CN101367511B - Method for preparing non-stoichiometry ratio nano TiNx with reaction ball milling method - Google Patents
Method for preparing non-stoichiometry ratio nano TiNx with reaction ball milling method Download PDFInfo
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- CN101367511B CN101367511B CN2008100555495A CN200810055549A CN101367511B CN 101367511 B CN101367511 B CN 101367511B CN 2008100555495 A CN2008100555495 A CN 2008100555495A CN 200810055549 A CN200810055549 A CN 200810055549A CN 101367511 B CN101367511 B CN 101367511B
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Abstract
The invention relates to a method for preparing the nonstoichiometry TiNx powder, which adopts the steps: Ti powder with the purity being more than 99.5 percent and the granularity being less than 10micrometers are mixed with analytically pure urea at a mol ratio of 3:1 to 4:1, and is filled into a ball-milling tank of a ball-milling machine; the mixture is sealed with a milling ball inside the ball-milling tank under the condition of the argon environment or under the condition of the atmosphere; the ratio between the ball and the mixture is 10:1 to 30:1, and the ball milling time is 30 to 70 hours. The Ti powder and the urea are ball milled at the room temperature in the way of the reaction ball milling way, so that the nanometer nonstoichiometry TiNx powder with the grain fineness being less than 10 nm is prepared. The powder phase is formed a single TiNx; when the mol ratio between the Ti powder and the urea is 3:1, the atom ratio Ti: N of the obtained TiNx is 1:0.59, namely, x isequal to 0.59; when the mol ratio between the Ti powder and the urea is 4:1, the atom ratio Ti: N of the obtained TiNx is 1:0.46, namely, x is equal to 0.46. The present invention has simple craftwork, and has low requirements on the device and the purity of the raw materials, and has less energy consumption and low cost. When the rotation velocity of the ball milling machine is improved, the ball milling reaction time can be shortened.
Description
Technical field
The present invention relates to a kind of synthetic method of TiN powder, particularly relate to a kind of reaction ball milling legal system and be equipped with the non-stoichiometric nano TiN
xThe method of powder.
Background technology
The synthetic method of TiN powder is a lot, and traditional method comprises metallic titanium powder or TiH
2Direct nitridation method, TiO
2The carbon reduction nitriding, the self propagating high temperature synthesis method.These method synthesis temperature height, usually more than 1000 ℃, therefore the crystal grain of the TiN powder that is synthesized is thick, and direct nitridation method and carbon reduction nitriding energy consumption height.Utilize microwave carbothermic method and mechanical alloying method can synthesize the tiny TiN of crystal grain.But complex process, equipment price costliness that the microwave carbothermic method is used.The organic solvent that utilizes hexagonal boron nitride (hBN) or contain N is that the N source and the Ti sphere of powder grind fully that TiN introduces TiB easily
2Or the difficult impurity of removing such as TiC, and at mobile N
2Or NH
3Ball milling Ti powder prepares the ball mill that the TiN powder needs particular design usually under the atmosphere.
Summary of the invention
In order to overcome the prior art above shortcomings, the invention provides a kind of reaction ball milling legal system and be equipped with the non-stoichiometric nano TiN
xThe method of powder, described method utilize the reaction ball milling method that Ti powder and urea are at room temperature carried out ball milling, the nano TiN of the non-stoichiometric of preparation
xGrain fineness number＜the 10nm of powder, the powder phase composite is single TiN
x
This reaction ball milling legal system is equipped with the non-stoichiometric nano TiN
xThe method of powder, its concrete steps are as follows:
(1) the Ti powder of purity＞99.9%, granularity＜10 μ m and analytical pure urea are mixed in molar ratio at 3～4: 1, as abrasive material;
(2) at ambient temperature, abrasive material and abrading-ball are packed among the ball grinder of ball mill simultaneously, the mass ratio of abrading-ball and abrasive material is 10～30: 1;
(3) after filling finishes, ball milling cover lid tightly and with mechanical pump is vacuumized, feed argon gas afterwards, once more the argon gas and the residual air that feed are found time, and then the feeding argon gas, so carry out 3～5 times, at last ball grinder is full of argon gas, seal aspirating hole then, to guarantee that no oxygen participates in reaction in the mechanical milling process; If above-mentioned filling step is carried out, just do not need to carry out above-mentioned finding time and the applying argon gas process in being full of the environment of argon gas;
(4) ball grinder after will loading and seal places and begins ball milling on the ball mill, and the ball milling time is 30～70 hours, and mechanical milling process at room temperature carries out;
(5) taking-up is through the material of ball milling from ball grinder under the argon gas condition, and through soaked in absolute ethyl alcohol, so that make remaining organism dissolving, the process seasoning finally obtains non-stoichiometric TiN
xPowder.
