CN1093760A - Potassium titanate crystal whiskers preparation method - Google Patents

Potassium titanate crystal whiskers preparation method Download PDF

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Publication number
CN1093760A
CN1093760A CN 93111038 CN93111038A CN1093760A CN 1093760 A CN1093760 A CN 1093760A CN 93111038 CN93111038 CN 93111038 CN 93111038 A CN93111038 A CN 93111038A CN 1093760 A CN1093760 A CN 1093760A
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potassium
preparation
raw material
containing compound
fusing assistant
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CN1035443C (en
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隗学礼
赵宽放
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Institute of Metal Research of CAS
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Abstract

A kind of preparation method who produces potassium titanate crystal whisker makes raw material with titanium-containing compound such as rutile-type perovskite powder, anatase octahedrite, titanium dioxide etc. and potassium-containing compound such as potassium hydroxide, saltpetre, Repone K, salt of wormwood etc.It is characterized in that: also added one of base metal nitrate, vitriol, muriate or its combination in the building-up process as fusing assistant.Its technological process is as follows: is 2~4: 1 (More's ratio) preparation with raw material by Ti: K, and the fusing assistant that adds 20~40wt% simultaneously mixes; Under 900~1300 ℃ of temperature, synthesized 30 minutes~4 hours; Drying is filtered in hydrolysis.The present invention improves synthesis efficiency and whisker quality, reduces cost, and makes things convenient for the big batch continuous production.

