CN110002880A - The preparation method of oxygen-containing non-stoichiometric titanium nitride material - Google Patents

The preparation method of oxygen-containing non-stoichiometric titanium nitride material Download PDF

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CN110002880A
CN110002880A CN201910289252.3A CN201910289252A CN110002880A CN 110002880 A CN110002880 A CN 110002880A CN 201910289252 A CN201910289252 A CN 201910289252A CN 110002880 A CN110002880 A CN 110002880A
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oxygen
tin
temperature
titanium nitride
powder
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邹芹
李艳国
王明智
熊建超
赵玉成
罗文奇
袁东方
娄志超
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Yanshan University
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/58007—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides
    • C04B35/58014—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on refractory metal nitrides based on titanium nitrides, e.g. TiAlON
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/38—Non-oxide ceramic constituents or additives
    • C04B2235/3895—Non-oxides with a defined oxygen content, e.g. SiOC, TiON

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Abstract

The present invention discloses a kind of preparation method of oxygen-containing non-stoichiometric titanium nitride material, specifically includes the following steps: S1, TiNx powder is laid in alumina crucible bottom, is put into Muffle furnace, wherein 0.3≤x≤1.1；Muffle furnace is warming up to 300~700 DEG C；5~30min is kept the temperature after rising to set temperature；It takes out later and is air-cooled to room temperature, uniformly oxygen-containing TiNx material, oxygen-containing TiN is madexMaterial includes TiNxOy、A‑TiO2、R‑TiO2At least one of；S2, oxygen-containing TiNx mixture is entered in graphite grinding tool, pre-molding, pre-molding sample is subjected to high temperature and pressure sintering in cubic hinge press, sintering temperature is 800~1100 DEG C, pressure is 4-7GPa, keeps the temperature 5~30min, obtains oxygen-containing non-stoichiometric titanium nitride sintered body.Preparation process of the present invention is simple, during Muffle stove heating, by control heating temperature and soaking time to change the oxygen content in product, further changes the ingredient of the oxygen-containing non-stoichiometric titanium nitride material ultimately generated, and oxygen-containing TiNxThe sintering temperature of material is compared with TiNxIt is low.