The nano TiN of the non-stoichiometric of described method preparation
xGrain fineness number＜the 10nm of powder, the powder phase composite is single TiN
x, when Ti powder and urea in the time of 3: 1 in molar ratio, gained TiN
xTi: the N atomic ratio is 1: 0.59, i.e. x=0.59; When Ti powder and urea in the time of 4: 1 in molar ratio, gained TiN
xTi: the N atomic ratio is 1: 0.46, i.e. x=0.46.
The invention has the beneficial effects as follows: the synthesis temperature of this invention low (room temperature), energy consumption are little, equipment and technology is simple, impurity is easily removed, synthetic TiN
xPowder grain is less than＜10nm.With N
2And NH
3Compare, urea is cheap, and because urea is solid at normal temperatures and pressures, under the standard state equal volume situation, the nitrogen content of urea is N
2498.4 times, be NH
3996.8 times, so need not to feed mobile N in the mechanical milling process
2Or NH
3, low for equipment requirements.Simultaneously, the TiN of acquisition
xPowder is a non-stoichiometric, has excellent activity, very helps sintering.
Description of drawings
Fig. 1 is that GN-2 type ball mill ball milling Ti and N mol ratio are the XRD spectra of powder behind 3: 1 different times;
Fig. 2 is that Ti and urea mol ratio are the XRD spectra of powder after the ball milling vacuum annealing in 3: 1,70 hours;
Fig. 3 is that Ti and urea mol ratio are 3: 1, the TEM photo of powder behind 70 hours ball millings, (a): the low power bright field image; (b): the intensified image in rectangle " A " zone among the figure (a); (c): the selected area electron diffraction style in " B " zone among the figure (b); (d): by scheming the dark field image that diffraction ring forms in " C " zone in (c);
Fig. 4 is that Ti and urea mol ratio are 3: 1, the EELS spectrogram of powder behind 70 hours ball millings;
Fig. 5 is that P4 type ball mill ball milling Ti and urea mol ratio are 3: 1, and the XRD spectra of back powder is handled in 30 hours ball millings and vacuum annealing;
Fig. 6 is that GN-2 type ball mill ball milling Ti and urea mol ratio are the XRD spectra of powder behind 4: 1 different times.
Embodiment
Embodiment 1
After Ti powder and the analytically pure urea of purity＞99.9%, granularity＜10 μ m mixed in 3: 1 in molar ratio, be sealed in the stainless steel jar mill in being full of the glove box of argon gas with the stainless steel abrading-ball, ratio of grinding media to material is 20: 1.Reaction ball milling carries out on GN-2 type high energy ball mill (Shenyang scientific instrument factory).The rotating speed of ball mill is 600r/min, and the ball milling time is 70 hours.Utilize X-ray diffractometer (XRD) that the powder of different ball milling after the time carried out the structural analysis (see figure 1), from Fig. 1 as seen, ball milling had only TiN after 70 hours in the material
xDiffraction peak, calculate the TiN of acquisition with thanking to the plan formula
xGrain-size is 6～7nm; Consider XRD to amorphous insensitive problem, again TiN to obtaining
xCarried out 800 ℃ of annealing, will form normal crystalline state under this temperature if any residual non-crystalline state Ti, XRD will clearly reflect, and evidence does not have residual Ti (see figure 2).Utilize transmission electron microscope (TEM) to observe the microscopic appearance and the structure (see figure 3) of the powder of ball milling after 70 hours simultaneously, Fig. 3 clearly shows the TiN of acquisition
xPattern and crystalline diffraction style, crystalline estimates that size is consistent with XRD calculation result.Utilize electron energy loss spectroscopy (EELS) (EELS) to analyze its composition (see figure 4), the result has only Ti, N (seeing table 1 for details).
