CN1417163A - Prepn of nano titanium nitride-silicon nitride composite material - Google Patents
Prepn of nano titanium nitride-silicon nitride composite material Download PDFInfo
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Abstract
The present invention relates to a preparation process of composite nanometer-level conductive TiO2-Si3N4 material with high strength. The preparation process includes non-homogeneous precipitation to prepare anatase type composite TiO2-Si3N4 nano powder, in-situ nitration to prepare composite TiN-Si3N4 powder, adding Y2O3 and Al2O3 as additive to prepare composite TiN-Si3N4-Al2O3-Y2O3 powder, pressure sintering composite TiN-Si3N4-Al2O3-Y2O3 powder to prepare high-strength conductive TiN-Si3N4 material. The composite material has TiN/Si3N4 volume ratio of 5/87 to 25/67 and crystal size of 40-50 nanometer.
Description
Technical Field
The invention relates to a preparation method of a high-strength and conductive titanium nitride-silicon nitride composite material.
Background
Silicon nitride ceramics are one of the most important structural ceramic materials due to their excellent room and high temperature strength and relatively high fracture toughness. In addition, the silicon nitride ceramics have high hardness, small thermal expansion coefficient, oxidation resistance and wear resistance, can be widely used as high-temperature parts of heat engines, wear-resistant sealing materials, cutting tools and the like, and have wide application prospects in chemical industry, metallurgy, aerospace and automobile industry.
TiN is a novel material, has the characteristics of high hardness (microhardness of 21Gpa), high melting point (2950 ℃) and good chemical stability, and is a good refractory wear-resistant material. Titanium nitride also has good conductivity (room temperature resistance of 3.34X 10)-7Omega. cm) can be used as conductive materials such as electrodes and electrical contacts for molten salt electrolysis. The addition of the conductive second phase particles such as TiN, TiC and the like into the silicon nitride matrix can not only improve the toughness of the matrix material, but also enable the prepared composite material to have the conductivity similar to metal, and the composite material has two advantages, firstly, the composite material can be used for processing ceramic products with complex shapes by adopting an electric spark technology (electric discharge machining), thereby greatly reducing the processing cost. Second, the composite material can be used in high temperature heaters, ignition devices, heat exchangers, wear resistant and structural components. TiN-Si because TiN has a lower coefficient of friction3N4The composite material is very suitable for cutting tools, and has a longer service life than pure Si3N4The material is much higher.
The conductive mechanism of the composite material is that the added conductive TiN particles form a conductive network in the matrix, so the size and the quantity of the second-phase conductive particles are important factors influencing the conductive performance of the composite material, and under the premise that the size and the quantity of the particles are the same, the conductive particles are uniformly dispersed in the matrix and are otherwise key factors influencing the conductive network. The general composite method is to mix the matrix material (Si)3N4) Ball milling with second phase conductive particles (usually micron TiN) has the greatest disadvantage of difficulty in mixingThe two substances are uniformly mixed, so that the agglomeration of an addition phase is often caused, or the partial component deviation is caused, impurities are easily brought in during ball milling, and the mechanical property and the conductivity of the composite material are finally influenced. The in situ compounding method can avoid the above problems. And micron-sized TiN powder is adopted as the second-phase conductive particles, and because the size of the conductive particles is large, a large amount of TiN is required to be added to form a conductive network, and 30 vol% of TiN is generally required, even 50 vol%. The nanometer titanium nitride is used for replacing the nanometer titanium nitride, the using amount of the titanium nitride can be expected to be reduced, and a more uniform conductive network can be formed, but the nanometer titanium nitride is difficult to prepare, and reports on improving the conductive performance of the silicon nitride ceramic by the nanometer titanium nitride are not available at present.
Disclosure of Invention
The invention aims to provide a novel method for preparing a high-strength and conductive titanium nitride-silicon nitride composite material. The preparation process firstly adopts a heterogeneous precipitation method to prepare the nano TiO2-Si3N4Preparing nano TiN-Si by in-situ nitridation compounding method using the composite powder as raw material3N4Composite powder of Al2O3And Y2O3And finally, performing hot-pressing sintering to obtain the titanium nitride-silicon nitride composite material. The material has the characteristics of uniform component distribution, good powder sintering property, high bending strength, high conductivity and the like.
