CN101407420A - Method for preparing non-grain boundary phase porous silicon nitride ceramic based on carbon thermal reduction - Google Patents
Method for preparing non-grain boundary phase porous silicon nitride ceramic based on carbon thermal reduction Download PDFInfo
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- CN101407420A CN101407420A CNA2008102320988A CN200810232098A CN101407420A CN 101407420 A CN101407420 A CN 101407420A CN A2008102320988 A CNA2008102320988 A CN A2008102320988A CN 200810232098 A CN200810232098 A CN 200810232098A CN 101407420 A CN101407420 A CN 101407420A
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Abstract
The invention discloses a method for preparing non-crystal boundary phrase porous silicon nitride ceramics based on carbon thermal reduction, which comprises the following steps: firstly, according to weight percent, the components of 93-95 percent of silicon nitride and 5-7 percent of sintering aid are mixed, and a porous silicon nitride sample with 35-55 percent of porosity is obtained by the conventional preparation technology for porous silicon nitride. The glass phases of the silicon nitride and the compounds formed by the sintering aid are removed by hydrofluoric acid, nitric acid and sulphuric acid; the sol of phenolic resin and silicon dioxide is confected proportionally; the porous silicon nitride substrate sample undergoing acid cleaning is dipped into the sol for a plurality of times, dried, sent to an atmosphere furnace, and heated to 1200 DEG C; after the inlet of nitrogen, the sample is warmed up to 1750-1800 DEG C and insulated for 1-2 hours under the condition that the nitrogen pressure is between 2 to 6 atmospheric pressures to obtain the non-crystal boundary phrase porous silicon nitride ceramics. The porous ceramics can be widely applied to the base materials of filters used for separating gas in high temperature and corrosive atmospheres, and the high temperature heat resisting materials used by gas turbines used for generating power, engines, space shuttles, radomes, and the like.
Description
Technical field
The present invention relates to the preparation method of porous silicon nitride ceramic, relate in particular to a kind of method for preparing non-grain boundary phase porous silicon nitride ceramic based on carbothermic reduction.
Background technology
Porous silicon nitride has excellent mechanical property such as high-wearing feature, high anti-complaisance and traumatic resistance, can be applied to strainer, support of the catalyst and bio-reactor under the high low temperature, and the enhancing of matrix material equates in the every field.Porous silicon nitride also has good thermostability, lower specific inductivity, low-dielectric loss, high erosive wear resistance, is regarded as most promising electromagnetic wave transparent material of new generation.Silicon nitride is the strong covalent bond compound, and its self-diffusion coefficient is very little, and necessary volume diffusion of densification and crystal boundary velocity of diffusion are very little, simultaneously its crystal boundary energy V
GbWith powder surface energy V
Sv, ratio (V
Gb/ V
Sv) more much bigger than ionic compound and metal, make that sintering motivating force Δ V is less, therefore pure silicon nitride is difficult to by solid state sintering, the silicon-dioxide zone of oxidation or the silicon nitride that must add sintering aid (normally metal oxide) and alpha-silicon nitride powders surface form low-melting congruent melting liquid, have promoted SINTERING FOR SILICON NITRIDE CERAM and densification by liquid phase sintering mechanism.So far, the porous silicon nitride ceramic preparation is adopted and is added MgO, Al
2O
3, Y
2O
3, Yb
2O
3Produce liquid phase sintering Deng the oxidesintering auxiliary agent, and method such as carbothermic reduction.The molding of opening the mixed powder formation that will contain silicon nitride particle and oxidesintering auxiliary agent among the 2000-225985 as the Japanese Patent spy heats in nitrogen, and the addition of control sintering temperature and sintering aid obtains silicon nitride porous ceramic material.The Japanese Patent spy opens among the 2001-206775, has proposed to contain silica dioxide granule, and the molding of the metallic silicon particle that carbon granule and median size 5um are following is heat-treated the preparation porous silicon nitride ceramic in nitrogen.
