CN100480213C - Tetragonal composite zirconia-titanium nitride nano-powder synthesized by in-situ selective nitrogenation - Google Patents
Tetragonal composite zirconia-titanium nitride nano-powder synthesized by in-situ selective nitrogenation Download PDFInfo
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- CN100480213C CN100480213C CNB02151111XA CN02151111A CN100480213C CN 100480213 C CN100480213 C CN 100480213C CN B02151111X A CNB02151111X A CN B02151111XA CN 02151111 A CN02151111 A CN 02151111A CN 100480213 C CN100480213 C CN 100480213C
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Abstract
A process for synthesizing nano-class t-ZrO2-TiN powder by in-situ selective nitriding is characterized by the high-temp in-situ selective nitriding of nano t-ZrO/TiO2 powder, which is prepared by precipitation method, in flowing ammonia atmosphere in tubular reactor. Its advantages are simple process, and low cost.
Description
Technical field
The present invention relates to nanometer tetragonal zircite-titanium nitride (t-ZrO
2-TiN) composite granule and original position are selected the nitrification established law, can be used for preparing high performance ceramic material.Or rather, preparation method provided by the invention adopts coprecipitation method to prepare nanometer tetragonal zircite/titanium oxide composite granule earlier, uses ammonia as nitridizing agent then, and original position is selected nitrogenize synthesis of nano tetragonal zircite-titanium nitride (t-ZrO
2-TiN) composite granule belongs to field of nanometer material technology.
Background technology
Tetragonal polycrystalline zirconia ceramic material has good intensity and toughness, but at high temperature because the reduction of the thermodynamic driving force of the martensitic transformation of four directions → monocline, the transformation toughening effect falls sharply, its mechanical behavior under high temperature is sharply descended, limited tetragonal polycrystalline zirconia ceramic material use at high temperature.Dispersed particle-strengthened is the toughened and reinforced mechanism of a kind of high temperature, because dispersed particle-strengthened supporting material preparation technology is simple, therefore has been subjected to paying attention to widely.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.Preparation t-ZrO
2The traditional method of-TiN material is to use t-ZrO
2Powder and TiN mechanically mixing, the back sintering is shaped.In the stupalith of this method preparation, because mechanically mixing is difficult to make TiN to be uniformly dispersed in ceramic matrix, can not give full play to TiN particulate disperse strengthening action, and, reduced the mechanical property of material in matrix usually because the TiN agglomeration of particles cracks.Synthetic TiN uniform particles is dispersed in t-ZrO
2In t-ZrO
2-TiN composite granule is to preparation high-performance t-ZrO
2-TiN stupalith is most important.HuaZhang Zhai etc. have reported that at Journal of MaterialChemistry 2001 vol.11 PP1092-1095 employing carbon heat reducing selection nitriding prepares t-ZrO
2-TiN composite granule, but this method one side nitriding temperature height, grain-size is 300-500nm after the nitrogenize, belongs to submicron powder; Need the secondary carbon removal on the other hand, the technology more complicated, and might form TiC.The nanometer scale ceramics particle as preparing nano composite ceramic in the disperse phase introducing ceramic matrix, had good enhancing toughening effect.Prepare nanometer t-ZrO
2-TiN composite ceramics at first will prepare its composite nano-powder.But, up to the present, do not see preparation nanometer t-ZrO
2The report of-TiN composite granule.
Summary of the invention
The object of the present invention is to provide a kind of nanometer tetragonal zircite-titanium nitride (t-ZrO
2-TiN) composite granule and original position are selected the nitrification established law.The present invention adopts the nanometer t-ZrO of coprecipitation method preparation
2-TiO
2Composite granule is a raw material, adopts ammonolysis process, carries out original position and select nitrogenizing reaction, the TiO in the composite granule under certain nitridation conditions
2Be nitrided into TiN, ZrO
2Still exist mutually, be uniformly distributed in t-ZrO in the tetragonal zircite thereby make a kind of TiN with the four directions
2-TiN composite granule.This preparation method's technology is simple, is easy to suitability for industrialized production, and the composite nano-powder that obtains has even, the characteristics such as particle diameter is little, good dispersity of forming.
