CN1147447C - Prepn of conductive composite nanometer titanium nitride-alumina material - Google Patents
Prepn of conductive composite nanometer titanium nitride-alumina materialInfo
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- CN1147447C CN1147447C CNB011323760A CN01132376A CN1147447C CN 1147447 C CN1147447 C CN 1147447C CN B011323760 A CNB011323760 A CN B011323760A CN 01132376 A CN01132376 A CN 01132376A CN 1147447 C CN1147447 C CN 1147447C
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- titanium nitride
- nanometer titanium
- alumina
- aluminum oxide
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Abstract
The present invention relates to a method for preparing electric conductivity nanometer titanium nitride-aluminum oxide composite material, which belongs to the field of aluminum oxide base composite material. The present invention is characterized in that firstly, nanometer titanium oxide-aluminum oxide composite powder is prepared from titaniferous compounds and aluminiferous compounds with a coprecipitation method; secondly, the nanometer titanium oxide-aluminum oxide composite powder is azotized in a tube-type reaction furnace at high temperature in the atmosphere of ammonia gas to prepare nanometer titanium nitride-aluminum oxide composite powder; finally, the electric conductivity nanometer titanium nitride-aluminum oxide composite material is prepared with a hot pressing sintering technology. The component range of the prepared nanometer composite material is TiN/ Al2 O3 (volume ratio)= 5/95 to 25/75. Under the optimization condition, the resistivity is from 1.5 to 8*10<-3> omega. Cm. The nanometer titanium nitride-aluminum oxide composite powder prepared with the method has the characteristics of uniform ingredient distribution and good sintering character. The prepared nanometer composite material has the advantages of good microstructure and higher electric conductivity, and the size of titanium nitride nanometer particles is smaller than 100 nanometers.
Description
Technical field
The present invention relates to the preparation method of conductive composite nanometer titanium nitride-alumina material.Belong to the alumina matrix composite field.
Background technology
Al
2O
3Be most widely used a kind of structural ceramic material, since Japanese scientist has reported at Al
2O
3Since the adding nano particle increases substantially the mechanical property of material in the matrix, Al
2O
3Base nano composite ceramic becomes the research field that material circle attracts people's attention.
TiN is a kind of type material, has hardness height (microhardness is 21GPa), fusing point height (2950 ℃), characteristics that chemical stability is good, is a kind of good infusibility high-abrasive material.Titanium nitride also has good electrical conductivity, and (room temperature resistivity is 3.34 * 10
-7Ω cm), can be used as electro-conductive materials such as the electrode of fused salt electrolysis and electrical contact.Since the physics and the chemical property of TiN excellence, recently, TiN particle REINFORCED Al
2O
3Composite study has caused the great interest of people, at Al
2O
3Introduce the TiN particle in the matrix and not only can improve its intensity, toughness and wear resisting property, and can improve its conductivity, make it be used to make high temperature heater (HTH), portfire and abrasion-proof structure parts, another advantage of this type of electro-conductive material is to adopt the ceramic component of spark technology manufacturing complex shapes, reduces processing charges significantly.Studies show that: the TiN particulate is introduced can make Al
2O
3Matrix strength raising 70%, toughness increase 30-70%.At present, the home and abroad is at TiN-Al
2O
3In the composite study, mostly with micron order or submicron order TiN, Al
2O
3Powder is a raw material, with Al
2O
3Powder mixes with TiN powder ball milling, and hot pressed sintering obtains TiN-Al then
2O
3Matrix material.Nano TiN-Al
2O
3Composite study is less, and in addition, mechanical ball milling blended method usually causes the reunion of adding phase, or causes local component deviation, finally influences the mechanical property and the conductivity of matrix material.In-situ compositing can be avoided the problems referred to above.
