CN101694009A - Method for auxiliary synthesis of potassium titanate crystal whisker by using high-energy ball mill method - Google Patents
Method for auxiliary synthesis of potassium titanate crystal whisker by using high-energy ball mill method Download PDFInfo
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- CN101694009A CN101694009A CN200910172492A CN200910172492A CN101694009A CN 101694009 A CN101694009 A CN 101694009A CN 200910172492 A CN200910172492 A CN 200910172492A CN 200910172492 A CN200910172492 A CN 200910172492A CN 101694009 A CN101694009 A CN 101694009A
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Abstract
The invention relates to a method for auxiliary synthesis of potassium titanate crystal whisker by using a high-energy ball mill method, belonging to the technical field of inorganic material preparation. The method is characterized by comprising the steps of mixing industrial-grade anatase titanium dioxide and industrial-grade anhydrous potassium carbonate as raw materials according to the theoretical mole ratio of K2O:TiO2=1:6 and processing the materials by the high-energy ball mill method, wherein the weight ratio of ball-milling material is 10:1 to 20:1, the rotating speed of ball-milling is 500 to 700 turns/minute, and the ball-milling time is 10 to 20 hours, taking the processed material out at a temperature of 700-800 DEG C and carrying out heat treatment to obtain the potassium titanate crystal whisker with single component and even dispersion, wherein the length-diameter ratio is 10 to 20. The invention has the characteristics of complete reaction, simple process, low cost, controllable technological parameter and sufficient crystal growth.
Description
Technical field:
The invention belongs to the inorganic materials preparing technical field, relate to a kind of method of high-energy ball milling auxiliary synthesis of potassium titanate crystal whisker.
Background technology:
In various potassium titanate crystal whisker, crystal whisker of hexa potassium titanate is most widely used at present, its unique tunnel structure makes it not only have excellent mechanical property, and has a physical property of a lot of uniquenesses, as higher intensity and Young's modulus, high-wearing feature, good electroconductibility, chemical stability and lower thermal conductivity etc., and its production cost is not high, has obtained in fields such as strongthener, friction materials and lagging materials using widely.
Synthesis preparation method commonly used at present mainly contains sintering process, hydrothermal method, scorification and KDC method etc.Hydrothermal method can obtain pattern quality whisker preferably, but complex process, cost are higher, and has certain danger, and this has also limited its application in large-scale commercial production.In the existing manufacturing technique, as application number is 01134183.1 patent, and its production method comprises: mixing, sintering, quenching, dispersion treatment, separation, washing, drying, high temperature crystallization sintering, secondary dispersion treatment, redrying are handled and step such as screening; Application number is that the step of synthesis of potassium titanate crystal whisker is in 200410054039.8 the patent: press TiO
2: K
2The molar ratio ingredient of O=1.9～2.5 after mixing by mechanical ball milling, places 900～1300 ℃ tunnel furnace to stop and obtained molten mass in 1～2 hour; Then pouring molten mass into the metal blade makes minitype particle; Minitype particle and pure water place reactor, heat 60～98 ℃, add diluted acid, stir to become suspension in 1～4 hour; Solid-liquid suspension is separated into amorphous hydrate and sloughs surface water being lower than under 100 ℃; Place 500～800 ℃ of tunnel furnace, sintering 1～4 hour; Use the pure water washing material; Material is sloughed surface water, and is dry under 200～300 ℃, can obtain the crystal whisker of hexa potassium titanate goods.
The equal more complicated of above-mentioned production technique is implemented comparatively difficulty in industrial mass production.Sintering process technology is simple, and cost is low, has the potentiality of using in large-scale commercial production, but its higher synthesis temperature (optimum synthesising temperature is at 1000～1200 ℃) makes K
2O is a large amount of loss through volatilizationes in reaction process, and this just requires to comprise in the proportioning raw materials excessive K
2O, otherwise along with the K that carries out that reacts
2O content can be more and more lower, can't synthesis of potassium titanate crystal whisker and cross when low when content, and remaining TiO will appear in the product
2Simultaneously because K
2The volatilization of O is serious, makes K in the reaction environment
2Dynamic change is constantly taking place in O content, therefore is difficult to accurate control K
2The content of O, this remarkably influenced steadily evenly carrying out of reaction process, and make and technological process control difficulty cause the reduction of whisker productive rate and quality.Present synthesis technique does not all propose rational solution for this problem, and this also becomes the major obstacle of crystal whisker of hexa potassium titanate industrial mass production.
