CN102674737B - Special external reactant for self-cleaning concrete and preparation method thereof - Google Patents
Special external reactant for self-cleaning concrete and preparation method thereof Download PDFInfo
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- CN102674737B CN102674737B CN201210184318.0A CN201210184318A CN102674737B CN 102674737 B CN102674737 B CN 102674737B CN 201210184318 A CN201210184318 A CN 201210184318A CN 102674737 B CN102674737 B CN 102674737B
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Abstract
The invention discloses a special external reactant for self-cleaning concrete and a preparation method thereof. The external reactant comprises the following ingredients in percentage by weight: 3-10% of Fe-doped nano titanium dioxide powder, 0.3-0.8% of surfactant and 89.5-96.5% of dispersant. The preparation method comprises the following steps of: firstly preparing the Fe-doped nano titanium dioxide powder with the average particle diameter of 60nm by a spontaneous combustion method; and then dispersing the obtained powder in a liquid phase so as to prepare the special external reactant for the self-cleaning concrete. The special external reactant disclosed by the invention has the following advantages that Fe<3+> solid is dissolved in a nano titanium dioxide system by utilizing a spontaneous combustion technology, so that the absorption threshold of a photocatalysis material is improved, and the solar energy utilization ratio is improved; and the nano powder is uniformly dispersed in a liquid phase system through the surfactant, so that the nano powder can be uniformly dispersed to a concrete system.
Description
Technical field
The present invention relates to building material field, particularly a kind of automatically cleaning concrete special additive and preparation method thereof.
Background technology
Along with the fast development of cement concrete technology, develop the concrete with self-cleaning function abroad.In this concrete, adulterate and there is the nano titanium oxide of photocatalysis.By the photocatalysis of nano titanium oxide, decompose the dirt of concrete surface, dirt is reduced at the sticking power of concrete surface, be easy to by rainwater and gasflow clean-up, therefore can keep the clean of concrete surface; Can also decompose the waste gas that the vehicles such as carbon monoxide, nitrogen peroxide and other oxynitride and factory discharge, thereby this concrete also has the effect purifying air simultaneously.
The advantages such as the nano titanium oxide adulterating in this kind of concrete has that spectrochemical property is stable, catalytic efficiency is high, oxidation capacity is strong, nontoxic, inexpensive, non-secondary pollution.But be 387nm because it absorbs threshold value, lower to the utilization ratio of sun power, because the recombination rate in light induced electron and hole is high, cause quantum yield low in addition, thereby greatly reduce catalytic activity.In addition, because the surfactivity of nanoparticle is higher, be highly susceptible to reuniting, directly add in concrete with powder form, under the mechanical force of stirrer, nano-powder is difficult in concrete system dispersed.
Summary of the invention
Goal of the invention: for above-mentioned the deficiencies in the prior art, the object of the present invention is to provide a kind of for preparing concrete special additive of automatically cleaning and preparation method thereof, adulterate and improve the absorption threshold value of photocatalyst material by Fe, expand the utilization ratio to sun power, by tensio-active agent, nano-powder is dispersed in liquid-phase system uniformly, can makes nano-powder be distributed to uniformly in concrete system.
Technical scheme: for solving the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of automatically cleaning concrete special additive, comprise the component of following weight percent: Fe doped nano titanium dioxide powder 3-10%, tensio-active agent 0.3-0.8%, dispersion agent 89.5-96.5%.
In the present invention, described Fe doped nano titanium dioxide powder is the Fe doped nano titanium dioxide powder that the median size that prepared by auto-combustion method is 60nm.
In the present invention, described tensio-active agent is one or more in citric acid, oleic acid, stearic acid.It act as the surface of clad nano particle, reduces the surface energy of nanoparticle, makes it stable existence in dispersion system.
In the present invention, described dispersion agent is any of methyl alcohol, ethanol and Virahol.