Description

Potassium titanate crystal whiskers preparation method
The present invention relates to the preparation method of Preparation of Whiskers technology, particularly potassium titanate crystal whisker.
Strengthen resin and metal with inorganic fibers,, come into one's own as high performance composite.Particularly POTASSIUM HEXATITANATE fiber can replace multiduty asbestos, avoids environmental pollution, more induces one to treat with special respect.But it is imperative to seek potassium titanate fiber manufacture method best in quality, suitability for industrialized production with low cost.
The method that in the past prepared potassium titanate fiber has hydrothermal method [1], sintering method [2], scorification [3], the quick cooling crystallization method [4,5]Gentle cold crystallization method [6]Deng.But above-mentioned these preparation methods have shortcoming in various degree, are unsuitable for large-scale commercial production.Adopt menstruum under the high temperature more than the stagnation point of water, high pressure, to synthesize as the hydro-thermal genealogy of law, in containing the solution of high potassium, essential security device, cost of equipment height, operate continuously difficulty; Burn till the genealogy of law raw mix is reacted synthon through solid state sintering, its resultant crystalline state is insufficient, and the fiber of generation is too short, has only several microns; The fusion genealogy of law is the raw mix high-temperature fusion, forms cooling curing crystallization again behind the melt.This method synthesis temperature height, the crystallization phases binding ratio of generation is tightr, and it is very difficult to separate fibre, and the diameter of gained fiber is bigger, generally greater than 10~30 μ m, and irregular, uniformity is poor, and it is bad to be used as the toughener effect; And the gentle crystallisation by cooling method of quick cooling crystallization method all is to generate unsettled two potassium titanates and potassium tetratitanate earlier, taking off potassium through pickling again handles and further thermal treatment, could generate POTASSIUM HEXATITANATE fiber, and adopt multistep processes to increase technical process, material consumption and cost of equipment undoubtedly, unfavorable to scale production.
The object of the present invention is to provide a kind of method of making potassium titanate fiber,, reduce cost, make things convenient for the big batch continuous production to improve synthesis efficiency and whisker quality.
The invention provides a kind of preparation method who produces potassium titanate crystal whisker, make raw material with titanium-containing compound such as rutile-type perovskite powder, anatase octahedrite, titanium dioxide etc. and potassium-containing compound such as potassium hydroxide, saltpetre, Repone K, salt of wormwood etc., it is characterized in that: also added one of base metal nitrate, vitriol, muriate or its combination in the building-up process as fusing assistant; Its technological process is as follows:
-be 2~4 with raw material by Ti: K: the 1(More than) preparation, the fusing assistant that adds 20~40wt.% simultaneously mixes;
-under 900~1300 ℃ of temperature, synthesized 30 minutes~4 hours;
Drying is filtered in-hydrolysis.
Adopting the method for the invention can generate diameter is that 1~5 μ m, length are the six potassium titanate (K of 20~80 μ m 2Ti 6O 13) whisker.Owing in the mixing of raw material, added the fusing assistant of suitable proportion, formed the uniform mixing of raw material and fusing assistant; The fusing assistant fusing point is lower, thereby greatly reduces the synthesis temperature of fiber growth; The flux melt forms the growth that the liquid phase space benefits potassium titanate fiber, helps to improve the whisker quality; The proportioning raw materials that the present invention adopts, helping step generation six potassium titanates (is K 2Ti 6O 13) fiber, than scorification, earlier synthetic unsettled two potassium titanates of the gentle cold crystallization method of quick cooling crystallization method and potassium tetratitanate, to take off potassium through pickling again and handle and further thermal treatment, the multistep processes that could generate POTASSIUM HEXATITANATE fiber seems superior.Below by embodiment in detail the present invention is described in detail.
Embodiment 1:
