CN1237025C - 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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- CN1237025C CN1237025C CN 02150906 CN02150906A CN1237025C CN 1237025 C CN1237025 C CN 1237025C CN 02150906 CN02150906 CN 02150906 CN 02150906 A CN02150906 A CN 02150906A CN 1237025 C CN1237025 C CN 1237025C
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- si3n4
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Abstract
The present invention relates to a method for making a nanometer TiO2-Si3N4 composite material with high strength and high electric conductivity. The present invention is characterized in that anatase type nanometer TiO2-Si3N4 composite powder is firstly made by using the heterogeneous phase precipitation method; the nanometer TiO2-Si3N4 composite powder is azotized into titanium oxide-silicon nitride composite powder in an in-situ azotizing mode; TiN-Si3N4 composite powder is made in an in-situ azotizing mode; Y2O3 and Al2O3 used as additives are added to the TiN-Si3N4 composite powder so as to make TiN-Si3N4-Al2O3-Y2O3 composite powder; the TiN-Si3N4-Al2O3-Y2O3 composite powder is made into the TiO2-Si3N4 composite material with high strength and high electric conductivity in a hot pressing sintering mode; and in the TiO2-Si3N4 composite material, the ratio of TiN to Si3N4 is 5: 87 to 25: 67, Al2O3 accounts for 3% by volume, and Y2O3 accounts for 5% by volume. In TiO2-Si3N4 made by using the method, the volume ratio of TiN to Si3N4 is 5: 87 to 25: 67. When the content of TiN is 20 to 25% by volome, the electric conductivity of the TiO2-Si3N4 is the highest; after the in situ azotizing, TiN granules evenly wrap up the surfaces of Si3N4 granules, and the grain size is 40 to 50 nanometers and is smaller than that of the TiO2-Si3N4 composite material with the TiN content of 30 to 50% by volume, which is reported in literature.
Description
Technical field
The present invention relates to the preparation method of high strength, electroconductibility titanium nitride-silicon nitride composite material.
Background technology
Silicon nitride ceramics makes it become one of most important structural ceramic material because of it has good room temperature and hot strength and relative higher fracture toughness property.In addition, the hardness height of silicon nitride ceramics, thermal expansivity are little, anti-oxidant, wear-resistant, can be widely used as hot machine high-temperature component, and abrasive sealing materials and cutting tool etc. have broad application prospects in chemical industry, metallurgy, space flight and automotive industry.
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 resistance is 3.34 * 10
-7Ω .cm), can be used as electro-conductive materials such as the electrode of fused salt electrolysis and electrical contact.The second phase particle that in the silicon nitride matrix, adds electroconductibility, as TiN, TiC etc., not only can improve the toughness of body material, and the matrix material that can make preparation has the electroconductibility of metalloid, this matrix material has two big advantages, the first, this matrix material can adopt spark technology (Electical discharge machining) to come the ceramic product of manufacturing complex shapes, reduces processing charges significantly.The second, this matrix material can be used for high temperature heater (HTH), portfire, heat exchanger, wear-resisting and structure unit.Because TiN has lower coefficient of friction, TiN-Si
3N
4Matrix material is suitable for cutting tool very much, and its life-span is than simple Si
3N
4Material is much higher.
The electrical conduction mechanism of this matrix material is that the electroconductibility TiN particle that adds has formed conductive network in matrix, so, the size of the second phase conducting particles and quantity are the important factors that influences the conductivity of composite material energy, under the size of the particle preceding topic identical with quantity, conducting particles is uniformly dispersed in matrix and otherwise is the key factor that influences conductive network.Common complex method is with body material (Si
3N
4) with second mutually conducting particles (being generally a micron TiN) ball milling mix, the disadvantage of this method is to be difficult to make two kinds of materials to mix, usually cause the reunion of adding phase, or cause local component deviation, and when ball milling, easily bring impurity into, finally influence the mechanical property and the conductivity of matrix material.In-situ compositing can be avoided the problems referred to above.And adopt micron order TiN powder as the second phase conducting particles, and because the conducting particles size is bigger, needs to add relatively large TiN and could form conductive network, generally need the TiN of 30vol%, even up to 50vol%.Replace nano level titanium nitride to be expected can reduce the consumption of titanium nitride and can form more uniform conductive network with nano level titanium nitride, but the nano level titanium nitride is difficult to preparation, not useful so far nano level titanium nitride improves the report of silicon nitride ceramics conductivity.
