 parts of cement, nitrating nanometer TiO22.5~7.5 parts of powder, 0.5~1.5 part of water-reducing agent, 20~30 parts of water.The present invention can be used for preparing nanometer modified photocatalytic self-cleaning concrete, be the centre that cement slurry is laid in upper and lower two layers of concrete substrate, and concrete is obtained after load pressurizes and conserves drying；The concrete 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 duration, has self-cleaning function.
Description
Technical field
The present invention relates to building material engineering technical fields, and in particular to one kind is mixed for nanometer modified photocatalytic self-cleaning
Coagulate the cement slurry and preparation method of soil.
Background technology
With the continuous social and economic development, atmosphere polluting problem has become one of main problem paid close attention to for the mankind.
The main reason for vehicle exhaust is as atmosphere pollution, contamination control become increasingly serious with continuing to increase for automobile quantity, tail
Gas total emission volumn is quite huge, how to effectively control caused by vehicle exhaust atmosphere pollution become industry inner height pay attention to
Technical field.
Research shows that utilize TiO2Light-catalyzed reaction principle can effectively realize elimination and the purpose for atmosphere pollution of degrading,
Grain size is less than the TiO of 15nm2Particle has apparent skin effect and quantum effect, has extraordinary oxidation under light action
Reducing power has excellent photocatalysis performance.Nano-TiO simultaneously2Crystalline structure, surface topography, specific surface area and chemistry
The factors such as potential all directly affect its photocatalysis performance, to nano-TiO2Nitrating processing is carried out, is not only greatly improved TiO2's
Photocatalysis efficiency can also expand its photoresponse wavelength, increase substantially photocatalysis performance.
The discharge section of general vehicle exhaust prepares high duration photocatalysis between 0.3m~2m using photocatalysis technology
Pavement concrete, using cement concrete as nano-TiO2Photocatalysis carrier, utilize TiO2Photocatalytic activity absorb automobile
Nitrogen oxides, SO in tail gas2Etc. harmful substances, it is made to be converted into nitric acid, sulfuric acid etc., be realize vehicle exhaust pollution-freeization
One important technical of processing.At present both at home and abroad to TiO2Application point in concrete is following two：1. it is mixed by interior
Method introduces nano-TiO in concrete2, there are nanoparticle agglomerates, nano particle waste, photocatalysis performance differences etc. for the method
Major defect.2. carrying out sprinkling processing on molded concrete substrate surface, make nano-TiO2Particle is attached in concrete
Portion's apparent gap, the method can effectively reduce nano particle waste, but high-Miller-index surface material support surfaces photochemical catalyst with
The contact area for polluting air is small, and time of contact is short, causes the problems such as concrete material photocatalysis efficiency is low, and duration is poor.
Although photocatalysis concrete starts of interest by more and more researchers, still deposited in actual fabrication process
In many insoluble problems, wherein the most importantly photocatalytic activity duration is shorter, cause its utility value low,
It is difficult to form good economic benefit, the serious Technique Popularizing for restricting photocatalysis concrete, this is because conventional concrete surface
Coarse, dust and catabolite easily cover catalyst, make it that can not be sufficiently exposed under gas and sunlight, not timing is clear
Reason is difficult persistently to play its photocatalysis performance, therefore, how to improve concrete surface flatness, develops a kind of self-cleaning
The excellent photocatalysis concrete of energy is an important technical for improving photocatalysis duration.
Invention content
The technical problem to be solved by the present invention is to overcome deficiency of the prior art, provide a kind of for nano modification light
It is catalyzed the cement slurry and preparation method of self-cleaning concrete.The present invention, which can effectively decompose concrete surface, has the object of stench
Matter, virus, bacterium etc. absorb the atmosphere pollution that motor vehicle emission is particularly in air, greatly improve the photocatalysis effect of concrete
Rate and photocatalysis duration.
To solve technical problem, solution of the invention is：
A kind of cement slurry for nanometer modified photocatalytic self-cleaning concrete is provided, is each group by following weight parts
Divide and mix：92.5~97.5 parts of cement, nitrating nanometer TiO22.5~7.5 parts of powder, 0.5~1.5 part of water-reducing agent, water 20
~30 parts.