Owing to add sintering aid,, form the porous silicon nitride ceramic that contains glassy phase among the above preparation method by liquid phase sintering.Owing to contain more glassy phase, intensity is lower, and at high temperature glassy phase is easily softening, so its high thermal resistance, performances such as insulativity and dielectricity all have certain influence.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of non-grain boundary phase porous silicon nitride ceramic improves the high-temperature behavior of existing porous silicon nitride ceramic and uses.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind ofly prepare the method for non-grain boundary phase porous silicon nitride ceramic, comprise the steps: based on carbothermic reduction
(1) by weight percentage, with following component: silicon nitride 93～95%, sintering aid 5～7% mix, and the preparation technology of porous silicon nitride routinely is at N
2In 1750 times sintering 2h, obtaining void content is the porous silicon nitride sample of 35-55% in the atmosphere;
(2) remove glassy phase and the formed compound of sintering aid in the porous silicon nitride sample with more than one pickling of hydrofluoric acid, nitric acid, sulfuric acid, acid is removed in alkali cleaning again, prepares the silicon nitride matrix sample of no crystal boundary;
(3) colloidal sol of formulated phenolic resin and silicon-dioxide, its resol cracked carbon and silica molar ratios are 1～3, and the nitride porous silicon substrate sample after the pickling is immersed in the colloidal sol, repeatedly infiltration is up to saturated;
The nitride porous silicon substrate sample drying that (4) will infiltrate saturated, place atmosphere furnace, with 5～30 the degree/minute heat-up rate be heated to 1200 ℃, feed nitrogen, rise to 1400～1600 ℃ behind 1～2h, being warming up to 1750～1800 ℃ behind 1～4h again, is to be incubated 1～2 hour under 2～6 normal atmosphere at nitrogen pressure, promptly obtains non-grain boundary phase porous silicon nitride ceramic.
In the aforesaid method, described sintering aid is at least a of aluminum oxide or trivalent rare earth metals oxide compound.Described sour Shen is the HNO with HF acid+98% of mass concentration 96%
3Acid, 60 ℃ of water-bath 2～4h remove glassy phase; H with mass concentration 98%
2SO
4Acid, 60 ℃ of water-bath 1h remove the compound of yttrium.Described alkali cleaning is to use the ammoniacal liquor of mass concentration 28%, and 69 ℃ of 1h remove acid.
The preparation method of described resol and silicon dioxide gel: get resol and be dissolved in the ethanol, the water bath with thermostatic control magnetic agitation, mix, tetraethoxy, dehydrated alcohol, hydromassage that are compared=1: mix at 2: 3, the water bath with thermostatic control magnetic agitation is even, adds the salt acid for adjusting pH value of mass concentration 38%, and hydrolysis obtains silicon dioxide gel, with two liquid uniform mixing, obtain the colloidal sol of resol and silicon-dioxide.
The present invention utilizes the normal pressure-sintered porous silicon nitride ceramic sample of preparing, and has guaranteed the good overlap joint of silicon nitride rod-like structure, utilizes the carbothermic reduction method to prepare the non-grain boundary phase porous silicon nitride ceramic that the silicon nitride that makes new advances is taken knot then.
The invention has the beneficial effects as follows,,, guarantee the homogeneity of infiltration by the colloidal sol of formulated phenolic resin and silicon-dioxide according to method of the present invention.By adjusting nitrogen pressure and sintering temperature, can obtain having the non-grain boundary phase porous silicon nitride ceramic of high porosity and excellent mechanical performances.Non-grain boundary phase porous silicon nitride ceramic of the present invention is compared with existing porous silicon nitride ceramic, owing to there is not the crystal boundary glassy phase, has excellent high-temperature behavior, the body material that can be widely used in the gas delivery usefulness strainer under high-temperature atmosphere and the aggressive atmosphere, generating internal combustion turbine, engine, space shuttle, the strengthening material of the heat-stable material that radome etc. use, the strengthening material of metal-base composites, and various thermal insulation, sound-absorbing, substrate etc.
Description of drawings
The XRD figure of Fig. 1 embodiment 1 normal pressure-sintered back sample.
The XRD figure of sample after Fig. 2 embodiment 1 carbothermic reduction.
The SEM of sample figure after Fig. 3 embodiment 1 carbothermic reduction
Embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
Porous silicon nitride ceramic, its composition is as shown in table 1, in the embodiment shown in the table 1 1～9, alpha-silicon nitride powders content is generally 93～95%, the addition of sintering aid is 5～7wt%, addition surpasses 7wt%, and the shrinking percentage of porous ceramics strengthens, and causes reducing and a large amount of intergranular glassy phases of void content.Sintering aid is meant the metal oxide that is varied to glassy phase in agglomerating high temperature field, can be expressed as M
2O
3Or MO (M is a metal), comprise that also a kind of oxide compound of or several compositions can become the mixture of glassy phase by reaction.The Y that adopts among such metal oxide such as table 1 embodiment
2O
3, Al
2O
3, Eu
2O
3Or Lu
2O
3At least a, according to circumstances also can add several hopcalites.