The preparation method of above-mentioned automatically cleaning concrete special additive, the method comprises the steps:
(1) auto-combustion method is prepared the Fe doped nano titanium dioxide powder that median size is 60nm;
(2) Fe doped nano titanium dioxide powder is placed in to dispersion agent, ultrasonic dispersion adds tensio-active agent after being uniformly dispersed, and obtains automatically cleaning concrete special additive.
As the further improvement of preparation method in the present invention, the concrete operation step of step (1) is as follows:
11) prepare Titanium Nitrate solution: it is in 40% hydrofluoric acid that titanium dioxide is dissolved in to mass concentration, obtain titanium tetrafluoride solution, be that 25% strong aqua generates titanium hydroxide precipitation to adding mass concentration in solution, with deionized water wash repeatedly afterwards with deionized water wash during repeatedly to the pH=7 of filtrate, be in 65% concentrated nitric acid by being precipitated and dissolved in mass concentration, obtain Titanium Nitrate solution;
12) iron nitrate that is 1:25 by mass ratio and Titanium Nitrate mixed dissolution, then in the Titanium Nitrate solution obtaining in step 11), add a certain amount of citric acid and ammonium nitrate, by ammoniacal liquor adjusting pH value to 6, in 80 ℃ of water-baths, constantly stir until form gel, then dry 12 hours formation xerogel in 80 ℃ of baking ovens; The mole number of citric acid equates with the total mole number of metal ion, 1/4 amount that the consumption of ammonium nitrate is citric acid, and wherein metal ion is iron ion and titanium ion contained in Fe doped nano titanium dioxide powder.
13) xerogel is placed in to crucible, on electric furnace, adds thermal initiation auto-combustion, form dendritic fluffy product, after product is ground, obtain the Fe doped nano titanium dioxide powder of 60nm.
Preferably, described Titanium Nitrate is to process by hydrofluoric acid, strong aqua, concentrated nitric acid the solution that titanium dioxide obtains, and Titanium Nitrate is the precursor that nano titanium oxide is prepared in auto-combustion.
Preferably, described iron nitrate is analytically pure chemical reagent.Iron nitrate is prepared Fe doped nano titanium dioxide for auto-combustion provides dopant ion Fe
3+.
Preferably, described citric acid is analytically pure chemical reagent, and citric acid is iron ion and titanium ion homodisperse sequestrant in gel, and provides auto-combustion needed fuel.
Preferably, described ammonium nitrate and ammoniacal liquor are analytically pure chemical reagent, its again acting as in system the needed oxygenant of auto-combustion and regulation system pH value are provided.
Beneficial effect: compared with prior art, advantage of the present invention is: by sequestering action and the auto-combustion reaction of citric acid, by dopant ion Fe
3+be solid-solubilized in uniformly Fe in titanium dioxide lattice
3+doping effectively promoted light induced electron to separate with hole, suppress that it is compound, improve photocatalytic activity.And can bring up to 490nm left and right by absorbing threshold value, can greatly improve the utilising efficiency to sun power.By the synergy of tensio-active agent and dispersion agent, make the nanoanalysis dispersion system of stable existence, and can make the finely dispersed automatically cleaning concrete of nano-powder.
Embodiment
Below by specific embodiment, the present invention is further described; it should be pointed out that for the person of ordinary skill of the art, under the premise without departing from the principles of the invention; can also make some modification and improvement, these also should be considered as belonging to protection scope of the present invention.
Embodiment 1: a kind of automatically cleaning concrete special additive, comprises the component of following weight percent: Fe doped nano titanium dioxide powder 3%, tensio-active agent 0.5%, dispersion agent 96.5%, wherein, tensio-active agent is citric acid; Dispersion agent is methyl alcohol.