The object of the invention is thus achieved: dissolving a titanium-containing compound and silicon nitride powder serving as main raw materials in absolute ethyl alcohol according to a certain proportion, hydrolyzing and precipitating under proper conditions, and calcining a precipitate to obtain nano titanium dioxide-silicon nitride composite powder; the nano titanium dioxide-silicon nitride composite powder is subjected to high-temperature nitridation in a tubular reaction furnace under the condition of flowing ammonia gas to prepare nano titanium nitride-silicon nitride composite powder, then a proper amount of sintering aid is added, and finally, the high-strength and conductive titanium nitride-silicon nitride composite material is prepared through hot-pressing sintering.
The specific implementation can be divided into four steps:
firstly, preparing anatase type nano titanium dioxide-silicon nitride composite powder by a heterogeneous precipitation method; secondly, in-situ nitriding the nano titanium dioxide-silicon nitride composite powder to prepare nano titanium nitride-silicon nitride composite powder; and thirdly, adding a sintering aid into the nano titanium nitride-silicon nitride composite powder, and performing ball milling and mixing to uniformly mix the components to obtain the sintered powder. Fourthly, preparing the high-strength and conductive titanium nitride-silicon nitride composite material by hot-pressing sintering. Now, the following are detailed respectively:
preparation of anatase type nano titanium dioxide-silicon nitride composite powder by heterogeneous precipitation method
Heterogeneous precipitation is a preparation method by which a precipitate is rapidly obtained by adding a precipitant to a liquid phase medium. The titanium-containing compound and silicon nitride powder are used as raw materials, and the hydrated titanium dioxide-silicon nitride precipitate can be obtained through hydrolysis and precipitation. The titanium-containing compound can be one of titanium tetrachloride, titanium sulfate, titanyl sulfate, metatitanic acid, butyl titanate and isopropyl titanate; these compounds are reacted with TiN/Si3N4Preparing anhydrous ethanol solution according to the proportion of 5/87-25/67, dropwise adding distilled water under vigorous stirring, and finally controlling the molar ratio of the butyl titanate to the distilled water as follows: ti: H2O＝1∶150。
The hydrolysis and precipitation reaction comprises the following steps:
filtering the product, washing twice with distilled water at normal temperature, washing twice with absolute ethyl alcohol, removing water in the precipitate, drying at 100-120 ℃ for 8-24 hours, and calcining the product at 500 ℃ for 2-4 hours to obtain the anatase type nano titanium dioxide-silicon nitride composite powder. The titanium dioxide is uniformly coated on the surface of the silicon nitride particles, and the average grain size is 10-15 nanometers.
Preparation of nano titanium nitride-silicon nitride composite powder
Putting the obtained anatase type nano titanium dioxide-silicon nitride composite powder into a quartz crucible, putting the quartz crucible into a tubular atmosphere furnace, introducing ammonia gas, heating to 800-. Obtaining the nano titanium nitride-silicon nitride composite powder, wherein the volume percent of TiN is 5-25%. TiN crystal grains are uniformly coated on Si3N4Surface, average grain size 40-50 nm.
Thirdly, selection and addition of sintering aid
The invention selects Al2O3And Y2O3The addition amount of the sintering aid is 3 vol% and 5 vol%, the sintering aid and the prepared nano titanium nitride-silicon nitride composite powder are dispersed in absolute ethyl alcohol, ball milling and mixing are carried out for 12-24 hours, the mixed slurry is dried for 8-24 hours at the temperature of 100 ℃ and 120 ℃, and grinding and 200-mesh sieving are carried out to obtain TiN-Si with different compositions3N4-Al2O3-Y2O3The composite powder of (1). The powder composition is shown in table 1:table 1: composition of powder
Composition # 1 sample # 2 sample #3 sample # 4 sample # 5 sample
TiN(vol％) 5 10 15 20 25
Si3N4(vol％) 87 82 77 72 67
Al2O3(vol％) 3 3 3 3 3
Y2O3(vol％) 5 5 5 5 5
Preparation of high-strength and conductive titanium nitride-silicon nitride composite material
The prepared composition is TiN-Si3N4-Al2O3-Y2O3The composite powder is prepared by putting a certain amount of composite powder into a graphite mould coated with boron nitride and sintering in a hot-pressing sintering furnace. The sintering temperature is 1600-1800 ℃, the sintering pressure is 30MPa, and the sintering time is 50-90 min. The experimental results show that: the resistivity of the composite material gradually decreases with increasing TiN content, and approaches the lowest value at 20-25 vol% TiN. In the "background art", we mention that "a larger amount (30-50 vol%) of TiN can form a conductive network", and when 20-25 vol% of TiN is added to the composite material prepared by the invention, the conductivity reaches the value reported in the literature. This is related to the fact that the composite powder prepared by the in-situ nitridation method provided by the invention has smaller titanium nitride crystal grains and better uniformity, so that the conductive network is more effective.
