CN100577896C - Potassium hexatitanate whisker and its preparation process - Google Patents
Potassium hexatitanate whisker and its preparation process Download PDFInfo
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- CN100577896C CN100577896C CN200610022304A CN200610022304A CN100577896C CN 100577896 C CN100577896 C CN 100577896C CN 200610022304 A CN200610022304 A CN 200610022304A CN 200610022304 A CN200610022304 A CN 200610022304A CN 100577896 C CN100577896 C CN 100577896C
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Abstract
The present invention relates to potassium hexatitanate whisker and its hydrothermal preparation process, and belongs to the field of material technology. The potassium hexatitanate (K2Ti6O13) whisker has diameter of 200-500 nm and length of 20000-30000 nm. It is prepared with titanium compound and potassium compound with the corresponding K2O/TiO2 molar ratio of 2-20, and through the technological steps of reaction, solid-liquid separation, washing, ultrasonic dispersion, drying, etc. The preparation process of the present invention has mild reaction condition, great operation flexibility, simple course and easy control, and the synthesized potassium hexatitanate whisker has high dispersion, homogeneous diameter, great length/diameter ratio and whisker yield over 83 %.
Description
Technical field
The present invention relates to a kind of potassium titanate crystal whisker and preparation method thereof, particularly relate to the method for a kind of crystal whisker of hexa potassium titanate and Hydrothermal Preparation crystal whisker of hexa potassium titanate thereof, belong to the material field.
Background technology
Potassium titanate crystal whisker is the very excellent composite fibre materials of gang's performance, and its composition is used K usually
2OnTiO
2(n=1,2,4,6,8) expression.Wherein, six potassium titanate (K
2O6TiO
2) be chain tunnel structure, chemical property is very stable, have good mechanics and physicals, excellent wear-and corrosion-resistant and heat-resisting heat-proof quality, therefore, crystal whisker of hexa potassium titanate is widely used in the materials such as automobile brake sheet, heat insulation and various compound enhancings.
The preparation method of crystal whisker of hexa potassium titanate mainly contains sintering process, flux method, scorification and hydrothermal method etc.
The sintering process synthesis of potassium titanate crystal whisker generally adopts the multistep processes sintering process, promptly adopts 500～800 ℃ earlier synthetic two potassium titanates of high temperature and potassium tetratitanate, and potassium is taken off in pickling, and then obtains six potassium titanates through 800～1200 ℃ secondary high-temperature heat treatment side.This method complex process, the energy consumption height, solids is non-uniform temperature when sintering, and whisker is of poor quality, and the leaching amount of potassium ion was difficult when potassium was taken off in pickling controls, and influences the purity of product.Also once sintering get final product crystal whisker of hexa potassium titanate, and potassium ion leaching amount is difficult to shortcomings such as control when having overcome pickling and taking off potassium, as application number is 00112275.4, denomination of invention is that the preparation method and the application number of crystal whisker of hexa potassium titanate is 03116985.6, and denomination of invention is the Chinese patent application of the manufacture method of crystal whisker of hexa potassium titanate, all be to make crystal whisker of hexa potassium titanate by a step sintering, but diameter of whiskers is big, and length-to-diameter ratio is little, also needs to separate in solution to knit.Particularly application number is 00112275.4 patent application, and whisker is separated in inorganic acid solution and knitted, thereby will give off a large amount of spent acid solutions.The crystal whisker of hexa potassium titanate though flux method can be grown under 900～1000 ℃ of lower temperature, yield is higher, and pattern is also better, fusing assistant price height, the separation costs height, thereby production cost is high naturally.The temperature of reaction of scorification is up to 1200～1500 ℃, and yield is low.Above sintering process prepares six potassium titanates and all has such-and-such defective.
