CN1239386C - Process for preparing nano titanium chromium nitride oxide powder - Google Patents
Process for preparing nano titanium chromium nitride oxide powder Download PDFInfo
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- CN1239386C CN1239386C CN 02111450 CN02111450A CN1239386C CN 1239386 C CN1239386 C CN 1239386C CN 02111450 CN02111450 CN 02111450 CN 02111450 A CN02111450 A CN 02111450A CN 1239386 C CN1239386 C CN 1239386C
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Abstract
The present invention provides a method for synthesizing nanometer titanium chromium nitride (Ti<1-Z>Cr<Z>O<X>N<Y>) powder. The present invention is mainly characterized in that the composite powder of nanometer titanium oxide (TiO2)/ chromium oxide (Cr2O3) prepared by a precipitation method is used as a raw material, and the composite powder is nitrided in an ammonia atmosphere, at a high temperature and in a tube reaction furnace to prepare nanometer titanium chromium oxynitride (Ti<1-Z>Cr<Z>O<X>N<Y>) powder. The nanometer titanium chromium oxynitride(Ti<1-Z>Cr<Z>O<X>N<Y>) (0<z<1)powder of different compositions can be obtained by changing the ratio of Ti to Cr in the composite powder of oxides. The nitriding speed and the particle size of the oxynitride powder can be regulated by changing the technological conditions of ammonia gas flow quantity, nitriding temperature, nitriding time, etc. The method has the characteristics of simple technology, low production cost, large scale production, etc.
Description
Technical field
The present invention relates to nano titanium chromium nitride oxide powder (Ti
1-zCr
zO
xN
y) the preparation method, can be used for preparing high-performance ceramic and high-abrasive material.Or rather, adopting coprecipitation method to prepare nano-titanium oxide/chromic oxide composite granule earlier, is the method for the synthetic new nano titanium chromium nitride oxide powder of nitridizing agent with ammonia then, belongs to field of nanometer material technology.
Background technology
Nitride powder receives much attention because of having the engineering application characteristic.Some transition metal nitrides show high strength, high rigidity, favorable conductive, thermal conductivity and catalysis characteristics.Therefore nitride is widely used at aspects such as packaged material, structured material, catalyzer.In binary or ternary transition metal oxide, oxygen is partly or entirely replaced by nitrogen, and positively charged ion more or less is reduced, and structure changes, and has new electricity, light, magnetic property.Industrial, contain the oxynitride (Si of sial
6-xAl
xO
xN
8-x) Sialon (match dragon) pottery of preparation has good thermal shock resistance, oxidation-resistance has the ability of very excellent anti-molten metal corrosion, and the hardness height is a kind of superhard tool material.Although (oxygen) nitride has the potential technical significance, known (oxygen) nitride is less relatively, and because synthetic polynary (oxygen) nitride has certain challenge, majority concentrates on the binary nitride.Polynary (oxygen) nitride is compared with the binary nitride has particular structure and performance, and synthetic new polynary (oxygen) nitride has received increasing concern.
S.T.Oyama etc. adopt nitrogenize bimetallic oxide V in US Pat.5444173 (1995)
2MoO
8Prepared V
2Mo (O
xN
y).M.Jansen etc. have prepared Ca in Europ.Pat.697373 (1995)
(1-x)La
xTaO
2-xN
1-x(0≤x≤1).J.Grins etc. are at Journal of MaterialChemistry Vol.4 (1994) the pp.1293-Zr that reported employing nitrogenize Zr-Ta preparing gel
xTa
1-x(ON)
yReported employing nitrogenize Ti-Ta preparing gel Ti at Journal of the European Ceramic Society Vol.17 (1997) pp1819-1824
xTa
1-x(ON)
yAbdelouahadEl-Himri etc. have reported that at Journal of Material Chemistry Vol.10 (2000) pp2537-2541 employing nitrogenize lyophilize presoma prepares V
1-zCr
z(O
xN
y), Cr
1-zMo
z(O
xN
y).S.H.Elder etc. have reported employing nitrogenize 1/2Na at Journal of Solid State Chemistry Vol 108 (1994) pp73-79
2O: 1Na
2WO
4Eutectic mixture prepares NaWO
3N.