The objective of the invention is to implement like this: with the compound that contains zirconium, yttrium (or magnesium, calcium), titanium is starting raw material, be mixed with ethanolic soln, under normal temperature, normal pressure, dropwise join in the basic solution that contains dispersion agent, with ammoniacal liquor is precipitation agent, produce precipitation, make amorphous white zirconium hydroxide/yttrium hydroxide (or magnesium, calcium)/titanium hydroxide composite granule, obtain nanometer t-ZrO through calcining through washing, oven dry
2-TiO
2Composite granule; With nanometer t-ZrO
2-TiO
2Composite granule is in tubular react furnace, and under mobile ammonia condition, high-temperature ammonolysis prepares nanometer t-ZrO
2-TiN composite granule.
This shows that the original position that the present invention proposes is selected nitriding synthesis of nano t-ZrO
2The concrete enforcement of-TiN composite granule can be divided into two and go on foot greatly:
The first step prepares nanometer t-ZrO
2-TiO
2Composite granule; The second step original position is selected nitrogenize nanometer ZrO
2-TiO
2Composite granule synthesis of nano t-ZrO
2-TiN composite granule.Now details are as follows respectively:
One. nanometer t-ZrO
2-TiO
2The preparation of composite granule
The compound that contains zirconium, yttrium (or magnesium, calcium), titanium involved in the present invention is respectively basic zirconium chloride, Yttrium trinitrate (or magnesium nitrate, nitrocalcite) and butyl (tetra) titanate.At first basic zirconium chloride, Yttrium trinitrate (or magnesium nitrate, nitrocalcite) and butyl (tetra) titanate are mixed with the 0.1-0.5M ethanol solution respectively, are made into mixing solutions then.Above-mentioned solution dropwise joins the PEG dispersion agent that contains 2-5wt%, and under 400-800 rev/min of rotating speed stirred, pH was in the basic solution of 8-9, drips the ammonia soln of 3M-6M simultaneously, kept the pH value of solution, produced 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 white unformed zirconium hydroxide/yttrium hydroxide/titanium hydroxide composite granule of favorable dispersity.This composite granule is dried, sieved, calcine 1-2h down, obtain nanometer t-ZrO at 450-800 ℃
2-TiO
2Composite granule.Precipitation temperature is 20～70 ℃, and time 1～24h, precipitated product drying condition are 100-120 ℃, 12-24h, grind 200 mesh sieves.The stablizer of tetragonal zircite can be Y
2O
3, CaO, MgO, preferentially recommend Y
2O
3, addition is 3-5mol%.
Two. nanometer t-ZrO
2The original position of-TiN composite granule selects nitrogenize synthetic
With (one) the prepared nanometer t-ZrO that arrives
2-TiO
2Composite granule is put into quartz boat, and the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 0.5～5 liter/minute, is warming up to 800～1300 ℃, and temperature rise rate is 5～10 ℃/minute, under this temperature, is incubated 3～6 hours, and original position is selected nitrogenize, makes TiO
2Be nitrided into TiN, under the ammonia that flows, naturally cool to room temperature then, obtain nanometer t-ZrO
2-TiN composite granule.By temperature of reaction control nanometer t-ZrO
2The composition of-TiN composite granule, particle diameter and nitriding velocity, temperature raises, and nitriding velocity is accelerated, and powder granularity increases, and the too high ZrN that has of temperature forms; By control temperature retention time of nitrogenization control nanometer t-ZrO
2The particle diameter of-TiN composite granule, 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 composition, particle diameter, output, these three parameters of choose reasonable, it is very important making it organic coupling.
With Y
2O
3Making stablizer is example, and reaction process is as follows:
Zr(OH)
4/Y(OH)
3/Ti(OH)
4↓+NH
4Cl+NH
4NO
3+BuOH (1)
Nanometer t-ZrO provided by the invention
2The characteristics of-TiN composite granule synthetic method are:
1. synthetic t-ZrO
2The temperature of-TiN composite granule is low, and the synthetic temperature range is big, and the Zr/Ti ratio is between 0-1;
2. synthetic t-ZrO
2The composition of-TiN composite granule evenly, particle diameter is between 20-50nm and good dispersity;
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 .800 ℃ of synthetic t-ZrO
2The X-ray diffractogram of-TiN composite granule.
Fig. 2 .800 ℃ of synthetic t-ZrO
2The transmission electron microscope photo of-TiN composite granule.