Summary of the invention
The object of the present invention is to provide a kind of novel method for preparing the high conductivity composite nanometer titanium nitride-alumina material.This preparation technology at first adopts coprecipitation method to prepare nano-TiO
2-Al
2O
3Composite granule adopts the nitridation in situ composite algorithm as raw material, preparation nano TiN-Al
2O
3Composite granule is after hot pressed sintering obtains composite nanometer titanium nitride-alumina material.This material has characteristics such as component is evenly distributed, powder sintering is good, material electroconductibility height.
The objective of the invention is to implement like this: with titaniferous compound and aluminiferous compound is main raw material, be dissolved in it in dehydrated alcohol by a certain percentage, hydrolysis under suitable condition, precipitation with the throw out calcining, obtain the composite granule of nano titanium oxide-aluminum oxide; In tubular react furnace, under mobile ammonia condition, high-temperature ammonolysis makes the composite granule of nanometer titanium nitride-alumina, makes conductive composite nanometer titanium nitride-alumina material through hot pressed sintering again with the composite granule of this nano titanium oxide-aluminum oxide.
Concrete enforcement can be divided into three and go on foot greatly:
The first step coprecipitation method prepares the composite granule of anatase-type nanometer titanium dioxide-aluminum oxide; Second step was prepared into the composite granule nitrogenize of nano titanium oxide-aluminum oxide the composite granule of nanometer titanium nitride-alumina; The 3rd step hot pressed sintering prepares conductive composite nanometer titanium nitride-alumina material.Now details are as follows respectively:
One, coprecipitation method prepares anatase-type nanometer titanium dioxide-aluminum oxide composite granule
By titaniferous and aluminiferous compound hydrolysis, precipitation, can obtain the precipitation of hydrated titanium dioxide-aluminium hydroxide.The mentioned titaniferous compound of the present invention can be a kind of in titanium tetrachloride, titanium sulfate, titanyl sulfate, metatitanic acid, butyl (tetra) titanate, the isopropyl titanate; Aluminiferous compound can be a kind of in aluminum isopropylate, aluminum nitrate, the aluminum chloride.These compounds are pressed TiN/Al
2O
3The ratio of (volume ratio)=5/95-25/75 is made into 10-30% (weight ratio) ethanol solution, under vigorous stirring, dropwise joins in the dilute ammonia solution of 3-6M 20-50 ℃ of hydrolysis, precipitation 8-24 hour.
Hydrolysis, precipitin reaction are:
M：Ti、Al
Product after filtration, wash secondary, use the absolute ethanol washing secondary again with distilled water at normal temperatures, remove water in the precipitation, at 100-120 ℃ of dry 8-24 hour, this product in 450-500 ℃ of calcining 2-4h, is obtained anatase-type nanometer titanium dioxide-aluminum oxide composite granule then.
Two, the preparation of nanometer titanium nitride-alumina composite granule
With the anatase-type nanometer titanium dioxide-aluminum oxide composite granule that obtains, put into quartz crucible, the tubular type of packing into atmosphere furnace feeds ammonia, ammonia flow is 0.5～5 liter/minute, be warming up to 800-1000 ℃, temperature rise rate is 10～25 ℃/minute, under this temperature, be incubated 2～5 hours, then, under the ammonia that flows, naturally cool to room temperature.Obtain the nanometer titanium nitride-alumina composite granule, wherein TiN vol% is 5-25%.
Three, the preparation of conductive composite nanometer titanium nitride-alumina material
Nanometer titanium nitride-alumina composite granule with preparation is a raw material, and a certain amount of composite granule is put into the graphite jig that scribbles boron nitride, and sintering forms in hot-pressed sintering furnace.Sintering temperature is 1400-1600 ℃, and sintering pressure is 30MPa, and sintering time is 30-60min.Experimental result shows: along with the increase of TiN content, the resistivity of matrix material reduces gradually, and when 20-25vol%TiN, the resistivity of matrix material is near Schwellenwert.
Conductive composite nanometer titanium nitride-alumina material preparation method's provided by the invention characteristics are:
1. Zhi Bei nanometer titanium nitride-alumina composite granule sintering character is good, and the two-phase component is evenly distributed, and the nano TiN size is less than 100 nanometers.