TiN has a series of good characteristics, and wear-resisting, resistance to chemical attack, metallic conductivity, high-melting-point (2950 ℃) are a kind of advanced person's stupaliths, and the interpolation that is widely used in coated material, the matrix material equates.CrN is considered to a kind of high-abrasive material with application prospect, is widely used as abrasion-proof ceramic coat, particularly on metal cutter, the mould.Guess thus, titanium-chromium containing (oxygen) nitride expection has good abrasion resistance, conductivity, and the interpolation that can be used as high-abrasive material and matrix material mutually.The research of titaniferous, chromium nitride film is more, but titaniferous, chromium nitride oxide powder rarely have report.
Summary of the invention
The object of the present invention is to provide a kind of synthetic new nanoscale oxynitride powder---Ti
1-zCr
zO
xN
yMethod.It is raw material that the present invention adopts the nano-titanium oxide/chromic oxide composite granule of coprecipitation method preparation, is the synthetic titanium chromium nitride oxide powder of nitridizing agent with ammonia.This preparation method's technology is simple, is easy to suitability for industrialized production, and the nanoscale oxynitride powder that obtains has characteristics such as particle diameter is little, good dispersity.
The objective of the invention is to implement like this: the compound with titaniferous, chromium is a starting raw material, be mixed with different Ti: the ethanolic soln of Cr ratio, under normal temperature, normal pressure, splash into and contain the dispersion agent basic solution, with ammoniacal liquor is precipitation agent, produce precipitation, make amorphous light green titanium hydroxide/chromium hydroxide powder through washing, oven dry, obtain nano-titanium oxide/chromic oxide composite granule through calcining; In tubular react furnace, under mobile ammonia condition, high-temperature ammonolysis makes nano titanium chromium nitride oxide (Ti with nano-titanium oxide/chromic oxide composite granule
1-zCr
zO
xN
y).
It is characterized in that:
(1) nano-TiO for preparing with coprecipitation method
2/ Cr
2O
3Composite granule is a raw material, in the ammonia that flows with nano-TiO
2/ Cr
2O
3Composite granule is heated to 800-900 ℃ in the tubular type atmosphere furnace, insulation 6-8h nitrogenize under the ammonia that flows, naturally cools to room temperature then, and the nitrogenize temperature rise rate is 5-10 ℃/minute, ammonia flow be the 0.5-5 liter/minute;
(2) described coprecipitation method prepares nano-TiO
2/ Cr
2O
3The composite granule processing step comprises:
(a) be starting raw material with butyl (tetra) titanate and chromium nitrate, at normal temperatures and pressures, be mixed with earlier the 0.1-0.5M ethanol solution respectively; Being mixed with titanium, chromium then is the mixed solution of 0＜Z＜1 than Z;
(b) add in the ammonia soln behind the non-ionic dispersing agent of 2-5wt% as precipitation agent;
(c) mixed solution that (a) made dropwise adds in (b), produces precipitation, it is to stir at 400-800 rev/min of rotating speed that precipitation drips processing condition, dropwise join in the basic solution that pH is 8-9, drip the ammonia soln of 3-6M simultaneously, keep the pH value of solution, produce precipitation, precipitation temperature is 20-70 ℃, time 1-24 hour, then throw out is filtered, washs, removes impurity, use the absolute ethanol washing secondary again, obtain unbodied light green titanium hydroxide/chromium hydroxide composite precipitation thing;
(d) the unbodied throw out drying of step (c) gained, the back of sieving be at 450-550 ℃, and 1-2h calcining obtains titanium oxide/chromic oxide composite granule of 10-20nm, and wherein the throw out drying condition is 100 ℃-120 ℃, 12-24 hour, grinds 200 mesh sieves.
This shows that the concrete enforcement that the present invention proposes the synthetic titanium chromium nitride oxide powder of nitriding can be divided into for two steps greatly:
The first step prepares nano-titanium oxide/chromic oxide composite granule; Second step nitrogenize nano-titanium oxide/chromic oxide composite granule synthesis of nano Ti
1-zCr
zO
xN
yNow details are as follows respectively:
One. the preparation of nano-titanium oxide/chromic oxide composite granule
The compound of titaniferous used in the present invention, chromium is respectively butyl (tetra) titanate and chromium nitrate.Earlier butyl (tetra) titanate and chromium nitrate are mixed with the 0.1-0.5M ethanol solution at normal temperatures and pressures respectively, are made into the mixing solutions that contains different titaniums, chromium ratio then, titanium chromium is 0＜Z＜1 than Z, preferentially recommends Z=0.2-0.8.(non-ionic dispersing agent commonly used is a polyoxyethylene glycol, PEG), then the above-mentioned mixture that contains different titaniums, chromium ratio is dropwise added, and produces precipitation to make precipitation agent in the ammonia soln behind the non-ionic dispersing agent of adding 2-5wt%.The processing condition that precipitation drips are under 400-800 rev/min of rotating speed stirs, and are added drop-wise in the basic solution that pH is 8-9, drip the ammonia soln of 3M-6M simultaneously, keep the pH value of solution, produce precipitation.Throw out is filtered, use distilled water wash, remove impurity, use the absolute ethanol washing secondary again, the moisture in the disgorging is avoided the generation of hard aggregation, can obtain the amorphous light green titanium hydroxide/chromium hydroxide composite precipitation thing of favorable dispersity, this throw out is dried, sieved, calcine 1～2h down, obtain titanium oxide/chromic oxide composite granule of 10-20nm at 450-550 ℃.Precipitation temperature is 20～70 ℃, and time 1～24h, precipitated product drying condition are 100 ℃-120 ℃, 12h-24h, grind 200 mesh sieves.