In the present invention, the nitrating nanometer TiO2Powder is prepared by following manner：By vulcanization press or ammonium sulfate with
Nano-TiO2Powder is uniformly mixed, and vulcanization is pressed or nitrogen and nano-TiO in ammonium sulfate2Titanium mass ratio in powder is 1: 4~12；
After 0.5~4h of rotating speed ball-milling treatment of 300~900r/min, 1~8h is calcined at 400~1200 DEG C, is mixed through cooling
Nitrogen nano-TiO2Powder.
Invention further provides the preparation methods of the cement slurry, include the following steps：
(1) each raw material components are weighed in the ratio；
(2) by cement and the nitrating nanometer TiO of brand-new2After powder mixes 0.5~1h in the ball mill, add in water-reducing agent and
Water simultaneously continues 2~3min of mixing, cement slurry is prepared, for use.
The present invention also provides the application methods of the cement slurry, are that cement slurry is laid in two layer concretes up and down
The centre of base material obtains nanometer modified photocatalytic self-cleaning concrete after load pressurizes and conserves drying；Its specific steps
For：
(1) each raw material components are weighed in the ratio：100 parts of cement, 100~130 parts of fine aggregate, coarse aggregate 100~120
Part, 0.5~2.5 part of water-reducing agent, 30~40 parts of water；
(2) each component is uniformly mixed, fresh concrete is prepared by concrete production specification, for use；
(3) concrete substrate of bottom is first laid with fresh concrete, cement slurry layer is laid on coagulation after the floating of surface
The surface of soil matrix material makes cement slurry that the surface of bottom concrete base material be completely covered using vibratory equipment；Stand 1~
After 1.5h, one layer of fresh concrete is re-layed on the surface of cement slurry, fresh concrete is completely covered using vibratory equipment
The surface of cement slurry, so as to form the concrete substrate on upper strata；
(4) it with the concrete substrate on film covering upper strata, is kept in the maintenance processes of concrete with 0.2~0.3kPa's
Load pressurizes；Load and film are removed after the completion of maintenance, obtains nanometer modified photocatalytic self-cleaning concrete.
In the present invention, the cement is commercially available PO 42.5R Portland cements, meets GB/T175-2007 execution
Standard；The nano-TiO2For anatase type nano TiO2, a diameter of 10~40nm；The fine aggregate is natural sand or quartz
Sand meets GB/T14684-2011 and performs standard, and clay content is less than 1%；The coarse aggregate is 2.36~4.76mm rubbles, is accorded with
It closes GB/T 14685-2011 and performs standard, elongated particles are less than 10%, and porosity is less than 47%, and clay content is less than 0.5%；
The water-reducing agent is polycarboxylate water-reducer, meets GB/T8076-2008 and performs standard, water-reducing rate is more than 20%.
It is described to be located at intermediate cement slurry through conserving dried thickness as 0.5mm~1mm in the present invention；It is described
Concrete substrate positioned at upper strata is through conserving dried thickness as 2mm~3mm.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, the present invention is to nano-TiO2Carry out nitrating processing, using N-O ionic radius, electronegativity etc. difference
Property, TiO can be effectively reduced2Energy gap, improve nano-TiO2To the response wave length of visible ray, nanometer can be increased substantially
TiO2Photocatalysis performance.
2nd, the present invention can be used for successively handling, and be further applied load in maintenance processes concrete, make cement slurry
Layer is bonded completely between upper strata and the concrete substrate of bottom, and the splendid self-cleaning of appearance is formed after demoulding maintenance and is mixed
Solidifying soil.It can effectively solve the problem that nanoparticle agglomerates, uniformity existing for traditional photocatalysis concrete inner blending method or surface cladding process
The bad main problem of difference, photocatalysis performance, photocatalysis performance greatly promote.
3rd, the nanometer modified photocatalytic self-cleaning concrete prepared using the present invention, can be by fluidised form cement slurry and concrete
Base material fully combines, the C-S-H gel grain size sizes and nano-TiO of formation2Close, concrete surface roughness is minimum,
Traditional photocatalysis concrete surface impurity covering and accumulation caused by coarse are avoided, leads to the reduction of photocatalysis duration
The problem of, concrete photocatalysis duration is greatly improved, has excellent self-cleaning function.