2. Zhi Bei composite nanometer titanium nitride-alumina material electroconductibility height.
3. use ammonia as reductive agent in the production process, than make reductive agent safety, reliable with hydrogen.
Description of drawings
Fig. 1 is the X-ray diffractogram of the conductive composite nanometer titanium nitride-alumina material of embodiment 1 and 2 preparations.
Fig. 2 is the back scattering stereoscan photograph of the polished surface of embodiment 1.
Fig. 3 is the stereoscan photograph of the fracture surface of embodiment 1.
Fig. 4 is the back scattering stereoscan photograph of the polished surface of embodiment 2.
Fig. 5 is the stereoscan photograph of the fracture surface of embodiment 2.
Embodiment
Embodiment further specifies embodiment and effect with following indefiniteness embodiment.
Embodiment 1 25vol%TiN-75vol%Al
2O
3The preparation of matrix material
Get butyl (tetra) titanate 92g, aluminum nitrate (Al (NO
3)
39H
2O) 266g is dissolved in the 1200ml ethanol solution, with the ethanol solution of butyl (tetra) titanate and aluminum nitrate, under vigorous stirring, dropwise join in the dilute ammonia solution of 6M, 30 ℃ of hydrolysis, the precipitation 15 hours, hydrolysis, precipitated product are filtered, use distilled water wash, remove impurity, use the absolute ethanol washing secondary again, filter cake at 120 ℃ of oven dry 8h, is ground, crosses 200 mesh sieves, then 450 ℃ of calcining 2h.Nano titanium oxide-aluminum oxide the composite granule that obtains is put into quartz crucible, and the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 2 liters/minute, is warming up to 950 ℃, and temperature rise rate is 15 ℃/minute.Insulation is 4 hours under this temperature, then, under the ammonia that flows, naturally cools to room temperature.Obtain the nanometer titanium nitride-alumina composite granule.A certain amount of this composite granule is put into the graphite jig that scribbles boron nitride, sinter molding in hot-pressed sintering furnace.Sintering temperature is 1550 ℃, and sintering pressure is 30MPa, and sintering time is 60min.
Fig. 1 is the X-ray diffractogram of the conductive composite nanometer titanium nitride-alumina material of present embodiment preparation, the diffraction peak that titanium nitride and Alpha-alumina are only arranged among the figure, show that what obtain is pure titanium nitride-alumina composite material, do not have chemical reaction to take place in the high-temperature sintering process between conductive phase titanium nitride and the matrix alumina.Fig. 2 is the back scattering stereoscan photograph of its polished surface, and the white particle among the figure is a titanium nitride, and most of particulate size is less than 100 nanometers.Fig. 3 is the stereoscan photograph of its fracture surface, picture display material uniform crystal particles, careful, and fracture mode mainly is along brilliant fracture.The resistivity of the conductive composite nanometer titanium nitride-alumina material of present embodiment preparation is: 1.5 * 10
-3Ω cm.
Get butyl (tetra) titanate 46g, aluminum chloride (AlCl
36H
2O) 164g is dissolved in the 1000ml ethanol solution, with the ethanol solution of butyl (tetra) titanate and aluminum chloride, under vigorous stirring, dropwise join in the dilute ammonia solution of 4M, 45 ℃ of hydrolysis, the precipitation 8 hours, hydrolysis, precipitated product are filtered, use distilled water wash, remove impurity, use the absolute ethanol washing secondary again, filter cake at 120 ℃ of oven dry 8h, is ground, crosses 200 mesh sieves, then 450 ℃ of calcining 2h.Nano titanium oxide-aluminum oxide the composite granule that obtains is put into quartz crucible, and the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 1 liter/minute, is warming up to 900 ℃, and temperature rise rate is 10 ℃/minute.Insulation is 5 hours under this temperature, then, under the ammonia that flows, naturally cools to room temperature.Obtain the nanometer titanium nitride-alumina composite granule.A certain amount of this composite granule is put into the graphite jig that scribbles boron nitride, sinter molding in hot-pressed sintering furnace.Sintering temperature is 1500 ℃, and sintering pressure is 30MPa, and sintering time is 45min.