The preparation method of porous silicon nitride: silicon nitride is mixed the ball grinder of packing into sintering aid by the proportioning of table 1, is ball-milling medium with the dehydrated alcohol, with silicon nitride abrading-ball ball milling 24h on rotary mill.Mixed slip is dry in 60 ℃ of loft drier, cross 200 mesh sieves.The powder for preparing is pressed into bar-shaped sample at the pressure forming machine single shaft, then the green compact that press is being put in a plumbago crucible that scribbles BN, plumbago crucible is put into Japan produce the HIGH-MULTI-5000 multifunctional furnace, at N
2In 1750 ℃ of following sintering 2h, obtaining void content is the porous silicon nitride sample (embodiment 1-embodiment 9) of 35-55% in the atmosphere.
The silicon nitride matrix preparation method of sample of no crystal boundary: the porous silicon nitride sample that with table 1 embodiment 1-embodiment 9 preparation void content is 35-55% is with 96% dense HF acid+98% dense HNO
3Acid, 60 ℃ of temperature, water-bath 2～4h, glassy phase is removed in pickling; 98% dense H
2SO
4Acid, 60 ℃ of 1h, the compound of yttrium is removed in pickling; 28% dense ammonia, 69 ℃ of temperature, time 1h, acid is removed in alkali cleaning, prepares the silicon nitride matrix sample of no crystal boundary.
The preparation method of colloidal sol: get resol (70%C) and be dissolved in the ethanol, the water bath with thermostatic control magnetic agitation mixes.(TEOS, density is 0.933gmL with tetraethoxy
-1), (density is 0.79gmL to dehydrated alcohol
-1), water mixes according to a certain percentage, and (the mol ratio ratio is 1: 2: 3), the water bath with thermostatic control magnetic agitation is even, and (density is 1.19gmL to add hydrochloric acid
-1, mass percent concentration is about 38%), regulate the pH value, the hydrochloric acid consumption is HCl/TEOS=0.01mol (mol ratio), is hydrolyzed, and obtains silicon dioxide gel, with two mixed solution uniform mixing, prepares the colloidal sol of resol and silicon-dioxide.
The mol ratio of the silicon-dioxide of resol cracked carbon and teos hydrolysis is 1: 3～3: 1.In the carbothermic reduction reaction, the optimum mole ratio of carbon and silicon-dioxide is 2, when less than 1 the time,, therefore can generate the composite ceramics of silicon nitride and silicon-dioxide because carbon content is few, when greater than 3 the time, carbon content increases, and loss on ignition increases, and influences the intensity of non-grain boundary phase porous silicon nitride ceramic greatly, carbon and silicon-dioxide form silicon carbide easily, therefore select mol ratio 1～3.
No crystal boundary silicon nitride matrix sample embodiment 1-embodiment 9 after the pickling is immersed in the colloidal sol of different carbon and silica molar ratios (table 1), repeatedly infiltration is up to saturated.Put into multi-functional atmosphere stove after the oven dry, with 5～30 degree/minute 1200 ℃ of heat-up rate heating, feed nitrogen, rise to 1400～1600 ℃ behind 1～2h, rise to 1750-1800 ℃ behind 1～4h, at nitrogen pressure is to be incubated 1～2 hour under 2～6 normal atmosphere, promptly obtains non-grain boundary phase porous silicon nitride ceramic.
The sintering temperature of above-mentioned molding is down to 1750-1800 ℃ at nitrogen atmosphere.If temperature is less than 1750 degree, silicon nitride changes mutually and can not thoroughly finish.If temperature surpasses 1800 ℃, silicon nitride grain is grown up unusually, cause particulate inhomogeneous, mechanical properties decrease.In carbothermic reduction reaction, carbon and silicon-dioxide can pyroreaction silicon carbide, therefore can stop the formation of silicon carbide by improving nitrogen pressure.Soaking time was less than 1 hour, and the transformation mutually of silicon nitride is insufficient, according to XRD as can be known, was incubated 2 hours alpha-betas and changed mutually and finish fully, and time lengthening causes the waste of the energy, so soaking time is preferably in 1-2 hour.