Description

The preparation method of oxygen-containing non-stoichiometric titanium nitride material
Technical field
The invention belongs to technical field of material, are related to a kind of preparation side of oxygen-containing non-stoichiometric titanium nitride material Method.
Background technique
The excellent characteristics of TiN is highly suitable as the bonding agent of PcBN cutter material.But conventional Ti N powder needs are higher Sintering temperature just sinterable densification, and sintered body mechanical performance does not reach requirement.Xu Shuai makes TiN1-x in its research Powder can successful sintering densification at a lower temperature, while the mechanical performance of sintered body is improved [Xu Shuai .TiN1-x It is reacted with covalent compound interface region and PcBN preparation research [D] University On The Mountain Of Swallows, 2015].Sun Jinfeng respectively to TiN and TiNx carries out antioxygenic property test, TiN initial oxidation temperature (487 DEG C) [Sun Jinfeng .MA preparation lower than (314 DEG C) of TiNx Research [D] the University On The Mountain Of Swallows of non-stoichiometric TiCx and TiNx and its sintering characteristic, 2010].ZhangYong et al. is to TiN The oxidation process of the research discovery TiN of coating antioxygenic property is exactly the process that O atom is spread in TiN in fact, certain when reaching When temperature, O atom enters TiN lattice, forms interstitial atom, then causes Ti-N key to be broken, N atom site is occupied, with Ti Atom combines and forms TiNxOy, when N atom is replaced completely by O atom, form TiO2[ZhangYong,Zhao Guangbing, Hou Lei,ZhangXinyuan,SunAixiang.Oxidationresistance ofTiN coating onthe surface ofcemented carbide byhot cathode on plating[J].Journal ofXihuaUniversityNatural Science,2010,(29):69-73].Du Shudi, which has studied, utilizes magnetron sputtering system Standby TiN/TiNxOyFilm, N atom and O atom can be replaced mutually with arbitrary proportion forms solid solution TiNxOy, due to excessive O Atom spreads the ordered structure before destroying in TiN, causes O atom to arrange in TiN and loses order to be formed Amorphous TiNxOy[Du Shudi .MAO oxide layer base TiNxOyResearch [D] the Xi'an University of Technology of film color and performance, 2014]。
Currently, the oxygen-containing TiN of non-stoichiometric titanium nitride material is madexOySintering temperature is higher, and preparation method is multiple It is miscellaneous, hardly possible manipulation.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparation side of oxygen-containing non-stoichiometric titanium nitride material Method prepares the TiNx material of different oxygen by changing heating temperature and soaking time, reduces the sintering temperature of TiNx.
The present invention is implemented as follows:
A kind of preparation method of oxygen-containing non-stoichiometric titanium nitride material, specifically includes the following steps:
S1, by TiNxPowder is laid in alumina crucible bottom, is put into Muffle furnace, wherein 0.3≤x≤1.1；By Muffle Furnace is warming up to 300~700 DEG C；5~30min is kept the temperature after rising to set temperature；It takes out later and is air-cooled to room temperature, be made uniformly oxygen-containing TiNxMaterial, the oxygen-containing TiNxMaterial includes TiNxOy、A-TiO2、R-TiO2At least one of, wherein 0 < y < 1；
S2, by oxygen-containing TiNxMixture enters in graphite grinding tool, pre-molding, by pre-molding sample cubic hinge press into The sintering of row high temperature and pressure, sintering temperature are 800~1100 DEG C, and pressure is 4~7GPa, keep the temperature 5~30min, obtain oxygen-containing non-ization It learns metering and compares titanium nitride material.
Preferably, the TiNxThe size of powder is nanoscale.
Preferably, TiNxThe crystallite dimension of powder is 50nm.
Preferably, the heating rate of Muffle furnace is 10~50 DEG C/min in step S1.
Preferably, the pressure of pre-molding is 3~10MPa.
Compared with prior art, the invention has the following advantages:
The present invention is with nanoscale TiNxPowder is raw material, Muffle stove heating is used under air atmosphere, in TiNxIn powder Oxygen element is introduced, due to TiNxThere are the vacancy N of high concentration in crystal grain, O atom occupies N atom site, is formed amorphous TiNxOy、A-TiO2Or R-TiO2.During Muffle stove heating, is changed by control heating temperature and soaking time and produced Oxygen content in object further changes the ingredient of the oxygen-containing non-stoichiometric titanium nitride material ultimately generated, obtained oxygen-containing The content of oxygen element is between 5~40% in non-stoichiometric titanium nitride material, and oxygen-containing non-stoichiometric nitrogenizes titanium The sintering temperature of material is compared with TiNxIt is low.
Detailed description of the invention
Fig. 1 is TiN0.3XRD diagram of the powder after different heating temperature, the oxidation of identical soaking time；
Fig. 2 is TiN0.3XRD diagram of the powder after 350 DEG C, different soaking time oxidations；
Fig. 3 is oxygen-containing TiN0.3XRD diagram of the sintered body in the different sintered heat insulating times；
Fig. 4 be oxidation after with unoxidized TiN0.3In different sintering temperatures, pressure 5GPa/ keeps the temperature the cause of 10min sintered body Density map；
Fig. 5 be oxidation after with unoxidized TiN0.3In different sintering temperatures, pressure 5GPa/ keeps the temperature the hard of 10min sintered body Degree figure；
Fig. 6 be oxidation after with unoxidized TiN0.3In different sintering temperatures, pressure 5GPa/ keeps the temperature the disconnected of 10min sintered body Split toughness figure.
Specific embodiment
Below with reference to the attached drawing exemplary embodiment that the present invention will be described in detail, feature and aspect of performance.
A kind of preparation method of oxygen-containing non-stoichiometric titanium nitride material, specifically includes the following steps:
S1, the TiN for being 50nm by crystallite dimensionxPowder is laid in alumina crucible bottom, is put into Muffle furnace, wherein 0.3≤x≤1.1；Muffle furnace is warming up to 300~700 DEG C；Heating rate is 10~50 DEG C/min, is protected after rising to set temperature 5~30min of temperature；It takes out later and is air-cooled to room temperature, uniformly oxygen-containing TiN is madexMaterial, the oxygen-containing TiNxMaterial includes TiNxOy、 A-TiO2、R-TiO2At least one of, wherein 0 < y < 1；