Two. synthesizing of nano titanium chromium nitride oxide powder
With the nano-titanium oxide/chromic oxide composite granule that obtains, put into quartz boat, the tubular type of packing into atmosphere furnace feeds ammonia, ammonia flow is 0.5～5 liter/minute, be warming up to 800～900 ℃, temperature rise rate is 5～10 ℃/minute, under this temperature, be incubated 6～8 hours, then, under the ammonia that flows, naturally cool to room temperature.Obtain nano titanium chromium nitride oxide powder.By the particle diameter and the nitriding velocity of temperature of reaction control nano titanium chromium nitride oxide, temperature raises, and nitriding velocity is accelerated, and powder granularity increases; By the particle diameter of control temperature retention time of nitrogenization control nanometer chrome nitride, soaking time prolongs, and helps the carrying out of nitrogenizing reaction, but powder granularity increases; By the control ammonia flow velocity adjustable joint reaction times.So the selection of these three parameters all has fundamental influence to reacted particle diameter, output, these three parameters of choose reasonable, it is very important making it organic coupling.
Reaction process is as follows:
The characteristics of nano titanium chromium nitride oxide powder synthetic method provided by the invention are:
1. can synthesize the nano titanium chromium nitride oxide powder that contains different titanium chromium ratios.
2. little, the good dispersity of synthetic titanium chromium nitride oxide powder particle diameter, purity height.
3. simple, the required production unit of synthesis technique is simple, is easy to realize suitability for industrialized production.
4. use ammonia as nitridizing agent in the production process, be more conducive to reaction, safer as nitridizing agent than add hydrogen with nitrogen.
Description of drawings
Fig. 1 is X-ray diffractogram (a) presoma (b) oxynitride of titanium chromium ratio synthetic presoma, nitride oxide powder when being 1: 4 (Z=0.8).
Fig. 2 is the transmission electron microscope photo of titanium chromium ratio synthetic nitride oxide powder when being 1: 4 (Z=0.8).
Fig. 3 is X-ray diffractogram (a) presoma (b) oxynitride of titanium chromium ratio synthetic presoma, nitride oxide powder when being 1: 1 (Z=0.5).
Fig. 4 is that titanium chromium ratio is the transmission electron microscope photo of 1: 1 (Z=0.5) synthetic nitride oxide powder.
Fig. 5 is X-ray diffractogram (a) presoma (b) oxynitride of titanium chromium ratio synthetic presoma, nitride oxide powder when being 4: 1 (Z=0.2).
Fig. 6 is the transmission electron microscope photo of titanium chromium ratio synthetic nitride oxide powder when being 4: 1 (Z=0.2).