The preparation method of the high-strength and conductive titanium nitride-silicon nitride composite material provided by the invention has the characteristics that:
1. the prepared nano titanium nitride-silicon nitride composite powder hasgood sintering performance and uniform component distribution, and the size of the nano TiN is 40-50 nanometers.
2. The prepared titanium nitride-silicon nitride composite material has high bending strength.
3. The prepared titanium nitride-silicon nitride composite material has high conductivity; the TiN content forming the conductive network is only 20-25 vol% lower than the value of 30-50 vol% reported in the literature.
4. The ammonia gas is used as the reducing agent in the production process, and is safer and more reliable than the hydrogen gas.
Drawings
FIG. 1(a) is a TEM photograph of a nano titanium dioxide-silicon nitride composite powder prepared in example 1
FIG. 1(b) is a TEM photograph of the nano-titanium nitride-silicon nitride composite powder prepared in example 1
Fig. 2 is a TEM photograph of the composite material prepared in example 1.
FIG. 3 is 25 vol% TiN-Si prepared in example 23N4SEM photograph of the fracture of the composite material.
Detailed Description
Detailed description of the preferred embodimentsthe following non-limiting examples further illustrate the embodiments and effects.
Example 1
20vol％TiN-Si3N4Preparation of composite materials
Taking 60g of butyl titanate, Si3N4Dissolving 23g of the powder in 1500ml of absolute ethanol solution, and mixing butyl titanate and Si3N4Under the condition of vigorous stirring, distilled water is added dropwise into the anhydrous ethanol solution of the powder, and the molar ratio of the butyl titanate to the distilled water is finally controlled as follows: ti: H2O is 1: 150. Hydrolyzing at 30 ℃, filtering the hydrolysis and precipitation product, washing with distilled water to remove impurities, washing twice with absolute ethyl alcohol, drying the filter cake at 120 ℃ for 8h, grinding, sieving with a 200-mesh sieve, and calcining at 450 ℃ for 2 h. Putting the obtained nano titanium dioxide-silicon nitride composite powder into a quartz crucible, putting the quartz crucible into a tubular atmosphere furnace, introducing ammonia gas, wherein the flow rate of the ammonia gas is 2 liters/minute, heating to 950 ℃, and the heating rate is 15 ℃/minute. The temperature was maintained at this temperature for 4 hours, and then, under flowing ammonia gas, the mixture was naturally cooled to room temperature. 33g of nano titanium nitride-silicon nitride composite powder was obtained. 1.2g of Al were added separately2O3And 2.68g Y2O3Dispersing the sintering aid and the prepared nano titanium nitride-silicon nitride composite powder in absolute ethyl alcohol as a sintering aid, performing ball milling and mixing for 24 hours, drying the mixed slurry at 120 ℃ for 8 hours, grinding and sieving by a 200-mesh sieve to obtain the nano titanium nitride-silicon nitride composite powder with the composition of 20 vol% TiN-72 vol% Si3N4-3vol％Al2O3-5vol％Y2O3The composite powder of (1). 25g of the composite powder is put into a graphite die coated with boron nitride and sintered and molded in a hot-pressing sintering furnace. The sintering temperature is 1650 ℃, the sintering pressure is 30MPa, and the sintering time is 60 min. Obtaining 20 vol% TiN-Si3N4Titanium nitride-silicon nitride composite materialAnd (5) feeding.
FIG. 1(a) is a TEM photograph of the nano-titania-silicon nitride composite powder prepared in this example;
(b) a TEM photograph of the nano titanium nitride-silicon nitride composite powder prepared in this example is shown. As can be seen from FIG. 1(a), the nano-titania particles are uniformly coated on the surface of the silicon nitride powder, and the particle size is about 10-15 nm. As can be seen from FIG. 1(b), the nano titanium nitride particles are uniformly coated on the surface of the silicon nitride powder, and the particle size is about 40-50 nm, which shows that the particle size of the titanium dioxide with smaller particles is increased when the titanium dioxide is converted into titanium nitride due to the high temperature during the nitridation process. Fig. 2 is a TEM photograph of the composite material prepared in this example. The high-strength and conductive titanium nitride-silicon nitride composite material prepared in this example had a bending strength of 1160MPa and a resistivity of: 0.25 omega cm.