Description of the drawings
Fig. 1 is 5 × 104Nanometer modified photocatalytic self-cleaning concrete surface form under multiple.
Specific embodiment
Following embodiment can make the technical staff of this professional skill field more fully understand the present invention, but not to appoint
Where formula limitation is of the invention.
Cement used in various embodiments of the present invention is commercially available PO 42.5R Portland cements, meets GB/T175-2007
Execution standard；The nano-TiO2For anatase type nano TiO2, a diameter of 10~40nm；The fine aggregate is natural sand or stone
Sand meets GB/T14684-2011 and performs standard, and clay content is less than 1%；The coarse aggregate is 2.36~4.76mm rubbles,
Meet GB/T 14685-2011 and perform standard, elongated particles are less than 10%, and porosity is less than 47%, and clay content is less than
0.5%；The water-reducing agent is polycarboxylate water-reducer, meets GB/T8076-2008 and performs standard, water-reducing rate is more than 20%.
Embodiment 1
(1) nitrating nanometer TiO2The preparation of powder：
Vulcanization is pressed or ammonium sulfate and nano-TiO2Powder is uniformly mixed, and vulcanization is pressed or nitrogen and nano-TiO in ammonium sulfate2
Titanium mass ratio in powder is 1: 4；After the rotating speed ball-milling treatment 0.5h of 300r/min, 1h is calcined at 400 DEG C, through cooling
Obtain nitrating nanometer TiO2Powder.
(2) preparation of cement slurry：
Cement slurry is mixed by each component of following weight parts：92.5 parts of cement, nitrating nanometer TiO2Powder 2.5
Part, 0.5 part of water-reducing agent, 20 parts of water；
Each raw material components are weighed in the ratio；By cement and the nitrating nanometer TiO of brand-new2Powder mixes in the ball mill
After 0.5h, add in water-reducing agent and water and continue to mix 2min, cement slurry is prepared, for use.
(3) preparation of nanometer modified photocatalytic self-cleaning concrete：
Nanometer modified photocatalytic self-cleaning concrete, by being located at the cement slurry in middle level and positioned at bilevel concrete
Base material is formed after load pressurizes and conserves drying；Cement slurry positioned at middle level is being through conserving dried thickness
0.5mm；The concrete substrate positioned at upper strata is 2mm through conserving dried thickness.
The concrete substrate is mixed by each component of following weight parts：100 parts of cement, 100 parts of fine aggregate,
100 parts of coarse aggregate, 0.5 part of water-reducing agent, 30 parts of water.
(3.1) cement, fine aggregate, coarse aggregate, water-reducing agent and water are mixed, is prepared newly by concrete production specification
Mixed concrete, for use；
(3.2) concrete substrate of bottom is first laid with fresh concrete, cement slurry layer is laid on mixed by surface after smoothing out
The surface of solidifying soil matrix material makes cement slurry that the surface of bottom concrete base material be completely covered using vibratory equipment；Standing 1h
Afterwards, one layer of fresh concrete is re-layed on the surface of cement slurry, makes fresh concrete that cement be completely covered using vibratory equipment
The surface of slurry, so as to form the concrete substrate on upper strata；
(3.3) it with the concrete substrate on film covering upper strata, is kept in the maintenance processes of concrete with the lotus of 0.2kPa
It is loaded into capable pressurization；Load and film are removed after the completion of maintenance, obtains nanometer modified photocatalytic self-cleaning concrete.
Embodiment 2
(1) nitrating nanometer TiO2The preparation of powder：
Vulcanization is pressed or ammonium sulfate and nano-TiO2Powder is uniformly mixed, and vulcanization is pressed or nitrogen and nano-TiO in ammonium sulfate2
Titanium mass ratio in powder is 1: 12；After the rotating speed ball-milling treatment 4h of 900r/min, 8h is calcined at 1200 DEG C, through cooling
Obtain nitrating nanometer TiO2Powder.