1. preparation of raw material: titanium-containing compound adopts anatase titanium dioxide breeze (TiO 2Account for more than 95%); Potassium-containing compound adopts Repone K (purity 96%), presses Ti/K Mol than 2.5 prescriptions, adds fusing assistant 20wt.% sodium-chlor and mixes; 2. put into cabinet-type electric furnace and be heated to 1000 ℃, be incubated 2 hours, then furnace cooling; 3. burned material is put in to soak in the water of 10 times (weight ratios) and blends; 4. filter and remove moisture, dry in electric oven; Resultant white needles thing is crystal whisker of hexa potassium titanate through X-ray diffraction analysis and scanning electron microscopic observation.Diameter is 1~4 μ m, and length is at 20~50 μ m, and quality is even, structural integrity.
Embodiment 2:
1. preparation of raw material: titanium-containing compound adopts rutile-type ilmenite powder (TiO 2Account for more than 95%); Potassium-containing compound adopts saltpetre (purity 98%), presses Ti: K Mol adds fusing assistant 30wt.% sodium-chlor, uniform mixing than 3 prescriptions; 2. raw materials mixed is placed in the punching block extrusion forming; 3. moulding sample piece is put into cabinet-type electric furnace and is heated to 1100 ℃, is incubated one hour, then furnace cooling; 4. burned material is put in to soak in the water of 10 times (weight ratios) and blends; 5. filter and remove moisture, dry in electric oven; Resultant white needles thing is crystal whisker of hexa potassium titanate through X-ray diffraction analysis and scanning electron microscopic observation.Diameter is 0.5~2 μ m, and length is at 20~50 μ m, and quality is even, structural integrity.
Embodiment 3:
1. preparation of raw material: titanium-containing compound adopts titanium oxide powder (TiO 2Account for more than 95%); Potassium-containing compound adopts saltpetre (purity 98%), presses Ti/K Mol than 3.8 prescriptions, adds fusing assistant 40wt.% sodium sulfate and mixes; 2. compound is put into cabinet-type electric furnace and be heated to 1300 ℃, be incubated 30 minutes, then furnace cooling; 3. burned material is put in to soak in the water of 10 times (weight ratios) and blends; 5. filter and remove moisture, dry in electric oven; Resultant white needles thing is crystal whisker of hexa potassium titanate through X-ray diffraction analysis and scanning electron microscopic observation.Diameter is 0.5~2 μ m, and length is at 20~60 μ m, and quality is even, structural integrity.
Embodiment 4(comparative example):
The quick cooling crystallization method [4,5]: 1. preparation of raw material: titanium-containing compound adopts rutile-type breeze (TiO 2Account for more than 95%); Potassium-containing compound adopts salt of wormwood (purity 99%), presses TiO 2/ K 2O Mol is than 3.0 prescriptions; Uniform mixing; 2. heating and melting: raw material is placed in the crucible, puts into cabinet-type electric furnace and is heated to 1300 ℃, is incubated 30 minutes; 3. quick cooling crystallization: with two roller foliation methods (roller footpath 80mm, two roller spacing 0.3mm, roller speed 90rpm) the foil-like solid; 4. pulverize: the foil-like solid is ground into granularity 0.5~10 μ m; 5. taking off potassium handles: crushed material is put in the water of 50 times (weight ratios) or the acetic acid soaks a few hours; 6. thermal treatment: filter and remove moisture, dry in electric oven, then 1000 ℃ of insulations 10~24 hours; 7. separate fibre: in the article after thermal treatment, add 10 times of water, stirred 15 minutes; 8. dehydrate: get the white needles thing,, be potassium tetratitanate and six potassium titanate blend fiber through X-ray diffraction analysis and scanning electron microscopic observation.Diameter is 0.5~2 μ m, and length is in 10~30 μ m, inferior quality.
Compared and can obviously be found out by embodiment and comparative example: method preparation technology of the present invention simplifies greatly, saved pulverizing, taken off multiple working procedures such as potassium and thermal treatment, and synthesis reaction temperature reduces greatly, and resulting fiber is longer, and quality is better.Application result shows: the prepared whisker of the inventive method has performances such as lightweight, high-strength, fire-resistant, heat insulation and abrasion resisting, can be used as the heat resisting coating additive, automobile brake sheet also is widely used in polymer matrix composites as strengthening constituent element, is the best product that replaces asbestos.By preparation technology provided by the invention, method is easy, with low cost, and non-environmental-pollution is applicable to industrial-scale production.
Pertinent literature:
[1] " ceramic industry association will ", 83, (1975) p.305~311
[2] " ceramic industry association will ", 88, (1980) p.84~91
[3] " ceramic industry association will ", 90, (1982) p.19~23
[4]JP 63-79799 [5]JP 63-79800
[6] " ceramic industry association will ", 91, (1983) p.189