The preparation method of above-mentioned automatically cleaning concrete special additive is as follows:
The first step, preparation Fe doped nano titanium dioxide powder, is specially:
First, prepare Titanium Nitrate solution: it is in 40% hydrofluoric acid that analytically pure titanium dioxide is dissolved in to analytically pure mass concentration, obtain titanium tetrafluoride solution, be that 25% strong aqua generates titanium hydroxide precipitation to adding analytically pure mass concentration in titanium tetrafluoride solution again, with deionized water wash repeatedly afterwards with deionized water wash during repeatedly to the pH=7 of filtrate, be in 65% concentrated nitric acid by being precipitated and dissolved in analytically pure mass concentration, obtain Titanium Nitrate solution;
Secondly, the iron nitrate that is 1:25 by mass ratio and Titanium Nitrate mixed dissolution, then in solution, add a certain amount of analytically pure citric acid and analytically pure ammonium nitrate, by ammoniacal liquor adjusting pH value to 6, in 80 ℃ of water-baths, constantly stir until form gel, then dry 12 hours formation xerogel in 80 ℃ of baking ovens; The mole number of citric acid equates with the total mole number of metal ion, 1/4 amount that the consumption of ammonium nitrate is citric acid, and wherein metal ion is iron ion and titanium ion contained in Fe doped nano titanium dioxide powder.
Finally, xerogel is placed in to crucible, on electric furnace, adds thermal initiation auto-combustion, form dendritic fluffy product, after product is ground, obtain the Fe doped nano titanium dioxide powder of 60nm.
Second step, it is 96.5.5% methyl alcohol that the Fe doped nano titanium dioxide powder of 60nm is placed in to mass percent, ultrasonic dispersion, after being uniformly dispersed, adding mass percent is 0.5% citric acid, obtains automatically cleaning concrete special additive.
Embodiment 2: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 4%, tensio-active agent 0.6%, dispersion agent 95.4%, wherein, tensio-active agent is stearic acid; Dispersion agent is methyl alcohol.
Embodiment 3: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 3.5%, tensio-active agent 0.5%, dispersion agent 96%, wherein, tensio-active agent is citric acid; Dispersion agent is methyl alcohol.
By the prepared automatically cleaning concrete special additive of embodiment 1 to 3, measure it and absorb the stability of threshold value and dispersion system and the automatically cleaning concrete that the prepares effect (concrete test block preparing is put into the glucose solution that 30 ℃ of concentration are 5%, test under illumination condition) of keeping a public place clean.The concrete experiments of each embodiment, in same raw materials, technical indicator (with normal concrete and the titanium doped concrete comparison of nanometer titanium dioxide) as shown in the table in the situation of identical proportioning:
| Embodiment | 1 | 2 | 3 | Nano titanium oxide | Normal concrete |
| Absorb threshold value (nm) | 495 | 495 | 495 | 387 | / |
| Stability of dispersions | 7d precipitates completely | 7d precipitates completely | 6d precipitates completely | 12h precipitates completely | / |
| Redispersion performance | Well | Well | Well | Well | / |
| The effect of keeping a public place clean | Do not grow microorganism, cleaning | Do not grow microorganism, cleaning | Do not grow microorganism, cleaning | Do not grow microorganism, cleaning | 2d surface grows mould |
As can be seen from the table, use after this special additive, concrete oneself keeps a public place clean functional.And for nano silica powder, the absorption threshold value of the stability of dispersed system and nano-powder has significantly to be improved.
Embodiment 4: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 3%, stearic acid 0.2%, oleic acid 0.3%, ethanol 96.5%.
Embodiment 5: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 10%, stearic acid 0.5%, Virahol 89.5%.
Embodiment 6: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 6%, oleic acid 0.8%, ethanol 93.2%.
Embodiment 7: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 6%, citric acid 0.2%, oleic acid 0.5%, stearic acid 0.1%, ethanol 93.2%.
Embodiment 8: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 10%, citric acid 0.2%, oleic acid 0.3%, ethanol 89.5%.
Embodiment 9: substantially the same manner as Example 1, difference is the component of automatically cleaning concrete special additive, is specially: Fe doped nano titanium dioxide powder 3.5%, stearic acid 0.2%, citric acid 0.6%, alcohol 95 .7%.