(2) preparation of cement slurry：
Cement slurry is mixed by each component of following weight parts：97.5 parts of cement, nitrating nanometer TiO2Powder 7.5
Part, 1.5 parts of water-reducing agent, 30 parts of water；
Each raw material components are weighed in the ratio；By cement and the nitrating nanometer TiO of brand-new2Powder mixes in the ball mill
After 1h, add in water-reducing agent and water and continue to mix 3min, cement slurry is prepared, for use.
(3) preparation of nanometer modified photocatalytic self-cleaning concrete：
Nanometer modified photocatalytic self-cleaning concrete, by being located at the cement slurry in middle level and positioned at bilevel concrete
Base material is formed after load pressurizes and conserves drying；Cement slurry positioned at middle level is being 1mm through conserving dried thickness；
The concrete substrate positioned at upper strata is 4mm through conserving dried thickness.
The concrete substrate is mixed by each component of following weight parts：100 parts of cement, 130 parts of fine aggregate,
120 parts of coarse aggregate, 2.5 parts of water-reducing agent, 40 parts of water.
(3.1) cement, fine aggregate, coarse aggregate, water-reducing agent and water are mixed, is prepared newly by concrete production specification
Mixed concrete, for use；
(3.2) concrete substrate of bottom is first laid with fresh concrete, cement slurry layer is laid on mixed by surface after smoothing out
The surface of solidifying soil matrix material makes cement slurry that the surface of bottom concrete base material be completely covered using vibratory equipment；Standing 1.5h
Afterwards, one layer of fresh concrete is re-layed on the surface of cement slurry, makes fresh concrete that cement be completely covered using vibratory equipment
The surface of slurry, so as to form the concrete substrate on upper strata；
(3.3) it with the concrete substrate on film covering upper strata, is kept in the maintenance processes of concrete with the lotus of 0.3kPa
It is loaded into capable pressurization；Load and film are removed after the completion of maintenance, obtains nanometer modified photocatalytic self-cleaning concrete.
Embodiment 3
(1) nitrating nanometer TiO2The preparation of powder：
Vulcanization is pressed or ammonium sulfate and nano-TiO2Powder is uniformly mixed, and vulcanization is pressed or nitrogen and nano-TiO in ammonium sulfate2
Titanium mass ratio in powder is 1: 7；After the rotating speed ball-milling treatment 2h of 600r/min, 5h is calcined at 800 DEG C, through cooling down
To nitrating nanometer TiO2Powder.
(2) preparation of cement slurry：
Cement slurry is mixed by each component of following weight parts：95 parts of cement, nitrating nanometer TiO24 parts of powder subtracts
1 part of aqua, 25 parts of water；
Each raw material components are weighed in the ratio；By cement and the nitrating nanometer TiO of brand-new2Powder mixes in the ball mill
After 40min, add in water-reducing agent and water and continue to mix 2.5min, cement slurry is prepared, for use.
(3) preparation of nanometer modified photocatalytic self-cleaning concrete：
Nanometer modified photocatalytic self-cleaning concrete, by being located at the cement slurry in middle level and positioned at bilevel concrete
Base material is formed after load pressurizes and conserves drying；Cement slurry positioned at middle level is being through conserving dried thickness
0.7mm；The concrete substrate positioned at upper strata is 2.5mm through conserving dried thickness.
The concrete substrate is mixed by each component of following weight parts：100 parts of cement, 120 parts of fine aggregate,
110 parts of coarse aggregate, 1.5 parts of water-reducing agent, 35 parts of water.
(3.1) cement, fine aggregate, coarse aggregate, water-reducing agent and water are mixed, is prepared newly by concrete production specification
Mixed concrete, for use；
(3.2) concrete substrate of bottom is first laid with fresh concrete, cement slurry layer is laid on mixed by surface after smoothing out
The surface of solidifying soil matrix material makes cement slurry that the surface of bottom concrete base material be completely covered using vibratory equipment；It is standing
After 70min, one layer of fresh concrete is re-layed on the surface of cement slurry, fresh concrete is made to cover completely using vibratory equipment
The surface of lid cement slurry, so as to form the concrete substrate on upper strata；
(3.3) it with the concrete substrate on film covering upper strata, is kept in the maintenance processes of concrete with the lotus of 0.25kPa
It is loaded into capable pressurization；Load and film are removed after the completion of maintenance, obtains nanometer modified photocatalytic self-cleaning concrete.
