CN1418820A - Nano Titanium dioxide, prepn. process and use thereof - Google Patents
Nano Titanium dioxide, prepn. process and use thereof Download PDFInfo
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- CN1418820A CN1418820A CN 02147872 CN02147872A CN1418820A CN 1418820 A CN1418820 A CN 1418820A CN 02147872 CN02147872 CN 02147872 CN 02147872 A CN02147872 A CN 02147872A CN 1418820 A CN1418820 A CN 1418820A
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Abstract
The present invention relates to a chrysanthemum-like nano titanium dioxide, its preparation method and application. It uses titanyl sulfate as main raw material, after alkali precipitation and washing treatment the titanyl sulfate can be converted into titanyl nitrate, after the additive is added, the titanyl nitriate is undergon the processes of hydrolysis at normal pressure, separation, washing, drying and proper heat treatment so as to can obtain the invented chrysanthemum-like nano titanium dioxide which can be used for preparing compound stealth material.
Description
Technical field the present invention relates to a kind of nano titanium oxide and its production and use, belongs to field of nanometer material technology.
Background technology in recent years, the nano material development is very fast, because nanoparticle has characteristics such as surface effects, quantum effect, small-size effect, macro quanta tunnel effect, thereby shows the notable feature that is different from general macroscopic material at aspects such as optics, mechanics, electricity, magnetics.
Titanium dioxide is nontoxic to human body, acid and alkali-resistance, corrosion-resistant, UV-light there is certain absorption, certain wave band infrared had reflection preferably, its specific refractory power height, dielectric properties are good, and chrysanthemum shape nano titanium oxide is because its special profile, makes it more unusual to ultraviolet and infrared absorption and scattering, the radiowave of certain frequency also had preferably absorb.
Be raw material liquid phase water solution at present with the titanium tetrachloride, or the method for hydrothermal method manufacturing whisker have report.These methods of making whisker can produce acicular whisker, and these needle-like whiskers are independent separately, can not be combined into definite shape, so can't produce synergistic effect.
Summary of the invention problem to be solved by this invention provides nano titanium oxide of a kind of specified shape and its production and use, and prepared nano titanium oxide is except that having the character of common form nano titanium oxide to light, also to 2～9GH
2Radiowave has stronger dielectric absorption.
Technical scheme provided by the invention is: a kind of nano titanium oxide, and its particle is the chrysanthemum shape, and every petal slightly is that 1～10 nanometer, length are 60～400 nanometers.
The present invention also provides the preparation method of above-mentioned nano titanium oxide, with the titanyl sulfate is that raw material mixes stirring with mineral alkali, get the titanic Acid precipitation, the gained throw out is after washing, make titanyl nitrate with nitric acid dissolve, in titanyl nitrate solution, add additive then and make the crystalline form initiator, adopt ordinary-pressure hydrolysis, separation, drying, thermal treatment promptly to get chrysanthemum shape nano titanium oxide again.
The concentration of the above-mentioned titanyl nitrate aqueous solution is controlled at 0.5～4 mol scope; The additive add-on of making the crystalline form initiator is: 0.5-17%, mass percent; The ordinary-pressure hydrolysis temperature is that 70～112 ℃ of times are 0.7～7 hour; Heat drying, temperature are 100～300 ℃, and the time is 1～12 hour; Thermal treatment temp is 300～700 ℃, and the time is 1～8 hour.
Above-mentioned additive is quadrol, sodium phthalate, sodium salicylate, sulfosalicylic acid sodium salt, oxamide, lemon acid amide, mandelic acid sodium, sodium malonate or vanillic acid sodium etc.
Gained nano titanium oxide of the present invention is a chrysanthemum shape nano titanium oxide, and chrysanthemum shape nano titanium oxide refers to that its profile is the chrysanthemum shape, and every petal is slightly in 1～10nm, and length can 60 nanometers to 400 nanometers.Both had the character of nano material just because of it, the character that has submicron material again, play weather-proof and effect so it not only can be used in the third generation special effects paint, also can be used to make various matrix materials: for example that it and plastics are compound, both can improve the uvioresistant character of plastics, can improve physical strength, toughness, shock resistance and the flame-retarding characteristic of plastics again.Be added to the scope that can widen its alternative metals in the engineering plastics greatly, also can utilize chrysanthemum shape nano titanium oxide to electromagnetic special absorbent properties (to 2～9GH
2Radiowave has stronger dielectric absorption) compound with other material, make novel composite stealthy material (absorbing material).
The outstanding feature that with the titanyl sulfate is main raw material prepares the method for chrysanthemumization shape nano titanium oxide provided by the invention is:
1. this technology is fit to national conditions, and raw material sources are abundant, and are cheap.