S2, by oxygen-containing TiNxMixture enters in graphite grinding tool, with the pressure pre-molding of 3~10MPa, by pre-molding Sample cubic hinge press carry out high temperature and pressure sintering, sintering temperature be 800~1100 DEG C, pressure be 4~7GPa, heat preservation 5~ 30min obtains oxygen-containing non-stoichiometric titanium nitride material.The final oxygen-containing non-stoichiometric obtained of the present invention nitrogenizes titanium Material is TiNxOy、A-TiO2Or R-TiO2, specific ingredient is true according to the heating temperature and soaking time of the Muffle furnace of step S1 It is fixed.
Embodiment 1
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 300 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 300 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (b) institute Show.
Embodiment 2
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 330 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 330 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (c) institute Show.
Embodiment 3
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 360 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 360 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (d) institute Show.
Embodiment 4
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 400 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 400 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (e) institute Show.
Embodiment 5
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 430 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 430 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (f) institute Show.
Embodiment 6
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 460 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 460 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (g) institute Show.
Embodiment 7
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 500 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 500 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (h) institute Show.
Embodiment 8
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 530 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 530 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (i) institute Show.
Embodiment 9
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 560 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 560 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (j) institute Show.
Embodiment 10
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 600 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 600 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (k) institute Show.
Embodiment 11
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 630 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 630 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (l) institute Show.
Embodiment 12
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 660 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 660 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (m) institute Show.
Embodiment 13
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 700 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 700 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, as shown in figure 1 (n) institute Show.
Fig. 1 is TiN0.3Powder is in 300~700 DEG C of (10 DEG C/min of heating rate；Soaking time 10min) oxidation after XRD Figure: (a) curve is TiN0.3Powder；(b) curve when being 300 DEG C of heating temperature of embodiment 1；It (c) is the heating of embodiment 2 Curve at 330 DEG C of temperature；(d) curve when being 360 DEG C of heating temperature of embodiment 3；It (e) is the heating temperature of embodiment 4 Curve at 400 DEG C；(f) curve when being 430 DEG C of heating temperature of embodiment 5；It (g) is 460 DEG C of heating temperature of embodiment 6 When curve；(h) curve when being 500 DEG C of heating temperature of embodiment 7；(i) when being 530 DEG C of heating temperature of embodiment 8 Curve；(j) curve when being 560 DEG C of heating temperature of embodiment 9；(k) song when being 600 DEG C of heating temperature of embodiment 10 Line；(l) curve when being 630 DEG C of heating temperature of embodiment 11；(m) curve when being 660 DEG C of heating temperature of embodiment 12； (n) curve when being 700 DEG C of heating temperature of embodiment 13.
From the atlas analysis of Fig. 1 it can be concluded that TiN0.3Powder aoxidizes in air is probably divided into three steps:
Start to generate TiN after i.e. 330 DEG C of heating temperaturexOy, start after 360 DEG C to generate A-TiO2, start to generate after 460 DEG C R-TiO2。
Embodiment 14
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 5min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, (a) institute in Fig. 2 Show.
Embodiment 15
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, (b) institute in Fig. 2 Show.
Embodiment 16
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 15min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, (c) institute in Fig. 2 Show.
Embodiment 17
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 20min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, (d) institute in Fig. 2 Show.
Embodiment 18
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 25min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, (e) institute in Fig. 2 Show.
Embodiment 19
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 30min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, and to oxygen-containing TiN obtained0.3Material carries out material phase analysis, (f) institute in Fig. 2 Show.
Fig. 2 is TiN0.3Powder is in 350 DEG C of (10 DEG C/min of heating rate；5~30min of soaking time) oxidation after XRD Figure: being (a) curve of the soaking time 5min of embodiment 14；It (b) is the curve of the soaking time 10min of embodiment 15；(c) it is The curve of the soaking time 15min of embodiment 16；It (d) is the curve of the soaking time 20min of embodiment 17；It (e) is embodiment The curve of 18 soaking time 25min；It (f) is the curve of the soaking time 30min of embodiment 19.It can be seen from the figure that A large amount of O atom diffuses into TiN in 350 DEG C of air0.3Lattice fills the vacancy N, and occupies interstitial void so as to cause in lattice Orderly atomic arrangement becomes disordering, according to diffusion process it is found that oxygen element content contains at gradient distribution, outside oxygen in particle Amount is higher than inside, i.e. these amorphous TiNxOyIt is mainly distributed on the outside of powder granule and wraps up particle, inside TiN0.3。
Embodiment 20
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 1000 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 5min；It is oxygen-containing to what is obtained TiN0.3Sintered body carries out material phase analysis, as shown in Fig. 3 (a).
Embodiment 21