Table 1 ball milling Ti and urea mol ratio are 3: 1, the EELS spectral element quantitative analysis results of powder after 70 hours
| Element | Actom ratio | Percent content |
| C | 0.00+/-0.009 | 0.00+/-0.5 |
| N | 0.59+/-0.083 | 37.09+/-4.6 |
| Ti | 1.00+/-0.000 | 62.91+/-7.8 |
| O | 0.00+/-0.088 | 0.00+/-4.9 |
After Ti powder and the analytically pure urea of purity＞99.9%, granularity＜10 μ m mixed in 3: 1 in molar ratio, be sealed in being full of the glove box of argon gas in the Wimet ball milling jar with the Wimet abrading-ball, ratio of grinding media to material is 10: 1.Reaction ball milling carries out on P4 type high-energy planetary ball mill machine (German Fritsch company), the deep bid rotating speed of P4 type high-energy planetary ball mill machine is 300r/min, the shallow bid rotating speed is-900r/min (negative sign "-" expression shallow bid is opposite with the deep bid sense of rotation) that the ball milling time is 30 hours.
Utilize X-ray diffractometer (XRD) that the powder that obtained behind the ball milling in 30 hours is carried out structural analysis (seeing under Fig. 5).The powder that obtains is carried out vacuum annealing handle, temperature is 800 ℃, and the time is 5 hours.Powder after the annealing is carried out XRD analysis (seeing on Fig. 5).Other analysis and embodiment 1 are together.
From Fig. 5 as seen, behind 30 hours ball millings of P4 type high-energy planetary ball mill machine, basic identical behind 70 hours ball millings of its XRD spectral line (seeing under Fig. 5) and embodiment 1GN-2 type high energy ball mill, just, in XRD analysis, there is the WC phase of minute quantity because the ball grinder, the abrading-ball that adopt are Hardmetal materials; The powder X-ray RD spectral line (seeing on Fig. 5) that same annealing conditions obtains down is also identical with embodiment 1, and other analytical results is also very close.
Embodiment 3
After Ti powder and the analytically pure urea of purity＞99.9%, granularity＜10 μ m mixed in 3: 1 in molar ratio, with the stainless steel abrading-ball at the atmospheric condition lower seal in stainless steel jar mill, ratio of grinding media to material is 20: 1.Before ball milling, ball grinder is vacuumized with oil-sealed rotary pump through the aspirating hole of ball grinder, charge into argon gas then, repeat 3 times.Reaction ball milling carries out on GN-2 type high energy ball mill.The rotating speed of ball mill is 600r/min, and the ball milling time is 70 hours.Other and embodiment 1 with, the result is same as embodiment 1.
Embodiment 4
After Ti powder and the analytically pure urea of purity＞99.9%, granularity＜10 μ m mixed in 3: 1 in molar ratio, with the stainless steel abrading-ball at the atmospheric condition lower seal in stainless steel jar mill, ratio of grinding media to material is 30: 1.Reaction ball milling carries out on GN-2 type high energy ball mill.The rotating speed of ball mill is 600r/min, and the ball milling time is 50 hours.Other and embodiment 1 with, the result is same as embodiment 1.
Embodiment 5
With purity＞99.9%, after Ti powder and the analytically pure urea of granularity＜10 μ m mixed in 4: 1 in molar ratio, in being full of the glove box of argon gas, be sealed in the stainless steel jar mill with the stainless steel abrading-ball, ratio of grinding media to material is 20: 1.Reaction ball milling carries out on GN-2 type high energy ball mill.The rotating speed of ball mill is 600r/min, and the ball milling time the longest is 70 hours.Other and embodiment 1 with, the XRD curve of different ball milling times is seen Fig. 7.From Fig. 7 as seen, after 40 hours, the powder of acquisition all is TiN at ball milling
x, with the EELS test, the atomic ratio of Ti and N is 1: 0.46 as calculated, other result is same as embodiment 1.