With electronics balance measurement sample mass, three-point bending method is measured flexural strength.Archimedes's drainage is measured the ventilate rate.X-ray diffraction (XRD) instrument analyte phase.Observe the microstructure of sample with scanning electron microscope (SEM).The composition of table 1 embodiment of the invention 1-9 and sintering process condition.The test performance of table 2 porous silicon nitride ceramic of the present invention.The XRD figure of the normal pressure-sintered back of embodiment 1 sample as shown in Figure 1, after the carbothermic reduction XRD figure of sample as shown in Figure 2, SEM schemes as shown in Figure 3.
The composition of table 1 embodiment of the invention 1-9 and sintering process condition
| Example | Proportioning | Void content (%) | Bending strength (MPa) | Carbon and silica molar ratios | Temperature (℃) | Insulation (h) | Nitrogen pressure |
| Embodiment 1 | 95％Si 3N 4 +5％Y 2O 3 | 53.1 | 139.2 | 2 | 1750 | 2 | 6 |
| Embodiment 2 | 94％Si 3N 4+5％ Y 2O 3+1％Al 2O 3 | 42.4 | 197.2 | 1 | 1750 | 1 | 2 |
| Embodiment 3 | 93％Si 3N 44+5％ Y 2O 3+2％Al 2O 3 | 35.1 | 216.8 | 1 | 1750 | 1 | 2 |
| Embodiment 4 | 95％Si 3N 4 +5％Lu 2O 3 | 54.1 | 148.3 | 2 | 1800 | 1.5 | 6 |
| Embodiment 5 | 94％Si 3N 4+5％ Lu 2O 3+1％Al 2O 3 | 44.4 | 206.3 | 2 | 1800 | 1.5 | 6 |
| Embodiment 6 | 93％Si 3N 4+5％ Lu 2O 3+2％Al 2O 3 | 37.1 | 234.2 | 2 | 1800 | 1.5 | 6 |
| Embodiment 7 | 95％Si 3N 4 +5％Eu 2O 3 | 53.6 | 143.4 | 3 | 1750 | 2 | 4 |
| Embodiment 8 | 94％Si 3N 4+5％ Eu 2O 3+1％Al 2O 3 | 43.1 | 217.5 | 3 | 1750 | 2 | 4 |
| Embodiment 9 | 93％Si 3N 4+5％ Eu 2O 3+2％Al 2O 3 | 36.7 | 229.4 | 3 | 1750 | 2 | 4 |
The test performance of table 2 porous silicon nitride ceramic of the present invention
Table 2 is as can be seen: substrate quality reduces 5～10% after the pickling, and the weightening finish of infiltration back sample is 9～14%, and quality reduces 4～7% after the carbothermic reduction, therefore fills the quality that erodes substantially, and the void content of sample increases by 2～3% after the pickling.In 1750～1800 ℃ the temperature sintering range, material has shown very high flexural strength under the void content of 35-55%, reach as high as 220.67MPa.Along with cracked carbon and silica molar ratios in the resol increase, mass loss increases.After the sample corrosion, connect the interstructural glassy phase of silicon nitride rod-like and eroded, only remaining club shaped structure, and between overlap joint not, so intensity reduces, almost reduce to half of original intensity.After the matrix sample infiltrates resol and silicon-dioxide, resol cracked carbon and silicon-dioxide and nitrogen carbothermic reduction reaction generate silicon nitride, bar-shaped silicon nitride is overlapped again, so intensity raises, with the former sintered sample non-grain boundary phase porous silicon nitride ceramic of same strength level almost.
Fig. 1 is as can be seen: normal pressure-sintered sample principal crystalline phase is β-Si
3N
4, also have a spot of crystal boundary crystal phase Y
2Si
3O
3N
4This shows α-Si
3N
4All be transformed into β-Si
3N
4, phase transformation is finished, a spot of Y
2Si
3O
3N
4Be by Y
2O
3And Si
3N
4And SiO
2Reaction generates.In addition, because sintering aid has participated in the formation of liquid phase, therefore a part of form with amorphous glass crystal boundary phase is present in the sintered specimen behind final sintering.