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 1000 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 10min；It is oxygen-containing to what is obtained TiN0.3Sintered body carries out material phase analysis, as shown in Fig. 3 (b).
Embodiment 22
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 1000 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 15min；It is oxygen-containing to what is obtained TiN0.3Sintered body carries out material phase analysis, as shown in Fig. 3 (c).
Embodiment 23
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 1000 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 20min；It is oxygen-containing to what is obtained TiN0.3Sintered body carries out material phase analysis, as shown in Fig. 3 (d).
Embodiment 24
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 1000 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 25min；It is oxygen-containing to what is obtained TiN0.3Sintered body carries out material phase analysis, as shown in Fig. 3 (e).
Embodiment 25
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 1000 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 30min；It is oxygen-containing to what is obtained TiN0.3Sintered body carries out material phase analysis, as shown in Fig. 3 (f).
Fig. 3 is oxygen-containing TiN0.3(1000 DEG C of sintering temperature of sintered body；Pressure 5GPa；Keep the temperature 5~30min) XRD diagram: (a) The curve that the sintered heat insulating time for embodiment 20 is 5min；(b) be embodiment 21 the sintered heat insulating time be 10min song Line；(c) be embodiment 22 the sintered heat insulating time be 15min curve；It (d) is sintered heat insulating time of embodiment 23 to be The curve of 20min；(e) be embodiment 24 the sintered heat insulating time be 25min curve；It (f) is the sintered heat insulating of embodiment 25 Time is the curve of 30min.
The oxygen-containing TiN that sintered body uses0.3Powder is to be heated to 350 DEG C of soaking time 10min (heating rates in Muffle furnace 10 DEG C/min) made from TiNxOy。TiNxOyR-TiO is further fully converted under high temperature sintering2, with TiN0.3Powder exists The extension of oxidization time in Muffle furnace, oxygen content increases in powder, and the oxide content of the Ti generated under high temperature increases, that is, works as powder In body when oxygen element content abundance, the oxidation product of sintered body is R-TiO2, so heating temperature and heat preservation in Muffle furnace Time is to determine oxygen-containing TiNxThe deciding factor of the ultimate constituent of material and key of the invention.
Embodiment 26
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 900 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 10min, oxygen-containing TiN is made0.3 Sintered body.
Embodiment 27
The TiN for being 50nm by 1g crystallite dimension0.3Powder is laid in alumina crucible bottom, is put into Muffle in Muffle furnace Furnace is warming up to 350 DEG C；Heating rate is 10 DEG C/min, and 10min is kept the temperature after rising to 350 DEG C, takes out be air-cooled to room temperature later, obtain Oxygen-containing non-stoichiometric titanium nitride material, by TiN0.3Powder is placed in graphite jig, the pre-molding under the pressure of 10MPa； High temperature and pressure sintering is carried out in cubic hinge press, 800 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 10min, oxygen-containing TiN is made0.3 Sintered body.
Embodiment 28
The TiN for being 50nm by 1g crystallite dimension0.3Powder is not oxidation-treated, is placed in graphite jig, in the pressure of 10MPa Pre-molding under power；High temperature and pressure sintering is carried out in cubic hinge press, 800 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 10min, Oxygen-containing TiN is made0.3Sintered body.
Embodiment 29
The TiN for being 50nm by 1g crystallite dimension0.3Powder is not oxidation-treated, is placed in graphite jig, in the pressure of 10MPa Pre-molding under power；High temperature and pressure sintering is carried out in cubic hinge press, 900 DEG C of sintering temperature, pressure 5GPa, keeps the temperature 10min, Oxygen-containing TiN0.3Sintered body is made.
Embodiment 30
The TiN for being 50nm by 1g crystallite dimension0.3Powder is not oxidation-treated, is placed in graphite jig, in the pressure of 10MPa Pre-molding under power；High temperature and pressure sintering is carried out in cubic hinge press, 1000 DEG C of sintering temperature, pressure 5GPa, is kept the temperature Oxygen-containing TiN is made in 10min0.3Sintered body.
Fig. 4, Fig. 5, Fig. 6 be respectively aoxidize after with unoxidized TiN0.3In different sintering temperatures, pressure 5GPa/ heat preservation Consistency figure, hardness figure, the fracture toughness figure of 10min sintered body.TiN after aoxidizing as seen from the figure0.3Sintering at 900 DEG C Body consistency, hardness, fracture toughness with unoxidized TiN0.3Sintered density at 1000 DEG C is close, it was demonstrated that after oxidation TiN0.3Reduce sintering temperature.
Referring to XRD spectrum, using K value method to XRD diffraction maximum carry out integral and with the RIR that checks in substance phase in sintered body Value, and then calculate the relative amount (wt.%) of homologue phase.Therefore oxide is TiO2, it can further be converted The oxygen element content obtained afterwards is between 5~40%.
To sum up, the invention has the following advantages that
The present invention is with nanoscale TiNxPowder is raw material, Muffle stove heating is used under air atmosphere, in TiNxIn powder Oxygen element is introduced, due to TiNxThere are the vacancy N of high concentration in crystal grain, O atom occupies N atom site, is formed amorphous TiNxOy、A-TiO2Or R-TiO2.During Muffle stove heating, is changed by control heating temperature and soaking time and produced Oxygen content in object further changes the ingredient of the oxygen-containing non-stoichiometric titanium nitride material ultimately generated, obtained oxygen-containing The content of oxygen element is between 5~40% in non-stoichiometric titanium nitride material, and oxygen-containing non-stoichiometric nitrogenizes titanium The sintering temperature of material is compared with TiNxIt is low.
Finally, it should be noted that above-described each embodiment is merely to illustrate technical solution of the present invention, rather than it is limited System；Although the present invention is described in detail referring to the foregoing embodiments, those skilled in the art should understand that: its It can still modify to technical solution documented by previous embodiment, or part of or all technical features are carried out Equivalent replacement；And these modifications or substitutions, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution Range.