Hydrothermal method synthetic potassium titanate crystal whisker crystalline fibers is long, quality good, and technology is simple, and reaction conditions is easy to control.The prior art that adopts the Hydrothermal Preparation potassium titanate to report has at present:
1, titanium dioxide and the potassium hydroxide that is about 4nm with the powder mean diameter is raw material, has synthesized eight potassium titanate (K through hydro-thermal reaction 48h
2Ti
8O
17).This method exists the reaction times longer, the defective that used raw material is not easy to prepare [Inorganic Chemistry 41 (2002) 4996-4998].2, be raw material with metal titanium and potassium hydroxide, go out K with Hydrothermal Preparation
4Ti
3O
8, KTiO
2(OH) and K
2Ti
2O
5NH
2O.The potassium titanate pattern of this method preparation is relatively poor, also needs further to carry out roasting [Journal of Materials Science 35 (2000) 3307-3311] with high temperature for obtaining six potassium titanates.3, be raw material with hydrated titanium dioxide and potassium hydroxide, prepare crystal whisker of hexa potassium titanate with the hydro-thermal evaporation, hydrothermal temperature is 390 ℃, and pressure is 15～20MPa, and soaking time is 6～50h[Journal of CrystalGrowth, 46 (1979) 331-338].This method adopts Metal Zn as dewatering agent, carries out under High Temperature High Pressure, and reactor also needs to make lining with platinum, and this is not only to the requirement harshness of reactor, and has increased cost.4, and for example Chinese patent application number is 03129114.7, and denomination of invention is the patent application of a kind of trigonal crystal structure potassium titanate and preparation method thereof, is raw material with titanium dioxide and potassium hydroxide, and hydro-thermal has been synthesized a kind of potassium titanate KTiO of trigonal crystal structure
2(OH).Hydrothermal reaction condition is 100～200 ℃, soaking time 2～48h.The product of this hydrothermal method is not six potassium titanates.5, be raw material with titanium tetraisopropylate and potassium hydroxide, go out crystal whisker of hexa potassium titanate with Hydrothermal Preparation, hydrothermal temperature is 350～450 ℃, and soaking time is 2～25h.This method pressure is up to 14～45MPa, and is dangerous big.[Chemical?Material13(2001)842-847]
Summary of the invention
Purpose of the present invention at existing defective in the prior art of preparation crystal whisker of hexa potassium titanate, provides the crystal whisker of hexa potassium titanate that a kind of diameter is little and uniform, length-to-diameter ratio is big, quality good, pattern is good just; And provide a kind of can be under relatively mild hydrothermal reaction condition, and technology is simple, is easy to control, the whisker productive rate is up to 83% or more, the method for direct synthesis of potassium titanate crystal whisker.
The objective of the invention is to realize by the technical scheme that following measure constitutes.
Crystal whisker of hexa potassium titanate (K provided by the invention
2Ti
6O
13) diameter between 200～500nm, be about between 20000～30000nm, and diameter of whiskers is even, quality is good, pattern is good.
The method of Hydrothermal Preparation crystal whisker of hexa potassium titanate provided by the invention is a raw material with titanium compound and potassium compound, it is characterized in that, comprises following processing step:
(1) described raw material is amounted to into TiO
2With K
2O presses K
2O: TiO
2=2: 1～20: 1 molar ratio ingredient;
(2) above-mentioned batching is added in the reaction vessel, add distilled water again, the weight percent concentration of regulating potassium compound is 10%～53%, then to the reaction vessel heat temperature raising, stirs hydro-thermal reaction down;
(3) above-mentioned reaction product is handled through solid-liquid separation, washing, ultra-sonic dispersion;
(4) will be through the product drying of above-mentioned processing, it is big promptly to make length-to-diameter ratio, and diameter of whiskers is even, and quality is good, six potassium titanates that pattern is good, the whisker productive rate can reach more than 83%.
In the technique scheme, described is temperature rise rate heating with 3 ℃/min to reactor heating, and its Heating temperature is 200～320 ℃, and soaking time is 2～24h.
In the technique scheme, described titanium compound is a rutile titanium dioxide, or anatase titanium dioxide.
In the technique scheme, described drying temperature 80-120 ℃, time of drying 2-4h.
Its diameter of the crystal whisker of hexa potassium titanate that Hydrothermal Preparation of the present invention goes out is about between 20000～30000um between 200～500nm, and length-to-diameter ratio is big, and the whisker productive rate is more than 83%.
The useful technique effect that the present invention compared with prior art has:
1, crystal whisker of hexa potassium titanate length-to-diameter ratio of the present invention is big, and diameter of whiskers is even, and quality is good,, pattern is intact.
2, method reaction conditions gentleness of the present invention, turndown ratio is big; Technology is simple, is easy to control, and does not have waste liquid and discharge, and helps large-scale industrial production.
3, the product that makes of method of the present invention can reach whisker dispersive purpose behind simple washing and ultra-sonic dispersion; And the better crystallinity degree of whisker.
4, the crystal whisker of hexa potassium titanate that makes of method of the present invention, not only diameter is even, quality is good, and pattern is intact, and productive rate reaches more than 83%.
5, the mother liquor reusable edible after the method solid-liquid separation of the present invention economizes in raw materials, and reduces cost.