Claims (1)
1. a reaction ball milling legal system is equipped with the non-stoichiometric nano TiN
xThe method of powder is characterized in that: described method utilizes the reaction ball milling method that Ti powder and analytical pure urea are at room temperature carried out ball milling, the nano TiN of the non-stoichiometric of preparation
xGrain fineness number＜the 10nm of powder, the powder phase composite is single TiN
x, when Ti powder and urea in the time of 3: 1 in molar ratio, gained TiN
xTi: the N atomic ratio is 1: 0.59, i.e. x=0.59; When Ti powder and urea in the time of 4: 1 in molar ratio, gained TiN
xTi: the N atomic ratio is 1: 0.46, i.e. x=0.46; The step of described method is as follows:
(1), mixes at 3～4: 1 in molar ratio with analytical pure urea, as abrasive material with the Ti powder of purity＞99.9% and granularity＜10 μ m;
(2) at ambient temperature, abrasive material and abrading-ball are packed among the ball grinder of high energy ball mill simultaneously, the mass ratio of abrading-ball and abrasive material is 10～30: 1;
(3) after filling finishes, ball milling cover lid tightly and with mechanical pump is vacuumized, feed argon gas afterwards, once more the argon gas and the residual air that feed are found time, and then the feeding argon gas, so carry out 3～5 times, at last ball grinder is full of argon gas, seal aspirating hole then, to guarantee that no oxygen participates in reaction in the mechanical milling process; If the filling step is carried out, just do not need to carry out above-mentioned finding time and the applying argon gas process in being full of the environment of argon gas;
(4) ball grinder after will loading and seal places and begins ball milling on the high energy ball mill, and the ball milling time is 30～70 hours, and mechanical milling process at room temperature carries out;
(5) taking-up is through the material of ball milling from ball grinder under the argon gas condition, and through soaked in absolute ethyl alcohol, so that make remaining organism dissolving, the process seasoning finally obtains the non-stoichiometric nano TiN
xPowder.
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101863659A (en) * | 2010-06-11 | 2010-10-20 | 广东工业大学 | Method for preparing stabilized zirconia superfine powder by stirring ball-milling reaction |
| CN102674272B (en) * | 2011-11-01 | 2013-10-23 | 南开大学 | Preparation method of catalyst TiN for synthesizing NaAlH4 |
| CN105439562A (en) * | 2015-12-09 | 2016-03-30 | 燕山大学 | Preparation method of multi-component transition metal covalent bond compound of single-phase simple crystal structure |
| CN106319270B (en) * | 2016-09-05 | 2017-12-05 | 重庆大学 | A kind of titanium matrix composite preparation method of nano TiN enhancing |
| CN107271461B (en) * | 2017-05-05 | 2019-09-10 | 燕山大学 | A method of obtaining annular dark field image under transmission electron microscope |
| CN109627010A (en) * | 2018-12-04 | 2019-04-16 | 燕山大学 | Composite material of silicon carbide and preparation method thereof |
| CN110684979B (en) * | 2019-11-01 | 2022-06-21 | 江苏锋泰工具有限公司 | Method for preparing hard alloy coating by cold spraying |
| CN110981489B (en) * | 2019-12-30 | 2021-01-15 | 燕山大学 | TiNx-Ti3SiC2Composite material and preparation method thereof |
| CN112441586A (en) * | 2020-11-26 | 2021-03-05 | 中铭富驰（苏州）纳米高新材料有限公司 | Preparation method of non-stoichiometric titanium carbide TiCx powder |
| CN113416078B (en) * | 2021-08-09 | 2022-09-27 | 燕山大学 | Non-stoichiometric titanium boride and high-entropy boride ceramic prepared from same |
| CN114105646B (en) * | 2021-12-20 | 2022-12-09 | 哈尔滨工业大学 | Preparation method of in-situ SiC-BN (C) -Ti (C, N) nanocrystalline complex phase ceramic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1844049A (en) * | 2006-04-18 | 2006-10-11 | 张芬红 | Method for preparing nanometer ceramic powder of titanium nitride |
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| CN1844049A (en) * | 2006-04-18 | 2006-10-11 | 张芬红 | Method for preparing nanometer ceramic powder of titanium nitride |
Non-Patent Citations (3)
| Title |
|---|
| JP特开2004-149892A 2004.05.27 |
| 周丽等.在氮气中球磨Ti粉制备纳米TiNx.硅酸盐通报 6.2004,(6),75-77. |
| 周丽等.在氮气中球磨Ti粉制备纳米TiNx.硅酸盐通报 6.2004,(6),75-77. * |
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