Claims (5)

1. a kind of preparation method of oxygen-containing non-stoichiometric titanium nitride material, it is characterised in that: itself specifically includes the following steps:
S1, by TiNxPowder is laid in alumina crucible bottom, is put into Muffle furnace, wherein 0.3≤x≤1.1；By Muffle furnace liter Temperature is to 300~700 DEG C；5~30min is kept the temperature after rising to set temperature；It takes out later and is air-cooled to room temperature, uniformly oxygen-containing TiN is madex Material, the oxygen-containing TiNxMaterial includes TiNxOy、A-TiO2、R-TiO2At least one of, wherein 0 < y < 1；
S2, by oxygen-containing TiNxMixture enters in graphite grinding tool, pre-molding, and pre-molding sample is carried out height in cubic hinge press Warm high-pressure sinter, sintering temperature are 800~1100 DEG C, pressure 4-7GPa, keep the temperature 5~30min, obtain containing oxygen nonstochiometry Than titanium nitride sintered body.
2. the preparation method of oxygen-containing non-stoichiometric titanium nitride material according to claim 1, it is characterised in that: described TiNxThe size of powder is nanoscale.
3. the preparation method of oxygen-containing non-stoichiometric titanium nitride material according to claim 2, it is characterised in that: TiNx The crystallite dimension of powder is 50nm.
4. the preparation method of oxygen-containing non-stoichiometric titanium nitride material according to claim 1, it is characterised in that: step The heating rate of Muffle furnace is 10~50 DEG C/min in S1.
5. the preparation method of oxygen-containing non-stoichiometric titanium nitride material according to claim 1, it is characterised in that: precompressed Molding pressure is 3~10MPa.
CN201910289252.3A 2019-04-11 2019-04-11 The preparation method of oxygen-containing non-stoichiometric titanium nitride material Pending CN110002880A (en)

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Citations (2)

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CN105565815A (en) * 2015-11-27 2016-05-11 陕西环珂生物科技有限公司 Method for preparing porous titanium nitride ceramics
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Publication number Priority date Publication date Assignee Title
CN105565815A (en) * 2015-11-27 2016-05-11 陕西环珂生物科技有限公司 Method for preparing porous titanium nitride ceramics
CN107434406A (en) * 2017-09-11 2017-12-05 河北建材职业技术学院 Nanocrystalline α Al2O3With the preparation method of titanium nitride composite material

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