Description of drawings
Fig. 1 analyzes six potassium titanate (K of gained the present invention preparation for adopting X ' Pert Pro MPD X-ray diffraction spectrograph
2Ti
6O
13) XRD figure spectrum;
Fig. 2, Fig. 3, Fig. 4 and Fig. 5 are the SEM photo figure of the crystal whisker of hexa potassium titanate that the present invention makes.
As can be seen from Figure 1, it and K
2Ti
6O
13Standard spectrogram (PDF card 74-0275) coincide better, diffraction peak is more bright and sharp, shows the better crystallinity degree of synthetic crystal whisker of hexa potassium titanate.
Embodiment
Also in conjunction with the accompanying drawings the present invention is further described specifically below by specific embodiment, but it only is used to illustrate embodiments more of the present invention, and should not be construed as qualification protection domain of the present invention.
Embodiment 1
1. preparation of raw material: with industrial anatase titanium dioxide (TiO
2), analytical pure potassium hydroxide (KOH) is raw material, wherein K
2O: TiO
2=2: 1 mol ratio, 2. charging: the material that will prepare mixes, and in the reactor that the band of packing into stirs, adds distilled water, and the weight percent concentration of regulating KOH is 10%, tightens sealed reactor then; 3. reaction: reactor is heated, and with the temperature rise rate of 3 ℃/min reactor is heated up, make temperature be raised to 320 ℃, stir simultaneously, rotating speed is 100r/min, at 320 ℃ of insulation 2h; 4. product is handled: after filtration after the solid-liquid separation, be washed with distilled water to pH ≈ 7.2 through product that above-mentioned reaction obtains, ultra-sonic dispersion 5min again, dry 4h in 80 ℃ baking oven, get final product crystal whisker of hexa potassium titanate.
The above-mentioned K that makes
2Ti
6O
13The about 200nm of the diameter of whisker is about 20um, and length-to-diameter ratio is 100, and productive rate reaches 83%, and SEM photo figure sees Fig. 2, and its whisker quality is even, and pattern is intact.
1. preparation of raw material: with industrial rutile TiO
2, analytical pure KOH is raw material, wherein K
2O: TiO
2=5: 1 mol ratio, 2. charging: the material that will prepare mixes, and in the reactor that the band of packing into stirs, adds distilled water, and the weight percent concentration of regulating KOH is 53%, tightens sealed reactor; 3. reaction: to reactor heating, and with the temperature rise rate of 3 ℃/min to the reactor heat temperature raising, make temperature be raised to 250 ℃, stir simultaneously, rotating speed is 300r/min, at 250 ℃ of insulation 5h; 4. product is handled: after filtration after the solid-liquid separation, be washed with distilled water to pH ≈ 7.3 through product that above-mentioned reaction obtains, use ultra-sonic dispersion 15min, dry 2h in 120 ℃ baking oven promptly gets crystal whisker of hexa potassium titanate.
The above-mentioned K that makes
2Ti
6O
13The about 200nm of the diameter of whisker is about 20～30um, and length-to-diameter ratio is 100, and productive rate reaches 87%, and SEM photo figure sees Fig. 3, and its whisker quality is even, and pattern is intact.
Embodiment 3
1. preparation of raw material: with industrial anatase titanium dioxide TiO
2, analytical pure KOH is raw material, wherein K
2O: TiO
2=7: 1 mol ratio, 2. charging: the material that will prepare mixes, and in the reactor that the band of packing into stirs, adds distilled water, and the weight percent concentration of regulating KOH is 13%; Tighten sealed reactor, 3. reaction: to reactor heating, and with the temperature rise rate of 3 ℃/min to the reactor heat temperature raising, making temperature is 300 ℃, opens stirring simultaneously, this moment, rotating speed was 350r/min, at 300 ℃ of insulation 6h; 4. product is handled: after filtration after the solid-liquid separation, be washed with distilled water to pH ≈ 7.5 through product that above-mentioned reaction obtains, use ultra-sonic dispersion 10min, dry 3h in 100 ℃ baking oven promptly gets crystal whisker of hexa potassium titanate.
The above-mentioned K that makes
2Ti
6O
13The about 500nm of the diameter of whisker is about 20um, and length-to-diameter ratio is 40, and productive rate reaches 94%, and SEM photo figure sees Fig. 4, and its whisker quality is even, and pattern is intact.