Compare with the standard machinery ball milling, high-energy ball milling has very high crushing efficiency, and externally under the effect of mechanical force, ball grinder, mill ball and feed particles are fully collided, particle has obtained extruding repeatedly, distortion, fracture and cold welding in mechanical milling process, make the defective of particle surface significantly increase, particle size obtains refinement gradually, the chemical bond of particle surface is interrupted simultaneously, produce a large amount of unsaturated link(age), unbound electron and ion, can increase in the crystal, the atom activity is improved, and has promoted the homogenizing of size distribution greatly.
Summary of the invention:
At the synthesis temperature height, the K that exist in the present synthesis technique
2The O volatilization is serious, technology controlling and process is difficult and the problem of unstable product quality, and the present invention proposes a kind of method of high-energy ball milling auxiliary synthesis of potassium titanate crystal whisker, to overcome the existing existing defective of synthesis technique.
Preparation method provided by the invention does raw material with technical grade anatase titanium dioxide and technical grade Anhydrous potassium carbonate, raw material is carried out high-energy ball milling under certain condition and handles, and obtains even, the monophasic crystal whisker of hexa potassium titanate of component through thermal treatment then.
The present invention adopts high-energy ball milling that raw material is handled, and synthesis temperature can be reduced to 700～800 ℃, in the process of in this temperature range, heat-treating, and the K in the raw material
2O is volatilization not, and fully reaction generates crystal whisker of hexa potassium titanate, in the time of so just can realizing preparing burden directly according to six potassium titanate (K
2Ti
6O
13) theoretical molar of whisker compares weighing, avoided the unsteady bigger problem of other technology proportioning raw materials in building-up process, help the accurate control of reaction process and steadily carry out uniformly, this method has the advantages that production cost is low, technology is simple, processing parameter is easily controlled, can produce in batches simultaneously.
The preparation method of crystal whisker of hexa potassium titanate provided by the invention comprises following content:
1, the selection of raw material: select for use cheap technical grade Anhydrous potassium carbonate and technical grade anatase titanium dioxide to do raw material, raw material is pressed K
2O: TiO
2=1: 6 theoretical molar is than batching.
2, the selection of ball milling method: high energy ball mill, adopt the mode of dry grinding.
3, the selection of mill ball: the selection Stainless Steel Ball is a mill ball, and the mill ball diameter is between 1～3 centimetre, and ball material weight ratio is 10: 1～20: 1.
4, the selection of ball milling speed: choose 500～700 rev/mins, high energy ball mill has higher grinding efficiency in this scope, helps mixing and further broken refinement of raw material.
5, the selection of ball milling time: the ball milling time is 10～20 hours, and feed particles can evenly also refinement of thorough mixing.
6, thermal treatment: 700～800 ℃ of thermal treatments 1 hour.
Adopt above technical scheme, outstanding feature of the present invention is:
1, the mode of the high-energy ball milling of the present invention's employing is mixed raw material and is broken, has improved the homogeneity of batch mixing, has promoted the refinement and the activation of feed particles simultaneously, helps the reduction of synthesis temperature.
2, the crystal whisker of hexa potassium titanate of gained of the present invention can synthesize 700～800 ℃ of thermal treatments in 1 hour, greatly reduced thermal treatment temp compared with the prior art, raw material K
2Therefore O does not have loss through volatilization in reaction process, can directly prepare burden by theoretical proportioning raw materials, can reduce the loss waste of raw material so greatly, promotes reaction process steadily to carry out uniformly, helps the control of reaction conditions and product yield, quality.
3, method preparation technology provided by the invention is simple, and is with low cost, and the whisker component that obtains is single, and length-to-diameter ratio is 10～20.
Description of drawings:
Fig. 1 is the XRD figure spectrum of the crystal whisker of hexa potassium titanate that obtains of synthetic method provided by the invention.The product that obtains as can be seen from the spectrogram is monophasic crystal whisker of hexa potassium titanate.