Example 2
25vol％TiN-Si3N4Preparation of composite materials
Taking 77g of butyl titanate, Si3N4Dissolving 21.3g of powder in 2000ml of absolute ethanol solution, and mixing butyl titanate and Si3N4Under the condition of vigorous stirring, distilled water is added dropwise into the anhydrous ethanol solution of the powder, and the molar ratio of the butyl titanate to the distilled water is finally controlled as follows: ti: H2O is 1: 150. Hydrolyzing at 30 ℃, filtering the hydrolysis and precipitation product, washing with distilled water to remove impurities, washing twice with absolute ethyl alcohol, drying the filter cake at 100 ℃ for 12h, grinding, sieving with a 200-mesh sieve, and calcining at 450 ℃ for2 h. Putting the obtained nano titanium dioxide-silicon nitride composite powder into a quartz crucible, putting the quartz crucible into a tubular atmosphere furnace, introducing ammonia gas, wherein the flow rate of the ammonia gas is 2 liters/minute, heating to 950 ℃, and the heating rate is 15 ℃/minute. The temperature was maintained at this temperature for 4 hours, and then, under flowing ammonia gas, the mixture was naturally cooled to room temperature. 35.5g of nano titanium nitride-silicon nitride composite powder is obtained. 1.2g of Al were added separately2O3And 2.68g Y2O3As a sintering aid, dispersing the sintering aid and the prepared nano titanium nitride-silicon nitride composite powder in absolute ethyl alcohol, ball-milling and mixing for 20 hours, and drying the mixed slurry for 12 hours at 100 DEG CThen, the mixture is ground and sieved by a 200-mesh sieve to obtain the TiN-67 vol% Si with the composition of 25 vol% to 67 vol%3N4-3vol％Al2O3-5vol％Y2O3The composite powder of (1). 25g of the composite powder is put into a graphite die coated with boron nitride and sintered and molded in a hot-pressing sintering furnace. The sintering temperature is 1750 ℃, the sintering pressure is 30MPa, and the sintering time is 60min, thus obtaining 25 vol% TiN-Si3N4Titanium nitride-silicon nitride composite material.
FIG. 3 shows 25 vol% TiN-Si prepared in this example3N4SEM photograph of the fracture of the composite material shows that the fracture mode of the material is fracture along crystal.
The resistivity of the high-strength and conductive titanium nitride-silicon nitride composite material prepared in this example is: 0.11 omega cm.
Claims (7)
1. Preparation of nano TiN-Si3N4The method of the composite material comprises the technological processes of precipitation, nitridation, sintering additive selection and hot-pressing sintering, and is characterized in that:
(1) firstly, preparing anatase type nano TiO by heterogeneous precipitation method2-Si3N4Composite powder;
(2) from nano TiO2-Si3N4The composite powder is nitrided in situ to prepare titanium oxide-silicon nitride composite powder, and then nitrided in situ to prepare TiN-Si3N4Composite powder;
(3) adding Y2O3、Al2O3Additive to prepare TiN-Si3N4-Al2O3-Y2O3Composite powder;
(4) mixing TiN-Si3N4-Al2O3-Y2O3The composite powder is hot pressed and sintered to prepare high-strength and conductive TiO2-Si3N4A composite material; TiN/Si in composite material3N4＝5/87～25/67，Al2O3Is 3, Y2O3Is 5(All at vol%).
2. The method for preparing titanium nitride-silicon nitride composite material according to claim 1, wherein the anatase type nano titanium oxide-silicon nitride composite powder is prepared by: (1) titanium-containing compound and silicon nitride powder are used as main raw materials, and TiN/Si is adopted as raw materials3N4Preparing anhydrous ethanol solution according to the volume ratio of 5/87-25/67, adding distilled water dropwise under vigorous stirring, and hydrolyzing butyl titanate to obtain TiO2Finally, the molar ratio of the butyl titanate to the distilled water is controlled as follows: ti: H2O is 1: 150. (2) Filtering the product, washing twice with distilled water at normal temperature, washing twice with anhydrous ethanol, drying at 100-120 deg.C for 8-24 hr, and calcining at 500 deg.C for 2-4 hr.