2. preparation technology is simple, and processing parameter is controlled easily, product repeatability and high conformity, and production cost is low.
Description of drawings Fig. 1, Fig. 2, Fig. 3 are respectively with the transmission electron microscope sheet of the chrysanthemum shape nano titanium oxide of method preparation provided by the invention, represent 400 nanometers for every centimeter among the figure.
Embodiment nano titanium oxide provided by the invention, its particle is cosmos, and every petal slightly is that 1～10 nanometer, length are 60～400 nanometers.
Above-mentioned chrysanthemumization shape nano titanium oxide prepares as follows: be that raw material mixes stirring with mineral alkali with the titanyl sulfate, get the titanic Acid precipitation, the gained throw out is after washing, make titanyl nitrate with nitric acid dissolve, in titanyl nitrate solution, add additive then and make the crystalline form initiator, adopt ordinary-pressure hydrolysis, separation, drying, thermal treatment promptly to get chrysanthemum shape nano titanium oxide again.
The concrete technological specification of each flow process is commented as follows:
1. mineral alkali is made the precipitation agent of titanyl sulfate, and during precipitation, pH value is controlled between 5～10, when titanyl sulfate mixes with alkali, should adopt the ice-water bath cooling, and the control mixing velocity, temperature is controlled at below 50 ℃, in case precipitation forms hard aggregation, influence is the step dissolving down.Used alkali can be selected sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, ammoniacal liquor etc.
2. precipitation gets positive metatitanic acid after filtration after the washing, and the content of titanium dioxide preferably is controlled at 2～23% (mass percents) in the positive metatitanic acid.
3. the concentration of nitric acid is controlled at 2～23 mol, should add ice-water bath when dissolving positive metatitanic acid, in case temperature surpasses 50 ℃, causes no control hydrolysis.
4. the titanyl nitrate of dissolving back generation is before hydrolysis, and concentration is controlled in 0.5～4 mol scope.Acidity control is in 1～8 volumetric molar concentration.
5. the add-on that adds in the titanyl nitrate solution when additive of Cai Yonging is made the crystalline form initiator is 0.5～17% (mass percent).
Used additive is quadrol, sodium phthalate, sodium salicylate, sulfosalicylic acid sodium salt, lemon acid amide, oxamide, mandelic acid sodium, sodium malonate, vanillic acid sodium etc. preferably.
6. hydrolysis temperature and time: ordinary-pressure hydrolysis is taked in hydrolysis, and hydrolysis temperature is that 70～112 ℃ of times are 0.7～7 hour.
7. product is through separating as separating with plate-and-frame filter press, and unnecessary acid and impurity in the flush away precipitation just obtains moisture titanium dioxide.
8. dry; In order to remove the moisture in the moisture titanium dioxide, can adopt heat drying, temperature is that 100～300 ℃ of times are 1～12 hour.Also available freezing and microwave drying.
9. thermal treatment: dried work in-process under 300～700 ℃ of temperature thermal treatment 1-8 hour again can obtain the chrysanthemumization shape nano titanium oxide of different thicknesses, length.
Below by embodiment, further illustrate outstanding feature of the present invention and marked improvement, only be the present invention is described and never limit the present invention.
Embodiment 1:
Vitriol oil oxygen titanium is added in the entry, make concentration adjustment to 0.45 mol, the NaOH solid is soluble in water, 1.2 mol with concentration adjustment, under ice-water bath, both are slowly mixed, temperature is controlled at below 10 ℃, and PH stopped by 5.2 o'clock, after the filtration, wash precipitation (positive metatitanic acid) with water, the nitric acid that adds concentration and be 5 mol in positive metatitanic acid dissolves it, makes to contain the solution that titanyl nitrate is 0.6 mol, and acidity control is in 3 mol, after adding the sodium salicylate of 0.5% (mass percent) therein, be heated to 6 hours postcooling of 80 ℃ of constant temperature, filter, washing, lyophilize is 48 hours again, again through 400 ℃ of thermal treatments 2 hours.Grain morphology as shown in Figure 1.This material joins in the polyester fiber, and the infrared wave reflection of this trevira 9 μ m reaches 90%.
Embodiment 2:
Vitriol oil oxygen titanium is added in the entry, with concentration furnishing 0.86 mol, the potassium hydroxide solution that with concentration is 2.5 mol again mixes in ice-water bath with it, temperature is controlled at below 30 ℃, stop during PH=7, with sedimentation and filtration, it is 12 mol nitric acid that the washing back adds concentration, and it is dissolved, and is made into to contain the solution that titanyl nitrate is 2.5 mol, acidity control is in 4.4 mol, and add 5.5% Trisodium Citrate post-heating, and 104 ℃ of constant temperature 2 hours, cooled and filtered, with after the filter cake washing in microwave drying after 1 hour, again through 550 ℃ of thermal treatments 3 hours.Grain morphology as shown in Figure 2.This sample is measured it at 2～9GH through microwave network analyzer
2Electrical loss angle tangent is all greater than 0.7 in the wave band.