Fig. 2 is the stereoscan photograph of the crystal whisker of hexa potassium titanate that obtains with synthetic method provided by the invention.As can be seen from the figure the crystal whisker of hexa potassium titanate that obtains by method provided by the invention is evenly distributed, and smooth surface is smooth, and length-to-diameter ratio is 10～20.
Embodiment:
The present invention will be further described below in conjunction with example, but be not limited thereto, and further illustrates advantage of the present invention and characteristics by two comparative examples simultaneously.
Embodiment 1:
1, technical grade Anhydrous potassium carbonate and technical grade anatase titanium dioxide are pressed K
2O: TiO
2Mol ratio takes by weighing batching at 1: 6;
2, the compound for preparing in the step 1 is put in the high-energy ball milling jar with mill ball, dry grinds in high energy ball mill, ball material weight ratio is 10: 1,10 hours ball milling time, 700 rev/mins of rotational speed of ball-mill;
3, the raw material after high-energy ball milling in the step 2 is handled was 800 ℃ of following thermal treatments 1 hour, and the whisker XRD figure that obtains is composed as shown in Figure 1, and the scanning electron microscope picture as shown in Figure 2.As seen, the product that obtains is monophasic crystal whisker of hexa potassium titanate, length-to-diameter ratio 10～20.
Embodiment 2:
1, technical grade Anhydrous potassium carbonate and technical grade anatase titanium dioxide are pressed K
2O: TiO
2Mol ratio takes by weighing batching at 1: 6;
2, the compound for preparing in the step 1 is put in the high-energy ball milling jar with mill ball, dry grinds in high energy ball mill, ball material weight ratio is 20: 1,10 hours ball milling time, 600 rev/mins of rotational speed of ball-mill;
3, the raw material after high-energy ball milling in the step 2 is handled was 750 ℃ of following thermal treatments 1 hour, and the product that obtains is monophasic crystal whisker of hexa potassium titanate, length-to-diameter ratio 10～20.
Embodiment 3:
1, technical grade Anhydrous potassium carbonate and technical grade anatase titanium dioxide are pressed K
2O: TiO
2Mol ratio takes by weighing batching at 1: 6;
2, the compound for preparing in the step 1 is put in the high-energy ball milling jar with mill ball, dry grinds in high energy ball mill, ball material weight ratio is 20: 1,20 hours ball milling time, 500 rev/mins of rotational speed of ball-mill;
3, the raw material after high-energy ball milling in the step 2 is handled was 800 ℃ of following thermal treatments 1 hour, and the product that obtains is monophasic crystal whisker of hexa potassium titanate, length-to-diameter ratio 10～20.
Embodiment 4:
1, technical grade Anhydrous potassium carbonate and technical grade anatase titanium dioxide are pressed K
2O: TiO
2Mol ratio takes by weighing batching at 1: 6;
2, the compound for preparing in the step 1 is put in the high-energy ball milling jar with mill ball, dry grinds in high energy ball mill, ball material weight ratio is 20: 1,20 hours ball milling time, 700 rev/mins of rotational speed of ball-mill;
3, the raw material after high-energy ball milling in the step 2 is handled was 700 ℃ of following thermal treatments 1 hour, and the product that obtains is monophasic crystal whisker of hexa potassium titanate, length-to-diameter ratio 10～20.
Comparative example 1:
1, technical grade Anhydrous potassium carbonate and technical grade anatase titanium dioxide are pressed K
2O: TiO
2Mol ratio takes by weighing batching at 1: 6;
2, the compound for preparing in the step 1 is put in the urethane ball grinder with mill ball, carries out ball milling in planetary ball mill, ball material weight ratio is 10: 1,20 hours ball milling time, 300 rev/mins of rotational speed of ball-mill;
3, with the raw material after the ball-milling processing in the step 2 800 ℃ of following thermal treatments 1 hour, the crystal whisker of hexa potassium titanate that only contains 40% massfraction in the product that obtains, synthetic yield is lower, and this is because the efficiency ratio of ball milling is lower, synthetic in a large number the temperature that need be higher of product;
Comparative example 2:
1, technical grade Anhydrous potassium carbonate and technical grade anatase titanium dioxide are pressed K
2O: TiO
2Mol ratio takes by weighing batching at 1: 6;
2, the compound for preparing in the step 1 is put in the urethane ball grinder with mill ball, carries out ball milling in planetary ball mill, ball material weight ratio is 10: 1,20 hours ball milling time, 300 rev/mins of rotational speed of ball-mill;
3, with the raw material after the ball-milling processing in the step 2 1100 ℃ of following thermal treatments 5 hours, the product that obtains is the crystal whisker of hexa potassium titanate of 70% massfraction, this be since under higher synthesis temperature K
2A large amount of loss through volatilizationes of O make actual K
2O: TiO
2＜1: 6, TiO
2Abundant residues has influenced degree of purity of production.