Embodiment 4
1. preparation of raw material: with industrial anatase titanium dioxide TiO
2Be raw material, the pure KOH to K of supplement Analysis in the mother liquor that has separated crystal whisker of hexa potassium titanate
2O: TiO
2=20: 1 mol ratio makes the weight percent concentration of KOH be about 10%; 2. charging: will be equipped with good material and mix, and in the reactor that the band of packing into stirs, tighten sealed reactor; 3. reaction: to reactor heating, and with the temperature rise rate of 3 ℃/min to the reactor heat temperature raising, making temperature is 200 ℃, opens stirring simultaneously, this moment, rotating speed was 500r/min, at 200 ℃ of insulation 24h; 4. product is handled: after filtration after the solid-liquid separation, be washed with distilled water to pH ≈ 7.0 through product that above-mentioned reaction obtains, use ultra-sonic dispersion 5min, 100 ℃ times dry 4h promptly get crystal whisker of hexa potassium titanate in baking oven.
The above-mentioned K that makes
2Ti
6O
13About 100～the 200nm of the diameter of whisker is about 30um, and length-to-diameter ratio is big, and productive rate reaches 85%, and SEM photo figure sees Fig. 5, and its whisker quality is even, and pattern is intact.
Claims (3)
1. the method for a Hydrothermal Preparation crystal whisker of hexa potassium titanate is a raw material with titanium compound and potassium compound, it is characterized in that, described titanium compound is a rutile titanium dioxide, or anatase titanium dioxide, comprises following processing step:
(1) described raw material is amounted to into K
2O and TiO
2, press K
2O: TiO
2=2: 1～20: 1 molar ratio ingredient;
(2) above-mentioned batching is added in the reaction vessel, add distilled water again, the weight percent concentration of regulating potassium compound is 10%～53%, then to the reaction vessel heat temperature raising, stirs hydro-thermal reaction down;
(3) above-mentioned reaction product is handled through solid-liquid separation, washing, ultra-sonic dispersion;
(4) will be through the product drying of above-mentioned processing, it is big promptly to make length-to-diameter ratio, and diameter of whiskers is even, and quality is good, six potassium titanates that pattern is good, the whisker productive rate reaches more than 83%.
2. the method for Hydrothermal Preparation crystal whisker of hexa potassium titanate according to claim 1 is characterized in that, heating is the temperature rise rate heating with 3 ℃/min to reactor, and Heating temperature is 200-320 ℃, and soaking time is 2-24h.
3. the preparation method of crystal whisker of hexa potassium titanate according to claim 1 is characterized in that, described drying temperature is 80～120 ℃, and be 2～4h time of drying.
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|---|---|---|---|---|
| CN112030221A (en) * | 2020-08-06 | 2020-12-04 | 西安近代化学研究所 | High length-diameter ratio K2Ti6O13Preparation method of whisker |
Families Citing this family (9)
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| CN102390864B (en) * | 2011-08-18 | 2013-10-23 | 中南大学 | Preparation method of flaky potassium hexatitanate |
| CN102691105A (en) * | 2012-06-12 | 2012-09-26 | 浙江大学 | Method for preparing barium titanate monocrystal nano particles of six-pin structural perovskite |
| CN103911664B (en) * | 2014-04-30 | 2016-06-29 | 潍坊中晶新材料科技有限公司 | A kind of synthetic method of lenticular potassium hexatitanate |
| CN104005080A (en) * | 2014-05-30 | 2014-08-27 | 中国科学院过程工程研究所 | Preparation method of titanium containing crystal whisker |
| CN105734670B (en) * | 2016-04-13 | 2017-11-14 | 唐山晶须复合材料制造有限公司 | A kind of synthetic method of potassium hexatitanate cylindrulite |
| CN106637408A (en) * | 2016-12-23 | 2017-05-10 | 张家港大塚化学有限公司 | Preparation method of acicular short fiber composite potassium hexatitanate crystal whisker |
| CN108315822B (en) * | 2018-02-10 | 2020-12-18 | 罗旭 | Method for preparing potassium hexatitanate whisker by epoxy-driven one-step method and photocatalytic application thereof |
| CN108166051A (en) * | 2018-03-08 | 2018-06-15 | 合肥工业大学 | A kind of morphology controllable potassium hexatitanate powder crystal material and its low energy consumption preparation method |
| CN110183240B (en) * | 2019-04-04 | 2021-11-02 | 武汉理工大学 | Preparation method of skutterudite with high mechanical strength |
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Non-Patent Citations (2)
| Title |
|---|
| 高长径比钛酸钾晶须的合成及其结构研究. 孟庆浩等.化学通报，第7期. 2002 |
| 高长径比钛酸钾晶须的合成及其结构研究. 孟庆浩等.化学通报，第7期. 2002 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112030221A (en) * | 2020-08-06 | 2020-12-04 | 西安近代化学研究所 | High length-diameter ratio K2Ti6O13Preparation method of whisker |
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