Fig. 2 is as can be seen: have only β-Si among the carbothermic reduction sintering XRD
3N
4Diffraction peak, the composition that sample is described is β-Si
3N
4, and the diffraction peak of SiC does not appear, illustrate that under nitrogen atmosphere resol cracked carbon and silicon-dioxide and nitrogen carbothermic reduction reaction generate β-Si
3N
4, high nitrogen pressure can promote the formation of silicon nitride, and suppresses the formation of silicon carbide.
Fig. 3 is as can be seen: newly-generated bar-like grains is got up the brilliant overlap joint mutually of original silicon nitride rod-like, has improved the intensity of sample, therefore can prepare the porous silicon nitride ceramic of no crystal boundary phase.
Claims (5)
1. one kind prepares the method for non-grain boundary phase porous silicon nitride ceramic based on carbothermic reduction, it is characterized in that, comprises the steps:
(1) by weight percentage, with following component: silicon nitride 93～95%, sintering aid 5～7% mix, and the preparation technology of porous silicon nitride routinely is at N
2In 1750 times sintering 2h, obtaining void content is the porous silicon nitride sample of 35-55% in the atmosphere;
(2) remove glassy phase and the formed compound of sintering aid in the porous silicon nitride sample with more than one pickling of hydrofluoric acid, nitric acid, sulfuric acid, acid is removed in alkali cleaning again, prepares the silicon nitride matrix sample of no crystal boundary;
(3) colloidal sol of formulated phenolic resin and silicon-dioxide, its resol cracked carbon and silica molar ratios are 1～3, and the nitride porous silicon substrate sample after the pickling is immersed in the colloidal sol, repeatedly infiltration is up to saturated;
The nitride porous silicon substrate sample drying that (4) will infiltrate saturated, place atmosphere furnace, with 5～30 the degree/minute heat-up rate be heated to 1200 ℃, feed nitrogen, rise to 1400～1600 ℃ behind 1～2h, being warming up to 1750～1800 ℃ behind 1～4h again, is to be incubated 1～2 hour under 2～6 normal atmosphere at nitrogen pressure, promptly obtains non-grain boundary phase porous silicon nitride ceramic.
2, as claimed in claim 1ly prepare the method for non-grain boundary phase porous silicon nitride ceramic, it is characterized in that described sintering aid is at least a of aluminum oxide or trivalent rare earth metals oxide compound based on carbothermic reduction.
3, as claimed in claim 1ly prepare the method for non-grain boundary phase porous silicon nitride ceramic, it is characterized in that described pickling is the HNO with HF acid+98% of mass concentration 96% based on carbothermic reduction
3Acid, 60 ℃ of water-bath 2～4h remove glassy phase; H with mass concentration 98%
2SO
4Acid, 60 ℃ of water-bath 1h remove the compound of yttrium.
4, as claimed in claim 1ly prepare the method for non-grain boundary phase porous silicon nitride ceramic based on carbothermic reduction, it is characterized in that described alkali cleaning is to use the ammoniacal liquor of mass concentration 28%, 69 ℃ of 1h remove acid.
5, the method for preparing non-grain boundary phase porous silicon nitride ceramic based on carbothermic reduction as claimed in claim 1, it is characterized in that, the preparation method of described resol and silicon dioxide gel: get resol and be dissolved in the ethanol, the water bath with thermostatic control magnetic agitation, mix, tetraethoxy, dehydrated alcohol, hydromassage that are compared=1: mix at 2: 3, the water bath with thermostatic control magnetic agitation is even, the salt acid for adjusting pH value that adds mass concentration 38%, hydrolysis obtains silicon dioxide gel, with two liquid uniform mixing, obtain the colloidal sol of resol and silicon-dioxide.
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| CN101734925B (en) * | 2009-12-04 | 2012-02-01 | 西安交通大学 | Silicon nitride porous ceramics with controllable porosity and preparation method thereof |
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| CN110981495A (en) * | 2019-12-31 | 2020-04-10 | 江西中材新材料有限公司 | Porous sound-absorbing material and preparation method thereof |
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| CN111196729B (en) * | 2020-01-09 | 2021-08-06 | 中国科学院上海硅酸盐研究所 | Method for preparing porous silicon nitride ceramic by using ultralow-content sintering aid |
| CN112898040A (en) * | 2021-02-04 | 2021-06-04 | 西安交通大学 | Method for preparing intercrystalline-free glass phase beta-Si by using high length-diameter ratio whisker3N4Method for producing porous ceramics |
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