Summary of the invention
The object of the present invention is to provide a kind of novel method for preparing high strength, electroconductibility titanium nitride-silicon nitride composite material.This preparation technology at first adopts heterogeneous precipitation method to prepare nano-TiO
2-Si
3N
4Composite granule adopts the nitridation in situ composite algorithm as raw material, preparation nano TiN-Si
3N
4Composite granule adopts Al
2O
3And Y
2O
3As sintering aid, after hot pressed sintering obtains titanium nitride-silicon nitride composite material.This material has characteristics such as component is evenly distributed, powder sintering is good, bending strength is high, electroconductibility height.
The objective of the invention is to implement like this: with titaniferous compound and beta-silicon nitride powder 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-silicon nitride; With this nano titanium oxide-silicon nitride composite powder in tubular react furnace, under mobile ammonia condition, high-temperature ammonolysis makes Nano titanium nitride-silicon nitride composite powder, the sintering aid that adds appropriate amount again, at last, make high strength, electroconductibility titanium nitride-silicon nitride composite material through hot pressed sintering.
Concrete enforcement can be divided into four and go on foot greatly:
The first step heterogeneous precipitation method prepares the composite granule of anatase-type nanometer titanium dioxide-silicon nitride; Second step was prepared into the composite granule nitridation in situ of nano titanium oxide-silicon nitride the composite granule of Nano titanium nitride-silicon nitride; The 3rd step added sintering aid in the composite granule of Nano titanium nitride-silicon nitride, mix through ball milling, and each component is mixed, and obtained the sintering powder.The 4th step hot pressed sintering prepares high strength, electroconductibility titanium nitride-silicon nitride composite material.Now details are as follows respectively:
One, heterogeneous precipitation method prepares anatase-type nanometer titanium dioxide-silicon nitride composite powder
Heterogeneous precipitation method is to obtain sedimentary a kind of preparation method fast by add precipitation agent in liquid phase medium.With titaniferous compound and beta-silicon nitride powder is raw material, by hydrolysis, precipitation, can obtain the precipitation of hydrated titanium dioxide-silicon nitride.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; These compounds are pressed TiN/Si
3N
4The ratio of (volume ratio)=5/87-25/67 is made into ethanol solution, under vigorous stirring, dropwise adds distilled water, finally controls the titanium of any one decomposition in the described titaniferous compound and the mol ratio of distilled water to be: Ti: H
2O=1: 150.
Hydrolysis, precipitin reaction are:
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-silicon nitride composite powder then.Titanium dioxide evenly is coated on the silicon nitride particle surface, average grain size 10-15 nanometer.
Two, the preparation of Nano titanium nitride-silicon nitride composite powder
With the anatase-type nanometer titanium dioxide-silicon nitride composite powder that obtains, put into quartz crucible, the tubular type of packing into atmosphere furnace, feed ammonia, ammonia flow is 0.5～5 liter/minute, is warming up to 800-1000 ℃, and temperature rise rate is 10～25 ℃/minute, under this temperature, be incubated 2～5 hours, reaction in, then, under the ammonia that flows, naturally cool to room temperature.Obtain Nano titanium nitride-silicon nitride composite powder, wherein TiN vol% is 5-25%.The TiN uniform crystal particles is coated on Si
3N
4The surface, average grain size 40-50 nanometer.
Three, the selection of sintering aid and adding
The present invention selects Al
2O
3And Y
2O
3As sintering aid, its add-on is respectively 3vol% and 5vol%, Nano titanium nitride-the silicon nitride composite powder of sintering aid and preparation is scattered in the dehydrated alcohol, ball milling mixing 12-24 hour, with mixed slurry at 100-120 ℃ of dry 8-24 hour, grind, cross 200 mesh sieves, obtain the different TiN-Si that form
3N
4-Al
2O
3-Y
2O
3Composite granule.Powder is formed as shown in table 1:
Table 1: the composition of powder
| Form | The 1# sample | The 2# sample | The 3# sample | The 4# sample | The 5# sample |
| TiN(vol％) | 5 | 10 | 15 | 20 | 25 |
| Si 3N 4(vol％) | 87 | 82 | 77 | 72 | 67 |
| Al 2O 3(vol％) | 3 | 3 | 3 | 3 | 3 |
| Y 2O 3(vol％) | 5 | 5 | 5 | 5 | 5 |
Four, the preparation of high strength, electroconductibility titanium nitride-silicon nitride composite material
The TiN-Si that consists of with preparation
3N
4-Al
2O
3-Y
2O
3Composite granule be raw material, a certain amount of composite granule is put into the graphite jig that scribbles boron nitride, sintering forms in hot-pressed sintering furnace.Sintering temperature is 1600-1800 ℃, and sintering pressure is 30MPa, and sintering time is 50-90min.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.In " background technology ", we have mentioned " TiN of relatively large (30-50vol%) could form conductive network ", and when having added 20-25vol%TiN in the matrix material of the present invention's preparation, specific conductivity has reached the numerical value that document is reported.Titanium nitride crystal grain is littler in the composite granule that this and nitridation in situ method provided by the invention prepare, and homogeneity is better, thereby conductive network is more effective relevant.