The X-ray diffractogram of the conductive composite nanometer titanium nitride-alumina material of present embodiment preparation is identical with the Fig. 1 among the embodiment 1.The diffraction peak that titanium nitride and Alpha-alumina are only arranged among the figure shows that what obtain is pure titanium nitride-alumina composite material, does not have chemical reaction to take place in the high-temperature sintering process between conductive phase titanium nitride and the matrix alumina.Fig. 4 is the back scattering stereoscan photograph of the conductive composite nanometer titanium nitride-alumina material polished surface of present embodiment preparation, and the white particle among the figure is a titanium nitride, and a part of particulate size is less than 100 nanometers.Fig. 5 is the stereoscan photograph of its fracture surface, picture display material uniform crystal particles, careful, and fracture mode mainly is along brilliant fracture.The resistivity of the conductive composite nanometer titanium nitride-alumina material of present embodiment preparation: 2.4 * 10
-2Ω cm.
Embodiment 3 10vol%TiN-90vol%Al
2O
3The preparation of matrix material
Get isopropyl titanate 30g, aluminum isopropylate 68g is dissolved in the 500ml ethanol solution, with this ethanol solution, under vigorous stirring, dropwise join in the distilled water, hydrolysate is filtered, use the distilled water wash secondary, remove impurity, use the absolute ethanol washing secondary again, filter cake at 120 ℃ of oven dry 10h, is ground, crosses 200 mesh sieves, then 450 ℃ of calcining 4h.Nano titanium oxide-aluminum oxide the composite granule that obtains is put into quartz crucible, and the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 3 liters/minute, is warming up to 850 ℃, and temperature rise rate is 10 ℃/minute.Insulation is 5 hours under this temperature, then, under the ammonia that flows, naturally cools to room temperature.Obtain the nanometer titanium nitride-alumina composite granule.A certain amount of this composite granule is put into the graphite jig that scribbles boron nitride, sinter molding in hot-pressed sintering furnace.Sintering temperature is 1550 ℃, and sintering pressure is 30MP, and sintering time is 60min.Obtain 10vol%TiN-90vol%Al
2O
3Composite nanometer titanium nitride-alumina material, its nano TiN particle size is less than 100 nanometers.
Claims (7)
1. the preparation method of an electroconductibility titanium nitride-alumina matrix material comprises co-precipitation, nitrogenize, hot-pressing sintering technique process, it is characterized in that preparation process divided for three steps: the preparation of (1) anatase type nano titanium dioxide-aluminum oxide composite granule; (2) nano-titanium oxide-aluminum oxide composite granule nitridation in situ is made the nanometer titanium nitride-alumina composite granule; (3) be raw material with the nanometer titanium nitride-alumina composite granule, under nitrogen atmosphere, utilize hot pressing and sintering technique to make conductive composite nanometer titanium nitride-alumina material.
2. by the described method for preparing conductive composite nanometer titanium nitride-alumina material of claim 1, the preparation that it is characterized in that anatase type nano titanium dioxide-aluminum oxide composite granule is: (1) utilizes titaniferous compound and aluminiferous compound to be main raw material, presses TiN/Al
2O
3Volume ratio be the ratio of 5/95-25/75 to be made into weight ratio be the 10-30% ethanol solution, under vigorous stirring, dropwise join in the dilute ammonia solution of 3-6M, 20-50 ℃ of hydrolysis, precipitation 8-24 hour; (2) product is washed secondary with distilled water after filtration at normal temperatures, uses the absolute ethanol washing secondary again, and under 100-120 ℃ of condition dry 8-24 hour then, then in 450-500 ℃ of calcining 2-4 hour.