Comparative example 1
Nano-photo catalytic concrete is prepared with cladding process, concrete substrate is by 100 parts of cement, 130 parts of fine aggregate, thick bone
30 parts of 100 parts of material, 2.5 parts of water-reducing agent, water ratio mix configurations, through mechanical compression molding.
With commercially available nano-TiO2For photochemical catalyst, high-efficiency water-reducing agent of poly-carboxylic acid is dispersant, and dispersant volume is nano-TiO2
The 1% of volume, by the nano-TiO of metering2It is added to the water with dispersant, is obtained after stirring evenly using planetary ball mill ball milling
The nano-TiO of 5% mass fraction2Dispersion liquid.
After base material concrete formation 3d, the big face face layer of concrete product is carried out at dipping using nano dispersion fluid
Reason impregnates height 12mm, dip time 3min, the concrete sample after dipping continue to carry out after maintenance to 28d test with
Using processing.
Comparative example 2
Nano-photo catalytic concrete is prepared with cladding process, concrete substrate is by 100 parts of cement, 130 parts of fine aggregate, thick bone
30 parts of 100 parts of material, 2.5 parts of water-reducing agent, water ratio mix configurations, through mechanical compression molding.
Nano-TiO is handled with nitrating2For photochemical catalyst, high-efficiency water-reducing agent of poly-carboxylic acid is dispersant, and dispersant volume is receives
Rice TiO2The 1% of volume, by the nano-TiO of metering2It is added to the water with dispersant, planetary ball mill ball milling is used after stirring evenly
Obtain the nano-TiO of 5% mass fraction2Dispersion liquid.
After base material concrete formation 3d, the big face face layer of concrete product is carried out at dipping using nano dispersion fluid
Reason impregnates height 12mm, dip time 3min, the concrete sample after dipping continue to carry out after maintenance to 28d test with
Using processing.
Test case 1：The test method of photocatalytic degradation methylene blue
The testing procedure of photocatalytic degradation methylene blue is as follows：
(1) methylene blue solution of 10mg/L is prepared, and dilution obtains 8mg/L, 6mg/L, 4mg/L, 2mg/L respectively
Methylene blue solution, methylene blue concentration is measured with ultraviolet specrophotometer and wavelength is line between the absorbance at 664nm
Sexual intercourse, and obtain standard curve；
(2) nanometer modified photocatalytic self-cleaning concrete is cut into the small specimen of 30 × 50 × 100mm, after the completion of cutting
It cleans up, spontaneously dries for 24 hours；
(3) methylene blue solution of 10mg/L is added in into container, is put into sample to be tested, opened ultraviolet lamp and carry out photocatalysis
Experiment；
(4) photocatalysis measures the absorbance of solution using ultraviolet-visible spectrophotometer after a certain period of time, according to standard song
Line calculates the concentration of methylene blue solution；
(5) catalytic efficiency of nanometer modified photocatalytic self-cleaning concrete is characterized according to the concentration of methylene blue：It is (initial
The concentration of concentration-photocatalysis after a certain period of time)/initial concentration
Test case 2：Photocatalytic degradation NOxTest method
Photocatalytic degradation NOxTest equipment includes photocatalyst reaction vessel, and top is furnished with simulated solar radiant.Light is urged
Change gas input device of one end connection with gas flow controller of reaction vessel, another termination gas output device.It surveys
During examination, sample (30 × 50 × 100mm of test specimen size) is placed in photocatalyst reaction vessel, sun radiant is opened and is shone
It penetrates.Gas input device provides dry air and NO2The mixed gas of calibrating gas.
Test procedure：
(1) by dry air and NO2Calibrating gas (NO2Gas concentration is about 60ppm) by 4：1 ratio mixes, and mixing is made
Gas, the mixed gas NO of preparation2Concentration is about 12ppm.
(2) sample is put into the photocatalysis container of sealing.
(3) a certain amount of reaction gas is inputted into reaction vessel, after mixed gas flow 80L/h, the 30min that ventilates
Open sun radiant.