Embodiment
Embodiment 1
Get butyl (tetra) titanate 27.2g, chromium nitrate 128g, be dissolved in respectively in 300ml, the 1200ml dehydrated alcohol, after stirring, be mixed into titaniferous, the chromium ratio is the ethanolic soln of 1: 4 (Z=0.8).With above-mentioned solution, dropwise join and contain 1.5g PEG dispersion agent.Dripping processing condition is under 600 rev/mins of rotating speeds stir, and in the 2000ml ammonia soln of PH＞9, drips the ammonia soln of 4M simultaneously, and keeping the pH value of solution is 8～9, produces precipitation.Precipitated product is filtered, use distilled water wash, remove negatively charged ion, 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 1h.With the nano-titanium oxide/chromic oxide composite granule that obtains, put into quartz boat, the tubular type of packing into atmosphere furnace, feed ammonia, ammonia flow is 1 liter/minute, is warming up to 800 ℃, and temperature rise rate is 10 ℃/minute, under this temperature, be incubated 8 hours, then, under the ammonia that flows, naturally cool to room temperature, obtain nano titanium chromium nitride oxide.(a) and (b) are respectively the X-ray diffractogram of present embodiment synthetic titanium oxide/chromic oxide composite granule, titanium chromium nitride oxide powder among Fig. 1, and (a) diffraction peak in is corresponding to rutile TiO
2, Cr
2O
3Diffraction peak, show that presoma is TiO
2, Cr
2O
3Composite granule.(b) TiO in
2, Cr
2O
3Diffraction peak disappear, three diffraction peaks correspond respectively to (111) crystal face, (200) crystal face of cubic structure phase, the diffraction peak of (220) crystal face.The position of diffraction peak illustrates that the synthetic powder is the sosoloid of titanium-chromium containing oxynitride between TiN, CrN peak position.The electronic probe microscopical analysis shows the Ti that consists of of synthetic powder
0.2iCr
0.79O
0.14N
0.58Fig. 2 is its transmission electron microscope photo, shows that its particle diameter is between 20-40nm.
Embodiment 2
Get butyl (tetra) titanate 68g, chromium nitrate 80g, be dissolved in respectively in the 800ml dehydrated alcohol, after stirring, be mixed into titaniferous, the chromium ratio is the ethanolic soln of 1: 1 (Z=0.5).Above-mentioned solution dropwise joined contain 1.5g PEG dispersion agent.Dripping processing condition is under 800 rev/mins of rotating speeds stir, and is added drop-wise in the 2000ml ammonia soln of PH＞9, produces precipitation.After dropwising, pH value to 8～9 of regulator solution are stirred, are precipitated 2 hours.Precipitated product is filtered, use distilled water wash, remove negatively charged ion, 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 1h.Nano-titanium oxide/chromic oxide the composite granule that obtains is put into quartz boat, the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 1 liter/minute, be warming up to 800 ℃, temperature rise rate is 10 ℃/minute, under this temperature, is incubated 8 hours, then, under the ammonia that flows, naturally cool to room temperature, obtain nano titanium chromium nitride oxide.Present embodiment synthetic titanium oxide/chromic oxide composite granule, titanium chromium nitride oxide powder X-ray diffractogram are as shown in Figure 3, and be similar to embodiment 1.Show that the synthetic powder is a titanium chromium nitride oxide.The electronic probe microscopical analysis shows the Ti that consists of of synthetic powder
0.50Cr
0.50O
0.20N
0.86Fig. 4 is its transmission electron microscope photo, shows that its particle diameter is between 20-30nm.
Embodiment 3
Get butyl (tetra) titanate 108.8g, chromium nitrate 32g, be dissolved in respectively in 1000ml, the 500ml dehydrated alcohol, after stirring, be mixed into titaniferous, the chromium ratio is the ethanolic soln of 4: 1 (Z=0.2).Method by embodiment 1 prepares nano-titanium oxide/chromic oxide composite granule.Nano-titanium oxide/chromic oxide the composite granule that obtains is put into quartz boat, the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 1 liter/minute, be warming up to 800 ℃, temperature rise rate is 10 ℃/minute, under this temperature, is incubated 8 hours, then, under the ammonia that flows, naturally cool to room temperature, obtain nano titanium chromium nitride oxide.Titanium oxide/chromic oxide the composite granule of present embodiment preparation, titanium chromium nitride oxide powder X-ray diffractogram are as shown in Figure 5, and be similar to embodiment 1,2.Show that the synthetic powder is a titanium chromium nitride oxide.The electronic probe microscopical analysis shows the Ti that consists of of synthetic powder
0.81Cr
0.19O
0.25N
0.70Fig. 6 is its transmission electron microscope photo, shows that its particle diameter is between 20-30nm.
Embodiment 4
Get butyl (tetra) titanate 54.38g, chromium nitrate 96g, be dissolved in respectively in the 800ml dehydrated alcohol, after stirring, be mixed into titaniferous, the chromium ratio is the ethanolic soln of 2: 3 (Z=0.6).Method according to embodiment 1 prepares nano-titanium oxide/chromic oxide composite granule, then the synthetic titanium chromium nitride oxide of nitrogenize.Test shows: institute's synthetic powder consists of Ti
0.40Cr
0.60O
0.42N
0.70, granularity is between 20-30nm.