3. by the preparation method of the described conductive composite nanometer titanium nitride-alumina material of claim 2, it is characterized in that described titaniferous compound is a kind of in titanium tetrachloride, titanium sulfate, titanyl sulfate, metatitanic acid, butyl (tetra) titanate, the isopropyl titanate; Aluminiferous compound is a kind of in aluminum isopropylate, aluminum nitrate, the aluminum chloride.
4. press the preparation method of the described conductive composite nanometer titanium nitride-alumina material of claim 1, it is characterized in that it is to be under 0.5-5 liter/minute mobile ammonia at flow that nano-titanium oxide-aluminum oxide composite granule nitridation in situ becomes nanometer titanium nitride-alumina composite granule condition, insulation is 2-5 hour under the 800-1000 ℃ of temperature, under the ammonia atmosphere that flows, naturally cool to room temperature then.
5. by the described conductive composite nanometer titanium nitride-alumina material preparation method of claim 4, it is characterized in that it is 10-25 ℃/minute that nano-titanium oxide-aluminum oxide composite granule nitridation in situ becomes the temperature rise rate of nanometer titanium nitride-alumina composite granule.
6. by the described conductive composite nanometer titanium nitride-alumina material preparation method of claim 1, it is characterized in that with the nanometer titanium nitride-alumina composite granule be raw material, under ammonia atmosphere, the processing parameter that adopts hot pressing and sintering technique to make conductive composite nanometer titanium nitride-alumina material is that sintering temperature is 1400-1600 ℃, pressure is 30MPa, and soaking time is 30-60 minute.
7. by the described conductive composite nanometer titanium nitride-alumina material preparation method of claim 6, it is characterized in that preparing composite nanometer titanium nitride-alumina material is that the nanometer titanium nitride-alumina composite granule is put into the graphite jig that scribbles boron nitride, sintering in hot pressing furnace.
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| CN100562506C (en) * | 2004-11-29 | 2009-11-25 | 京瓷株式会社 | Aluminum oxide-titanium nitride class sintered compact and manufacture method thereof, magnetic head substrate, ultrasonic motor, dynamic pressure bearing |
| CN100347124C (en) * | 2005-11-23 | 2007-11-07 | 中国科学院上海硅酸盐研究所 | Preparation process of conducting aluminium oxide base nano ceramic material |
| EP2054228B1 (en) * | 2006-07-06 | 2016-05-25 | Arkema Inc. | Flexible multilayer vinylidene fluoride tubes |
| CN100404465C (en) * | 2006-10-30 | 2008-07-23 | 陕西科技大学 | Method for preparing TiN/Al2O3 composite materials |
| CN102826852B (en) * | 2012-08-31 | 2016-01-13 | 中国地质大学（北京） | A kind of preparation method of titanium nitride-alumina multi-phase wear-resistant high temperature ceramic material |
| CN104123976B (en) * | 2014-02-09 | 2016-07-06 | 深圳唯一科技股份有限公司 | A kind of handset touch panel electric slurry and preparation method thereof |
| CN105439635B (en) * | 2015-11-19 | 2017-11-14 | 中国海洋大学 | A kind of low temperature preparation method of high-dielectric composite material |
| CN107434406B (en) * | 2017-09-11 | 2020-09-15 | 河北建材职业技术学院 | Nanocrystalline α -Al2O3And preparation method of titanium nitride composite material |
| CN110015895A (en) * | 2019-04-01 | 2019-07-16 | 中国有色桂林矿产地质研究院有限公司 | A kind of aluminium oxide-zirconium oxide-yttrium oxide-titanium nitride nano composite ceramic material and preparation method thereof |
| CN114149273B (en) * | 2021-12-28 | 2022-10-21 | 湖南省嘉利信陶瓷科技有限公司 | Preparation method of alumina ceramic powder for electronic ceramics |
| CN117003552B (en) * | 2023-06-16 | 2024-02-23 | 辽宁煜鑫高科技术新材料有限公司 | Preparation method and application of plate-shaped corundum-based composite refractory material |
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