3. The method of preparing a titanium nitride-silicon nitride composite material according to claim 2, wherein the titanium-containing compound is one of titanium tetrachloride, titanium sulfate, titanyl sulfate, metatitanic acid, butyl titanate, and isopropyl titanate.
4. A process for preparing a titanium nitride-silicon nitride composite material according to claim 2 or 3, characterized in that TiO2Is uniformly wrapped on Si3N4Surface of powder, TiO2The grain size is 10-15 nanometers.
5. The method for preparing titanium nitride-silicon nitride composite material as claimed in claim 1, wherein the conditions of in-situ nitridation of the nano titanium oxide-nitride composite powder to form the nano titanium nitride-composite powder are that under flowing ammonia gas with a flow rate of 0.5-5 l/min, a heating rate of 10-25 ℃/min, a heat preservation at 800-1000 ℃ for 2-5 hours, in-situ nitridation, and after the reaction, natural cooling to room temperature under flowing ammonia atmosphere.
6. The method for preparing a titanium nitride-silicon nitride composite material according to claim 5, wherein the TiN particles are uniformly coated after the in-situ nitridationWrapped in Si3N4The size of TiN crystal grains on the surface of the powder is 40-50 nanometers.
7. The method for preparing a titanium nitride-silicon nitride composite material according to claim 1, wherein the composition is TiN-Si3N4-Al2O3-Y2O3The composite powder is sintered in ammonia atmosphere, the sintering temperature is 1600-1800 ℃, the pressure is 30MPa, and the heat preservation time is 50-90 minutes.
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| EP1770075A1 (en) * | 2005-10-03 | 2007-04-04 | Oertli Werkzeuge AG | Ceramic matrix composite cutting blade for wood machining and the method of manufacturing the cutting blade |
| CN100408511C (en) * | 2006-08-11 | 2008-08-06 | 中国科学院上海硅酸盐研究所 | Method for preparing silicon nitride/titanium nitride nano composite material |
| CN100408510C (en) * | 2006-07-28 | 2008-08-06 | 东北大学 | Process of preparing heterogenous conducting Si3N4/Tin ceramic material tail iron ore |
| CN102584246A (en) * | 2012-03-09 | 2012-07-18 | 东北大学 | Silicon nitride based ceramic cutting tool material and preparation method thereof |
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| EP1770075A1 (en) * | 2005-10-03 | 2007-04-04 | Oertli Werkzeuge AG | Ceramic matrix composite cutting blade for wood machining and the method of manufacturing the cutting blade |
| WO2007038889A1 (en) * | 2005-10-03 | 2007-04-12 | Oertli Werkzeuge Ag | Ceramic matrix composite cutting blade for wood machining and the method of manufacturing the cutting blade |
| CN100408510C (en) * | 2006-07-28 | 2008-08-06 | 东北大学 | Process of preparing heterogenous conducting Si3N4/Tin ceramic material tail iron ore |
| CN100408511C (en) * | 2006-08-11 | 2008-08-06 | 中国科学院上海硅酸盐研究所 | Method for preparing silicon nitride/titanium nitride nano composite material |
| CN102584246A (en) * | 2012-03-09 | 2012-07-18 | 东北大学 | Silicon nitride based ceramic cutting tool material and preparation method thereof |
| CN102584246B (en) * | 2012-03-09 | 2014-04-02 | 东北大学 | Silicon nitride based ceramic cutting tool material and preparation method thereof |
| CN108395257A (en) * | 2018-05-18 | 2018-08-14 | 哈尔滨工业大学 | A kind of nitride silicon based composite material and preparation method thereof |
| CN112939609A (en) * | 2019-12-11 | 2021-06-11 | 新疆晶硕新材料有限公司 | Silicon nitride clamping cap, preparation method thereof and silicon core fixing assembly for polycrystalline silicon reduction furnace |
| CN114044682A (en) * | 2021-11-29 | 2022-02-15 | 上海材料研究所 | Method for preparing high-thermal-conductivity silicon nitride ceramic by water-based slurry gel injection molding |
| CN114149273A (en) * | 2021-12-28 | 2022-03-08 | 湖南省嘉利信陶瓷科技有限公司 | Preparation method of alumina ceramic powder for electronic ceramics |
| 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 |
| CN116693303A (en) * | 2023-03-31 | 2023-09-05 | 江苏东浦精细陶瓷科技股份有限公司 | TiN-Si 3 N 4 Near net shape forming method for composite material |
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