Embodiment 5
Get butyl (tetra) titanate 81.58g, chromium nitrate 64g, be dissolved in respectively in the 800ml dehydrated alcohol, after stirring, be mixed into titaniferous, the chromium ratio is the ethanolic soln of 3: 2 (Z=0.4).Method according to embodiment 1 prepares nano-titanium oxide/chromic oxide composite granule, then the synthetic titanium chromium nitride oxide of nitrogenize.Test shows: institute's synthetic powder consists of Ti
0.61Cr
0.39O
0.25N
0.70, granularity is between 20-30nm.
Claims (3)
1. the preparation method of a nano titanium chromium nitride oxide powder is characterized in that:
(1) nano-TiO for preparing with coprecipitation method
2/ Cr
2O
3Composite granule is a raw material, in the ammonia that flows with nano-TiO
2/ Cr
2O
3Composite granule is heated to 800-900 ℃ in the tubular type atmosphere furnace, be incubated nitrogenize in 6-8 hour, under the ammonia that flows, naturally cools to room temperature then, and the nitrogenize temperature rise rate is 5-10 ℃/minute, ammonia flow be the 0.5-5 liter/minute;
(2) described coprecipitation method prepares nano-TiO
2/ Cr
2O
3The composite granule processing step comprises:
(a) be starting raw material with butyl (tetra) titanate and chromium nitrate, at normal temperatures and pressures, be mixed with earlier the 0.1-0.5M ethanol solution respectively; Being mixed with titanium, chromium then is the mixed solution of 0＜Z＜1 than Z;
(b) add in the ammonia soln behind the non-ionic dispersing agent of 2-5wt% as precipitation agent;
(c) mixed solution that (a) made dropwise adds in (b), produces precipitation, it is to stir at 400-800 rev/min of rotating speed that precipitation drips processing condition, dropwise join in the basic solution that pH is 8-9, drip the ammonia soln of 3-6M simultaneously, keep the pH value of solution, produce precipitation, precipitation temperature is 20-70 ℃, time 1-24 hour, then throw out is filtered, washs, removes impurity, use the absolute ethanol washing secondary again, obtain unbodied light green titanium hydroxide/chromium hydroxide composite precipitation thing;
(d) the unbodied throw out drying of step (c) gained, sieve after, at 450-550 ℃, calcined in 1-2 hour, obtain titanium oxide/chromic oxide composite granule of 10-20nm, wherein the throw out drying condition is 100 ℃-120 ℃, 12-24 hour, grinds 200 mesh sieves.
2. by the preparation method of the described nano titanium chromium nitride oxide powder of claim 1, it is characterized in that titanium, chromium compare Z=0.2-0.8.
3. by the preparation method of right 1 or 2 described nano titanium chromium nitride oxide powders, it is characterized in that described non-ionic dispersing agent is a polyoxyethylene glycol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1304277C (en) * | 2004-05-24 | 2007-03-14 | 东华大学 | Preparation of nano V-Cr oxygen nitride powders |
| CN102408122A (en) * | 2011-11-23 | 2012-04-11 | 陕西科技大学 | Co-precipitation method for preparing lanthanum cuprate (La2CuO4) powder |
| CN106349897B (en) * | 2016-08-27 | 2019-04-12 | 南京理工大学 | Bismuth/nitrogen-doped titanic acid aluminium base infrared composite material and preparation method thereof |
| CN106243944B (en) * | 2016-08-27 | 2019-05-07 | 南京理工大学 | Cerium/nitrogen-doped titanic acid aluminium base infrared composite material and preparation method thereof |
| CN106318161B (en) * | 2016-08-27 | 2019-02-22 | 南京理工大学 | Cerium/nitrogen-doped titanic acid lanthanum base infrared composite material and preparation method thereof |
| CN106366875B (en) * | 2016-08-27 | 2019-02-22 | 南京理工大学 | Iron/nitrogen-doped titanic acid aluminium base infrared composite material and preparation method thereof |
| CN106366878B (en) * | 2016-08-27 | 2019-04-16 | 南京理工大学 | Manganese/N doping aluminic acid zinc-base infrared composite material and preparation method thereof |
| CN106318162B (en) * | 2016-08-27 | 2019-06-21 | 南京理工大学 | Iron/nitrogen-doped titanic acid magnesium-based infrared composite material and preparation method thereof |
| CN106336789B (en) * | 2016-08-27 | 2019-02-22 | 南京理工大学 | Iron/nitrogen-doped titanic acid cerium base infrared composite material and preparation method thereof |
| CN110128148B (en) * | 2019-04-26 | 2021-11-02 | 山东科技大学 | Preparation method of chromium nitride ceramic membrane |
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