Fig. 3 .900 ℃ of synthetic t-ZrO
2The X-ray diffractogram of-TiN composite granule.
Fig. 4 .900 ℃ of synthetic t-ZrO
2The transmission electron microscope photo of-TiN composite granule.
Fig. 5 .1300 ℃ of synthetic t-ZrO
2The X-ray diffractogram of-TiN composite granule.
Embodiment
Embodiment 1
Get butyl (tetra) titanate 34g, basic zirconium chloride 62.49g, Yttrium trinitrate 2.30g, be dissolved in respectively in 200ml, 200ml, the 50ml dehydrated alcohol, after stirring, be mixed into titaniferous, zirconium (yttrium that contains 3mol%) than being the ethanolic soln of 1:2.With above-mentioned solution, dropwise join and contain 2g PEG dispersion agent, under 600 rev/mins of rotating speeds stir, PH in 9 the 2000ml ammonia soln, drip the ammonia soln of 4M simultaneously, keeping the pH value of solution is 8～9, produces to precipitate.Precipitated product is filtered, use distilled water wash, remove negatively charged ion, use the absolute ethanol washing secondary again, filter cake grinds, crosses 200 mesh sieves at 100 ℃ of oven dry 12h, then 450 ℃ of calcining 2h.With the nanometer t-ZrO that obtains
2-TiO
2Composite granule is put into quartz boat, and 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 5 hours, then, under the ammonia that flows, naturally cool to room temperature, obtain nanometer t-ZrO
2-TiN composite granule.Present embodiment synthetic nanometer t-ZrO
2The X-ray diffractogram of-TiN composite granule as shown in Figure 1, diffraction peak is corresponding to t-ZrO
2With the diffraction peak of TiN, show that synthetic powder is t-ZrO
2The composite granule of-TiN.Fig. 2 is its transmission electron microscope photo, and the particle diameter that shows composite granule is between 20-30nm.
Embodiment 2
Prepare nanometer t-ZrO by embodiment 1 described method
2-TiO
2Composite granule.Nanometer t-ZrO with preparation
2-TiO
2Composite granule is put into quartz boat, and the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 1 liter/minute, be warming up to 900 ℃, temperature rise rate is 10 ℃/minute, under this temperature, is incubated 5 hours, then, under the ammonia that flows, naturally cool to room temperature, obtain nanometer t-ZrO
2-TiN composite granule.Present embodiment synthetic nanometer t-ZrO
2The X-ray diffractogram of-TiN composite granule as shown in Figure 3, and is similar to embodiment 1.Show that the synthetic powder is nanometer t-ZrO
2-TiN composite granule.Fig. 4 is its transmission electron microscope photo, and the particle diameter that shows composite granule is between 30-50nm.
Embodiment 3
Prepare nanometer t-ZrO by embodiment 1 described method
2-TiO
2Composite granule.Nanometer t-ZrO with preparation
2-TiO
2Composite granule is put into quartz boat, and the tubular type of packing into atmosphere furnace feeds ammonia, and ammonia flow is 1 liter/minute, is warming up to 1300 ℃.(temperature rise rate is: room temperature-800 ℃, 10 ℃/minute; 800-1300 ℃, 5 ℃/minute.) under this temperature, be incubated 5 hours, then, under the ammonia that flows, naturally cool to room temperature, obtain t-ZrO
2-TiN composite granule.Present embodiment synthetic nanometer t-ZrO
2The X-ray diffractogram of-TiN composite granule as shown in Figure 5, and is similar to embodiment 1.Do not find the diffraction peak of ZrN, show that the synthetic powder remains t-ZrO
2The composite granule of-TiN.Powder particle size 40-50nm.
Claims (5)
1, a kind of original position is selected nitriding synthetic nanometer tetragonal zircite-titanium nitride composite granule, it is characterized in that:
(1) 0＜Zr/Ti＜1 in the described composite nano-powder;
(2) particle diameter of described composite nano-powder is 20-50nm.
2, a kind of original position is selected the preparation method of nitriding synthetic nanometer tetragonal zircite-titanium nitride composite granule, it is characterized in that:
(a) the nanometer tetragonal zircite/titanium oxide composite granule with prepared by co-precipitation is a raw material, in the ammonia that flows, selects the condition of nitrogenize to be nanometer tetragonal zircite/titanium oxide composite granule original position in pipe reaction:
(1) the nitrogenizing reaction temperature is controlled at 800 ℃-1300 ℃;
(2) ammonia flow is 0.5～5 liter/minute;
(3) temperature retention time of nitrogenization 3-6h;
(4) the nitrogenize temperature rise rate is 5-10 ℃/minute.