High strength provided by the invention, electroconductibility titanium nitride-silicon nitride composite material preparation method's characteristics are:
1. Zhi Bei Nano titanium nitride-silicon nitride composite powder sintering character is good, and component is evenly distributed, and nano TiN is of a size of the 40-50 nanometer.
2. the bending strength height of Zhi Bei titanium nitride-silicon nitride composite material.
3. the electroconductibility height of Zhi Bei titanium nitride-silicon nitride composite material; The TiN content that forms conductive network only is lower than the 30-50vol% value of bibliographical information for 20-25vol%.
4. use ammonia as reductive agent in the production process, than make reductive agent safety, reliable with hydrogen.
Description of drawings
Fig. 1 (a) is the TEM photo of the nano titanium oxide-silicon nitride composite powder of embodiment 1 preparation
Fig. 1 (b) is the TEM photo of the Nano titanium nitride-silicon nitride composite powder of embodiment 1 preparation
Fig. 2 is the TEM photo figure of the matrix material of embodiment 1 preparation.
Fig. 3 is the 25vol% TiN-Si of embodiment 2 preparations
3N
4The SEM photo of matrix material fracture.
Embodiment
Embodiment further specifies embodiment and effect with following indefiniteness embodiment.
Embodiment 1
20vol% TiN-Si
3N
4The preparation of matrix material
Get butyl (tetra) titanate 60g, Si
3N
4Powder 23g is dissolved in the 1500ml ethanol solution, with butyl (tetra) titanate and Si
3N
4The ethanol solution of powder under vigorous stirring, dropwise adds distilled water, and the mol ratio of finally controlling butyl (tetra) titanate and distilled water is: Ti: H
2O=1: 150.30 ℃ of hydrolysis, 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-the silicon nitride composite powder 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 Nano titanium nitride-silicon nitride composite powder 33g.Add 1.2g Al respectively
2O
3With 2.68g Y
2O
3As sintering aid, Nano titanium nitride-the silicon nitride composite powder of sintering aid and preparation is scattered in the dehydrated alcohol, and ball milling mixed 24 hours, with mixed slurry 120 ℃ of dryings 8 hours, grind, cross 200 mesh sieves, obtain consisting of 20vol% TiN-72vol% Si
3N
4-3vol% Al
2O
3-5vol% Y
2O
3Composite granule.This composite granule of 25g is put into the graphite jig that scribbles boron nitride, sinter molding in hot-pressed sintering furnace.Sintering temperature is 1650 ℃, and sintering pressure is 30MPa, and sintering time is 60min.Obtain 20vol% TiN-Si
3N
4Titanium nitride-silicon nitride composite material.
Fig. 1 (a) is the TEM photo of the nano titanium oxide-silicon nitride composite powder of present embodiment preparation;
(b) be the TEM photo of the Nano titanium nitride-silicon nitride composite powder of present embodiment preparation.Can see that from Fig. 1 (a) titanium dioxide nanoparticle is coated on the silicon nitride powder surface uniformly, particle diameter is about the 10-15 nanometer.From Fig. 1 (b), can see the evengranular silicon nitride powder surface that is coated on of Nano titanium nitride, particle diameter is about the 40-50 nanometer, illustrates in nitridation process, because action of high temperature, the less titanium dioxide of particle is when changing into titanium nitride, and it is big that particle grain size becomes.Fig. 2 is the TEM photo of the matrix material of present embodiment preparation.The high strength of present embodiment preparation, the bending strength of electroconductibility titanium nitride-silicon nitride composite material are that 1160MPa, resistivity are: 0.25 Ω .cm.