Embodiment 3
Vitriol oil oxygen titanium is added in the entry, with concentration furnishing 1.5 mol, the ammoniacal liquor that with concentration is 7 mol again mixes in ice-water bath with it, temperature is controlled at below 50 ℃, stop during PH=9, with sedimentation and filtration, after the washing, the salpeter solution that adds concentration and be 19 mol is with resolution of precipitate, be mixed with and contain titanyl nitrate 3.5 mol, acidity control is in 7 mol, becomes and adds 16% sodium oxalate post-heating, 107 ℃ of constant temperature 1 hour, cooled and filtered, to descend dry 1 hour at 300 ℃ after the filter cake washing, and then through 700 ℃ of thermal treatments 2 hours, grain morphology as shown in Figure 3.This sample through microwave network analyzer measure its in 2～9GH2 wave band electrical loss angle tangent all greater than 0.65.
Claims (7)
1. nano titanium oxide, its particle is the chrysanthemum shape, and every petal slightly is that 1～10 nanometer, length are 60～400 nanometers.
2. the preparation method of the described nano titanium oxide of claim 1, with the titanyl sulfate be raw material mix with mineral alkali stir the titanic Acid precipitation, the gained throw out is after washing, make titanyl nitrate with nitric acid dissolve, in titanyl nitrate solution, add additive then and make the crystalline form initiator, adopt ordinary-pressure hydrolysis, separation, drying and thermal treatment promptly to obtain chrysanthemum shape Nano titanium dioxide again.
3. method according to claim 2 is characterized in that: drying means is heat drying, lyophilize or microwave drying.
4. method according to claim 2 is characterized in that: the concentration of the titanyl nitrate aqueous solution is controlled at 0.5～4 mol scope; The additive add-on of making the crystalline form initiator is: 0.5-17%, mass percent; The ordinary-pressure hydrolysis temperature is that 70～112 ℃ of times are 0.7～7 hour; Heat drying, temperature are 100～300 ℃, and the time is 1～12 hour; Thermal treatment temp is 300～700 ℃, and the time is 1～8 hour.
5. according to claim 2 or 3 or 4 described methods, it is characterized in that: pH value was controlled between 5～10 when titanyl sulfate mixed with mineral alkali, lower the temperature with ice-water bath, and control mixing velocity, temperature is controlled at below 50 ℃, and used mineral alkali is sodium hydroxide, potassium hydroxide, yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus or ammoniacal liquor.
6. according to claim 2 or 3 or 4 described methods, it is characterized in that: the additive that uses is quadrol, sodium phthalate, sodium salicylate, sulfosalicylic acid sodium salt, oxamide, lemon acid amide, mandelic acid sodium, sodium malonate or vanillic acid sodium.
7. the described nano titanium oxide of claim 1 is used to prepare composite stealthy material.
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| CNB021478724A CN1180983C (en) | 2002-12-18 | 2002-12-18 | Nano titanium dioxide, prepn. process and use thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653416A (en) * | 2011-03-01 | 2012-09-05 | 同济大学 | Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking |
| CN104466155A (en) * | 2014-12-23 | 2015-03-25 | 北京理工大学 | Method for preparing high-coulombic-efficiency lithium ion battery negative pole material chrysanthemum-shaped nanometer titania |
| CN109364904A (en) * | 2018-12-04 | 2019-02-22 | 大连宜安科技有限公司 | A kind of indoor air pollutants liquid scavenger and preparation method thereof |
-
2002
- 2002-12-18 CN CNB021478724A patent/CN1180983C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653416A (en) * | 2011-03-01 | 2012-09-05 | 同济大学 | Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking |
| CN102653416B (en) * | 2011-03-01 | 2014-01-29 | 同济大学 | Method for preparing titanium dioxide nanosphere by titanocene dichloride cracking |
| CN104466155A (en) * | 2014-12-23 | 2015-03-25 | 北京理工大学 | Method for preparing high-coulombic-efficiency lithium ion battery negative pole material chrysanthemum-shaped nanometer titania |
| CN104466155B (en) * | 2014-12-23 | 2018-01-09 | 北京理工大学 | A kind of preparation method of high coulombic efficiency lithium ion battery negative material chrysanthemum shape nano titanium oxide |
| CN109364904A (en) * | 2018-12-04 | 2019-02-22 | 大连宜安科技有限公司 | A kind of indoor air pollutants liquid scavenger and preparation method thereof |
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| CN1180983C (en) | 2004-12-22 |
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