(b) preparation of described nanometer tetragonal zircite/titanium oxide composite granule be with a kind of in basic zirconium chloride, butyl (tetra) titanate and Yttrium trinitrate or magnesium nitrate or the nitrocalcite be starting raw material, at normal temperatures and pressures, be mixed with ethanol solution earlier, the ammonia soln that contains dispersion agent is as precipitation agent, dropwise add above-mentioned ethanolic soln, obtain precipitation; After washing, the oven dry, make unbodied white zirconium hydroxide/yttrium hydroxide/titanium hydroxide composite precipitation thing, throw out obtains the tetragonal zircite/titanium oxide composite granule of stabilized nano yttrium oxide through high-temperature calcination.
3, press the preparation method of the described nanometer tetragonal zircite of claim 2-titanium nitride composite granule, it is characterized in that: contain that ethanolic soln concentration a kind of and titanium is 0.1-0.5M in zirconium, yttrium or magnesium or the calcium, dispersion agent is a polyoxyethylene glycol, add-on is 2-5wt%, at rotating speed is under the 400-800 rev/min of stirring, dropwise join in the basic solution that pH is 8-9, drip the ammonia soln of 3M-6M simultaneously, the pH value that keeps solution, control produces sedimentary speed, generates amorphous zirconium hydroxide/yttrium hydroxide/titanium hydroxide composite precipitation.
4, by the described nanometer tetragonal zircite of claim 3-titanium nitride composite granule preparation method, it is characterized in that described generation deposition condition is: precipitation temperature is 20-70 ℃, and the time is 1-24h, and the throw out drying condition is 100-120 ℃, 12h-24h.
5, by the preparation method of the described nanometer tetragonal zircite of claim 2-titanium nitride composite granule, it is characterized in that the calcining temperature of described amorphous zirconium hydroxide/yttrium hydroxide/titanium hydroxide composite precipitation thing is 450-800 ℃, time 1-2h.
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| 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 |
| CN103740164B (en) * | 2013-12-27 | 2015-03-25 | 淄博广通化工有限责任公司 | Special nano zirconium dioxide composite powder material for glass reflective insulation paint |
| CN103740165B (en) * | 2013-12-27 | 2015-07-15 | 淄博广通化工有限责任公司 | Special nano zirconium dioxide composite powder material for architectural outer wall insulation paint |
| CN110015895A (en) * | 2019-04-01 | 2019-07-16 | 中国有色桂林矿产地质研究院有限公司 | A kind of aluminium oxide-zirconium oxide-yttrium oxide-titanium nitride nano composite ceramic material and preparation method thereof |
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| BE1010825A7 (en) * | 1996-12-24 | 1999-02-02 | Leuven K U Res & Dev | Ceramic composites |
| CN1220248A (en) * | 1997-12-19 | 1999-06-23 | 化学工业部天津化工研究院 | Method for preparing zirconium oxide-aluminum oxide composite and its use |
| CN1369461A (en) * | 2002-03-22 | 2002-09-18 | 中国科学院上海硅酸盐研究所 | Magnesium oxide and yttrium oxide stabilized square polycrystal zirconium oxide ceramics and its preparing process |
-
2002
- 2002-12-06 CN CNB02151111XA patent/CN100480213C/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5030597A (en) * | 1989-03-03 | 1991-07-09 | Toray Industries, Inc. | Process for producing ceramic composites |
| CN1046879A (en) * | 1989-05-02 | 1990-11-14 | 隆察股份公司 | Sintered zirconium oxide powder and the preparation thereof |
| CN1143819A (en) * | 1995-07-21 | 1997-02-26 | 松下电器产业株式会社 | Laminated by-pass capacitor |
| BE1010825A7 (en) * | 1996-12-24 | 1999-02-02 | Leuven K U Res & Dev | Ceramic composites |
| CN1220248A (en) * | 1997-12-19 | 1999-06-23 | 化学工业部天津化工研究院 | Method for preparing zirconium oxide-aluminum oxide composite and its use |
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