Embodiment 2
25vol% TiN-Si
3N
4The preparation of matrix material
Get butyl (tetra) titanate 77g, Si
3N
4Powder 21.3g is dissolved in the 2000ml ethanol solution, with butyl (tetra) titanate and Si
3N
4The ethanol solution of powder under vigorous stirring, dropwise adds distilled water, and the mol ratio of finally controlling butyl (tetra) titanate and distilled water is: Ti: H
2O=1: 150.30 ℃ of hydrolysis, hydrolysis, precipitated product are filtered, use distilled water wash, remove impurity, use the absolute ethanol washing secondary again, filter cake at 100 ℃ of oven dry 12h, is ground, crosses 200 mesh sieves, then 450 ℃ of calcining 2h.Nano titanium oxide-the silicon nitride composite powder 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 Nano titanium nitride-silicon nitride composite powder 35.5g.Add 1.2g Al respectively
2O
3With 2.68g Y
2O
3As sintering aid, Nano titanium nitride-the silicon nitride composite powder of sintering aid and preparation is scattered in the dehydrated alcohol, and ball milling mixed 20 hours, with mixed slurry 100 ℃ of dryings 12 hours, grind, cross 200 mesh sieves, obtain consisting of 25vol% TiN-67vol% Si
3N
4-3vol% Al
2O
3-5vol% Y
2O
3Composite granule.This composite granule of 25g is put into the graphite jig that scribbles boron nitride, sinter molding in hot-pressed sintering furnace.Sintering temperature is 1750 ℃, and sintering pressure is 30MPa, and sintering time is 60min, obtains 25vol% TiN-Si
3N
4Titanium nitride-silicon nitride composite material.
Fig. 3 is the 25vol% TiN-Si of present embodiment preparation
3N
4The SEM photo of matrix material fracture, the fracture mode that can see material from photo is for rupturing along brilliant.
The high strength of present embodiment preparation, the resistivity of electroconductibility titanium nitride-silicon nitride composite material are: 0.11 Ω .cm.
Claims (5)
1, a kind of preparation nano level TiN-Si
3N
4The method of matrix material comprises the selected and hot-pressing sintering technique process of precipitation, nitrogenize, sinter additives, it is characterized in that:
(1) at first prepares anatase type nano TiO with heterogeneous precipitation method
2-Si
3N
4Composite granule;
(2) by nano-TiO
2-Si
3N
4The composite granule nitridation in situ is made TiN-Si
3N
4Composite granule;
(3) add Y
2O
3, Al
2O
3Additive is made TiN-Si
3N
4-Al
2O
3-Y
2O
3Composite granule;
(4) with TiN-Si
3N
4-Al
2O
3-Y
2O
3The composite granule hot pressed sintering and make the TiN-Si of high strength, electroconductibility
3N
4Matrix material; TiN and Si in the matrix material
3N
4The percent by volume ratio be 5/87～25/67, Al
2O
3Be 3 volume %, Y
2O
3Be 5 volume %.
2, by the described method for preparing titanium nitride-silicon nitride composite material of claim 1, the preparation that it is characterized in that anatase type nano titanium oxide-silicon nitride composite powder is: (1) utilizes any one titaniferous compound and the beta-silicon nitride powder in titanium tetrachloride, titanium sulfate, titanyl sulfate, metatitanic acid, butyl (tetra) titanate, the isopropyl titanate to be main raw material, presses TiN and Si
3N
4Percent by volume than being made into ethanol solution for the ratio of 5/87-25/67, under vigorous stirring, dropwise add distilled water, make described titanium-containing compound generation hydrolysis, generation TiO
2, finally control the Ti that decomposes in the described titanium-containing compound and the mol ratio of distilled water and be: Ti: H
2O=1: 150; (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 described method for preparing titanium nitride-silicon nitride composite material of claim 2, it is characterized in that TiO
2Evenly be wrapped in Si
3N
4Powder surface, TiO
2Grain-size 10-15 nanometer.
4, by the described method for preparing titanium nitride-silicon nitride composite 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-silicon nitride composite powder nitridation in situ becomes the condition of Nano titanium nitride-silicon nitride composite powder, temperature rise rate is 10-25 ℃/minute, under the 800-1000 ℃ of temperature under 2-5 hour condition of insulation, nitridation in situ, the reaction back naturally cools to room temperature under the ammonia atmosphere that flows.
5, by the described method for preparing titanium nitride-silicon nitride composite material of claim 4, it is characterized in that nitridation in situ after the TiN uniform particles be wrapped in Si
3N
4Powder surface, TiN grain-size 40-50 nanometer.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11332408B2 (en) * | 2019-04-01 | 2022-05-17 | China Nonferrous Metals (Guinlin) Geology And Mining Co., Ltd. | Al2O3—ZrO2—Y2O3—TiN nanocomposite ceramic powder 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 |
| 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 |
| CN102584246B (en) * | 2012-03-09 | 2014-04-02 | 东北大学 | Silicon nitride based ceramic cutting tool material and preparation method thereof |
| CN108395257B (en) * | 2018-05-18 | 2021-04-02 | 哈尔滨工业大学 | Silicon nitride-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 |
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| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| US11332408B2 (en) * | 2019-04-01 | 2022-05-17 | China Nonferrous Metals (Guinlin) Geology And Mining Co., Ltd. | Al2O3—ZrO2—Y2O3—TiN nanocomposite ceramic powder and preparation method thereof |
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