After the light-catalyzed reaction of certain time, the NO of input and output is measured by sampling2Gas concentration.
According to the gas concentration of input and output, NO is calculated2Light-catalyzed reaction efficiency (the initial NO of degradation2Concentration-light is urged
Change NO after reacting2Concentration)/initial NO2Concentration.
Test case 3：Concrete surface form test method
Sample preparation is carried out by SEM observation sample preparation standards, using TESCAN VEGA 2LMU electron microscope observation concrete knots
Sample surfaces cleaning is strictly carried out on structure surface before observation, observation is prevented to be interfered.
Table 1 is photocatalysis concrete made from 1~embodiment of embodiment 3 and 1~comparative example of comparative example 2 to methylene blue
Photocatalytic degradation effect.By table 1 as it can be seen that 1 photocatalysis concrete photocatalysis for 24 hours of the comparative example effect prepared using traditional cladding process
Rate is only 25.6%, TiO2Nitrating processing influences the degradation effect of methylene blue little；The nanometer prepared using novel process
The photocatalysis efficiency of the methylene blue for 24 hours of 1~embodiment of modified self-cleaning photocatalysis concrete embodiment 3 can be increased to 50%
More than, and with nano-TiO2The increase of volume and increase, with tradition coat photocatalysis concrete compared with, methylene blue degradation effect
Rate improves notable.
1 nanometer modified photocatalytic self-cleaning concrete of table is to the photocatalytic degradation efficiency of methylene blue
| Sample | Methylene blue initial concentration/mg/L | Photocatalysis efficiency/% for 24 hours |
| Embodiment 1 | 10 | 59.3 |
| Embodiment 2 | 10 | 51.5 |
| Embodiment 3 | 10 | 56.2 |
| Comparative example 1 | 10 | 25.6 |
| Comparative example 2 | 10 | 28.7 |
The photocatalysis concrete that table 2 is obtained for 1~embodiment of embodiment 3 and 1~comparative example of comparative example 2 is to NOx photocatalysis
Degradation effect.By table 2, as a result, it has been found that, under the conditions of comparative example 1, the photocatalysis efficiency of NOx photocatalysis for 24 hours is only that 28.7%, 5d is held
Continuous photocatalysis efficiency is reduced to 16.4%, and 2 photocatalysis efficiency of comparative example significantly improves after nitrating is handled, the NOx for 24 hours of comparative example 2
Photocatalysis efficiency is 38.4%, and increase rate is up to 33.8%；After nano-photo catalytic self-cleaning concrete is made,
NOx photocatalysis efficiencies further improve for 24 hours, and with nano-TiO2The increase of volume and increase, 7.5% nitrating TiO2
For photocatalysis efficiency up to 54.4%, the photocatalysis efficiency in density concrete is relatively high during volume.In addition, nano-TiO2
Nitrating processing has a remarkable result to improving photocatalysis concrete duration, and it is reachable that the 5d of Examples 1 to 3 continues photocatalysis efficiency
More than 35%, the significantly larger than lasting photocatalysis efficiency of comparative example 1~2, table 2 the result shows that, nanometer modified photocatalytic self-cleaning
The more common photocatalysis concrete photocatalysis performance of concrete is excellent, can significantly improve the photocatalysis duration of concrete.
2 nanometer modified photocatalytic self-cleaning concrete of table is to NOxPhotocatalytic degradation efficiency
| Sample | Mixed gas flow/L/h | Photocatalysis efficiency/% for 24 hours | 5d continues photocatalysis efficiency/% |
| Embodiment 1 | 80 | 54.4 | 41.1 |
| Embodiment 2 | 80 | 46.6 | 35.6 |
| Embodiment 3 | 80 | 49.3 | 36.7 |
| Comparative example 1 | 80 | 28.7 | 16.4 |
| Comparative example 2 | 80 | 38.4 | 23.2 |
Fig. 1 is that the concrete surface form SEM of embodiment 1 schemes, the results showed that, nanometer modified photocatalytic concrete has good
Good mirror effect, C-S-H gel grain size sizes are minimum, and concrete surface roughness is minimum, can effectively avoid tradition
Photocatalysis concrete surface impurity covering and accumulation caused by coarse, concrete flatness can fully meet self-cleaning
Functional requirement greatly improves concrete photocatalysis duration.