Claims (5)
1. an automatically cleaning concrete special additive, it is characterized in that, comprise the component of following weight percent: Fe doped nano titanium dioxide powder 3-10%, tensio-active agent 0.3-0.8%, dispersion agent 89.5-96.5%, described Fe doped nano titanium dioxide powder is the Fe doped nano titanium dioxide powder that the median size that prepared by auto-combustion method is 60nm; Described tensio-active agent is one or more in citric acid, oleic acid, stearic acid; Described dispersion agent is any of methyl alcohol, ethanol and Virahol.
2. the preparation method of automatically cleaning concrete special additive according to claim 1, is characterized in that, the method comprises the steps:
(1) auto-combustion method is prepared the Fe doped nano titanium dioxide powder that median size is 60nm; The concrete operation step of step (1) is as follows:
11) prepare Titanium Nitrate solution: it is in 40% hydrofluoric acid that titanium dioxide is dissolved in to mass concentration, obtain titanium tetrafluoride solution, be that 25% strong aqua generates titanium hydroxide precipitation to adding mass concentration in solution, be in 65% concentrated nitric acid by being precipitated and dissolved in mass concentration with deionized water wash during repeatedly to the pH=7 of filtrate, obtain Titanium Nitrate solution;
12) iron nitrate that is 1:25 by mass ratio and Titanium Nitrate mixed dissolution, then in solution, add a certain amount of citric acid and ammonium nitrate, by ammoniacal liquor adjusting pH value to 6, in 80 ℃ of water-baths, constantly stir until form gel, then dry 12 hours formation xerogel in 80 ℃ of baking ovens;
13) xerogel is placed in to crucible, on electric furnace, adds thermal initiation auto-combustion, form dendritic fluffy product, after product is ground, obtain the Fe doped nano titanium dioxide powder of 60nm;
(2) Fe doped nano titanium dioxide powder is placed in to dispersion agent, ultrasonic dispersion adds tensio-active agent after being uniformly dispersed, and obtains automatically cleaning concrete special additive.
3. the preparation method of automatically cleaning concrete special additive according to claim 2, is characterized in that, described titanium dioxide is analytically pure chemical reagent.
4. the preparation method of automatically cleaning concrete special additive according to claim 2, is characterized in that: described iron nitrate is analytically pure chemical reagent.
5. the preparation method of automatically cleaning concrete special additive according to claim 2, is characterized in that: described citric acid is analytically pure chemical reagent.
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| CN104744003A (en) * | 2015-03-31 | 2015-07-01 | 徐州中联混凝土有限公司 | Ecological decoration material with functions of purifying air and inhibiting bacteria and sizing agent used by same |
| CN107176820B (en) * | 2017-06-22 | 2019-08-06 | 盐城工学院 | A kind of concrete of durability concrete photocatalysis slurry and removable NOx |
Citations (3)
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| CN101704641A (en) * | 2009-11-23 | 2010-05-12 | 浙江大学 | Preparation method of nano-photocatalytic admixture for cement-based material |
| CN102167535A (en) * | 2010-12-27 | 2011-08-31 | 南京倍立达实业有限公司 | Preparation method and application of nano glass fiber reinforced concrete material |
| CN102219555A (en) * | 2011-04-02 | 2011-10-19 | 中南大学 | Multifunctional concrete structure endurance protective agent, preparation and application method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB0916329D0 (en) * | 2009-09-17 | 2009-10-28 | Tioxide Europe Ltd | Stable nano titania sols and a process for their production |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704641A (en) * | 2009-11-23 | 2010-05-12 | 浙江大学 | Preparation method of nano-photocatalytic admixture for cement-based material |
| CN102167535A (en) * | 2010-12-27 | 2011-08-31 | 南京倍立达实业有限公司 | Preparation method and application of nano glass fiber reinforced concrete material |
| CN102219555A (en) * | 2011-04-02 | 2011-10-19 | 中南大学 | Multifunctional concrete structure endurance protective agent, preparation and application method thereof |
Non-Patent Citations (1)
| Title |
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| 王志坚等.Fe掺杂纳米二氧化钛的光催化活性研究.《长春理工大学学报（自然科学版）》.2010,第33卷(第4期), * |
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