Claims (2)

1, a kind of preparation method who produces potassium titanate crystal whisker, make raw material with titanium-containing compound such as rutile-type perovskite powder, anatase octahedrite, titanium dioxide etc. and potassium-containing compound such as potassium hydroxide, saltpetre, Repone K, salt of wormwood etc., it is characterized in that: also added one of base metal nitrate, vitriol, muriate or its combination in the building-up process as fusing assistant; Its technological process is as follows:
-with raw material by Ti: K (More than) preparation that is 2~4: 1, the fusing assistant that adds 20~40wt.% simultaneously mixes;
-under 900~1300 ℃ of temperature, synthesized 30 minutes~4 hours;
Drying is filtered in-hydrolysis.
2, by the described Preparation of Whiskers method of claim 1, it is characterized in that: raw material compacting to mixing before synthetic.
CN93111038A 1993-04-10 1993-04-10 Potassium titanate crystal whiskers preparation method Expired - Fee Related CN1035443C (en)

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074391C (en) * 1997-06-12 2001-11-07 中国科学院固体物理研究所 fibrous nanometer potasium titanate and its preparing method
CN101250751B (en) * 2007-11-30 2010-06-09 江苏大学 Method for preparing crystal wisker of potassium hexatitanate
CN101962808A (en) * 2010-06-17 2011-02-02 马玉馨 High-efficiency and energy-saving potassium titanate whisker preparation method
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
CN101144186B (en) * 2006-09-12 2011-11-23 江西隆亨新材料有限公司 Method for synthesizing potassium hexatitanate crystal whisker
CN102677173A (en) * 2012-05-22 2012-09-19 中国科学院青海盐湖研究所 Preparation method of lead titanate whiskers
CN102787359A (en) * 2012-09-03 2012-11-21 中国科学院青海盐湖研究所 Preparation method for calcium titanate whiskers
CN102849790A (en) * 2012-09-27 2013-01-02 攀枝花学院 Preparation method of columnar hexagonal potassium titanate
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
CN104894636A (en) * 2015-04-29 2015-09-09 华东理工大学 Preparation method of potassium octatitanate whisker
CN105734670A (en) * 2016-04-13 2016-07-06 唐山晶须复合材料制造有限公司 Synthesizing method for potassium hexatitanate column crystals
CN108315822A (en) * 2018-02-10 2018-07-24 罗旭 Epoxy drive, which moves a step, prepares crystal whisker of hexa potassium titanate method and its photocatalytic applications
CN110697767A (en) * 2019-11-07 2020-01-17 河钢股份有限公司承德分公司 Method for preparing alkali metal fluorotitanate by using alkali metal titanate
CN111116156A (en) * 2019-12-19 2020-05-08 江苏盐砼新材料科技有限公司 Low-damage high-strength aerated concrete block and preparation method thereof
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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CN100348275C (en) * 2005-05-18 2007-11-14 河北工业大学 Method for preparing surface microporous titanium of titanium-based biological medical material

Family Cites Families (1)

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Publication number Priority date Publication date Assignee Title
JPH0283300A (en) * 1988-09-21 1990-03-23 Toho Titanium Co Ltd Heat treatment of potassium titanate whisker

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1074391C (en) * 1997-06-12 2001-11-07 中国科学院固体物理研究所 fibrous nanometer potasium titanate and its preparing method
CN101144186B (en) * 2006-09-12 2011-11-23 江西隆亨新材料有限公司 Method for synthesizing potassium hexatitanate crystal whisker
CN101250751B (en) * 2007-11-30 2010-06-09 江苏大学 Method for preparing crystal wisker of potassium hexatitanate
CN101962808A (en) * 2010-06-17 2011-02-02 马玉馨 High-efficiency and energy-saving potassium titanate whisker preparation method
CN101962808B (en) * 2010-06-17 2012-05-23 马玉馨 High-efficiency and energy-saving potassium titanate whisker preparation method
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
CN102677173A (en) * 2012-05-22 2012-09-19 中国科学院青海盐湖研究所 Preparation method of lead titanate whiskers
CN102787359A (en) * 2012-09-03 2012-11-21 中国科学院青海盐湖研究所 Preparation method for calcium titanate whiskers
CN102787359B (en) * 2012-09-03 2015-04-15 中国科学院青海盐湖研究所 Preparation method for calcium titanate whiskers
CN102849790B (en) * 2012-09-27 2014-10-01 攀枝花学院 Preparation method of columnar hexagonal potassium titanate
CN102849790A (en) * 2012-09-27 2013-01-02 攀枝花学院 Preparation method of columnar hexagonal potassium titanate
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
CN104894636A (en) * 2015-04-29 2015-09-09 华东理工大学 Preparation method of potassium octatitanate whisker
CN104894636B (en) * 2015-04-29 2017-10-27 华东理工大学 The preparation method of eight potassium titanate crystal whiskers
CN105734670A (en) * 2016-04-13 2016-07-06 唐山晶须复合材料制造有限公司 Synthesizing method for potassium hexatitanate column crystals
CN108315822A (en) * 2018-02-10 2018-07-24 罗旭 Epoxy drive, which moves a step, prepares crystal whisker of hexa potassium titanate method and its photocatalytic applications
CN110697767A (en) * 2019-11-07 2020-01-17 河钢股份有限公司承德分公司 Method for preparing alkali metal fluorotitanate by using alkali metal titanate
CN110697767B (en) * 2019-11-07 2022-08-05 河钢股份有限公司承德分公司 Method for preparing alkali metal fluorotitanate by using alkali metal titanate
CN111116156A (en) * 2019-12-19 2020-05-08 江苏盐砼新材料科技有限公司 Low-damage high-strength aerated concrete block and preparation method thereof
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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