Based on foregoing description, the actual scope of the present invention not only includes the disclosed embodiments, is additionally included in claim
All equivalent schemes of the present invention are practiced or carried out under book.
Claims (7)
1. a kind of cement slurry for nanometer modified photocatalytic self-cleaning concrete, which is characterized in that be by following weight parts
Each component mix：92.5~97.5 parts of cement, nitrating nanometer TiO22.5~7.5 parts of powder, water-reducing agent 0.5~1.5
Part, 20~30 parts of water.
2. cement slurry according to claim 1, which is characterized in that the nitrating nanometer TiO2Powder passes through following manner
It prepares：Vulcanization is pressed or ammonium sulfate and nano-TiO2Powder is uniformly mixed, and vulcanization is pressed or nitrogen and nano-TiO in ammonium sulfate2
Titanium mass ratio in powder is 1: 4~12；After 0.5~4h of rotating speed ball-milling treatment of 300~900r/min, 400~1200
1~8h is calcined at DEG C, nitrating nanometer TiO is obtained through cooling2Powder.
3. cement slurry according to claim 1, which is characterized in that the cement is the commercially available common silicic acid of PO 42.5R
Salt cement meets GB/T175-2007 and performs standard；The nano-TiO2For anatase type nano TiO2, a diameter of 10~40nm；
The water-reducing agent is polycarboxylate water-reducer, meets GB/T8076-2008 and performs standard, water-reducing rate is more than 20%.
4. the preparation method of cement slurry described in claims 1 to 3 any one, which is characterized in that include the following steps：
(1) each raw material components are weighed in the ratio；
(2) by cement and the nitrating nanometer TiO of brand-new2After powder mixes 0.5~1h in the ball mill, water-reducing agent and water are added in simultaneously
Continue 2~3min of mixing, cement slurry is prepared, for use.
5. the application method of cement slurry described in claims 1 to 3 any one, which is characterized in that be to apply cement slurry
Set on the centre of upper and lower two layers of concrete substrate, obtain nanometer modified photocatalytic self-cleaning through load pressurization and after conserving drying and mix
Solidifying soil；Its specific steps are：
(1) each raw material components are weighed in the ratio：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；
(2) each component is uniformly mixed, fresh concrete is prepared by concrete production specification, for use；
(3) concrete substrate of bottom is first laid with fresh concrete, cement slurry layer is laid on coagulation soil matrix after the floating of surface
The surface of material makes cement slurry that the surface of bottom concrete base material be completely covered using vibratory equipment；After 1~1.5h is stood,
One layer of fresh concrete is re-layed on the surface of cement slurry, makes fresh concrete that cement slurry be completely covered using vibratory equipment
Surface, so as to form the concrete substrate on upper strata；
(4) it with the concrete substrate on film covering upper strata, is kept in the maintenance processes of concrete with the load of 0.2~0.3kPa
It pressurizes；Load and film are removed after the completion of maintenance, obtains nanometer modified photocatalytic self-cleaning concrete.
6. according to the method described in claim 5, it is characterized in that, the cement is commercially available PO 42.5R normal silicate water
Mud meets GB/T175-2007 and performs standard；The nano-TiO2For anatase type nano TiO2, a diameter of 10~40nm；It is described
Fine aggregate is natural sand or quartz sand, meets GB/T14684-2011 and performs standard, clay content is less than 1%；The coarse aggregate is
2.36~4.76mm rubbles meet GB/T 14685-2011 and perform standard, and elongated particles are less than 10%, and porosity is less than
47%, clay content is less than 0.5%；The water-reducing agent is polycarboxylate water-reducer, meets GB/T8076-2008 and performs standard, diminishing
Rate is more than 20%.
7. according to the method described in claim 5, it is characterized in that, described be located at intermediate cement slurry after maintenance is dry
Thickness be 0.5mm~1mm；The concrete substrate positioned at upper strata is 2mm~3mm through conserving dried thickness.
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