Claims (3)
1. the method for a high-energy ball milling auxiliary synthesis of potassium titanate crystal whisker is characterized in that: the raw material that is adopted is cheap technical grade anatase titanium dioxide and technical grade Anhydrous potassium carbonate, and described raw material is pressed K
2O: TiO
2=1: 6 theoretical molar compares weigh batching, put into the high-energy ball milling jar with mill ball, carry out high-energy ball milling, ball material weight ratio during high-energy ball milling is 10: 1～20: 1, the high energy ball mill rotating speed is 500～700 rev/mins, ball milling took out after 10～20 hours, obtained crystal whisker of hexa potassium titanate in 1 hour in 700～800 ℃ of following thermal treatments again.
2. according to the method for the described high-energy ball milling auxiliary synthesis of potassium titanate crystal whisker of claim 1, the mill ball of selecting for use when it is characterized in that high-energy ball milling is a Stainless Steel Ball, and the mill ball diameter is between 1～3 centimetre.
3. according to the method for the described high-energy ball milling auxiliary synthesis of potassium titanate crystal whisker of claim 1～2, it is characterized in that: described method synthetic crystal whisker of hexa potassium titanate is formed single, does not have other impurity, length-to-diameter ratio is 10～20, plane of crystal is smooth smooth, and crystal development is abundant, and K in the reaction process
2O fully reacts, and does not have loss through volatilization.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070188A (en) * | 2010-12-09 | 2011-05-25 | 江南大学 | Method for preparing difficult-to-harden potassium titanate with low hygroscopicity and high bulk density |
| CN107815733A (en) * | 2017-11-17 | 2018-03-20 | 武汉科技大学 | A kind of crystal whisker of hexa potassium titanate based on titaniferous waste material and preparation method thereof |
| CN107829140A (en) * | 2017-11-17 | 2018-03-23 | 武汉科技大学 | Using titaniferous waste material as magnesium titanate potassium whisker of raw material and preparation method thereof |
| CN113264551A (en) * | 2021-05-19 | 2021-08-17 | 句容亿格纳米材料厂 | Preparation method of potassium titanate and application of potassium titanate in welding electrode |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1346803A (en) * | 2001-11-16 | 2002-05-01 | 无锡市宏杰轻工有限公司 | Process for preparing crystal wisker of potassium hexatitanate |
| CN1740408A (en) * | 2004-08-26 | 2006-03-01 | 上海捷晔复合材料有限公司 | Production process of serial potassium titanate whisker products |
| CN101148779B (en) * | 2007-07-24 | 2011-07-27 | 山东大学 | Preparation method for potassium titanate crystal whisker |
-
2009
- 2009-10-01 CN CN2009101724921A patent/CN101694009B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070188A (en) * | 2010-12-09 | 2011-05-25 | 江南大学 | Method for preparing difficult-to-harden potassium titanate with low hygroscopicity and high bulk density |
| CN107815733A (en) * | 2017-11-17 | 2018-03-20 | 武汉科技大学 | A kind of crystal whisker of hexa potassium titanate based on titaniferous waste material and preparation method thereof |
| CN107829140A (en) * | 2017-11-17 | 2018-03-23 | 武汉科技大学 | Using titaniferous waste material as magnesium titanate potassium whisker of raw material and preparation method thereof |
| CN113264551A (en) * | 2021-05-19 | 2021-08-17 | 句容亿格纳米材料厂 | Preparation method of potassium titanate and application of potassium titanate in welding electrode |
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| CN101694009B (en) | 2012-01-18 |
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