CN1060457C - Composite porcelain containing hexagonal boron nitride and preparation method thereof - Google Patents
Composite porcelain containing hexagonal boron nitride and preparation method thereof Download PDFInfo
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- CN1060457C CN1060457C CN97100379A CN97100379A CN1060457C CN 1060457 C CN1060457 C CN 1060457C CN 97100379 A CN97100379 A CN 97100379A CN 97100379 A CN97100379 A CN 97100379A CN 1060457 C CN1060457 C CN 1060457C
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- boron nitride
- boron oxide
- hexagonal boron
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Abstract
The present invention relates to a high-technology compound ceramic containing hexagonal boron nitride and a making method thereof. In the method, boron oxide and/or other boron containing raw materials are uniformly mixed with required ceramic materials for shaping, and through nitrogen treatment, the boron oxide is transformed into hexagonal boron nitride. The method of the present invention does not adopt the high-temperature high-pressure sintering method, and thus, the making cost is low; the high-technology compound ceramic containing hexagonal boron nitride of the present invention has the advantages of low price and improved toughness, thermal shock resistance and isotropy performance. The present invention develops an extensive prospect for the further application of high-technology compound ceramics.
Description
The present invention relates to a kind of hi-tech composite ceramics and preparation method thereof, more specifically say to relate to a kind of hi-tech composite ceramics that contains hexagonal boron nitride and preparation method thereof.
As everyone knows, high-performance ceramics is a kind of brand-new material, has its particular performances, as the high strength and high hardness high heat resistance.Thereby have purposes widely, be subjected to people's attention more and more widely.
The preparation method of high-performance ceramics generally comprises following steps at present:
Material is prepared: ceramic raw material that will be required is broken and grind to form the powder of certain particle size, and is mixed together evenly with sinter additives.
Moulding: the raw material powder that mixes is shaped to the sintering blank, and the most frequently used forming method is compression molding.Also can adopt not extrusion forming method.
Sintering: basic sintering method has following three kinds:
(1) solid state sintering: sintering temperature is generally more than 1500 ℃, and the sintering temperature of some material is up to 1800-2000 ℃, for some specific function material, and in order to obtain high-performance such as high-clarity, high thermal conductivity, sintering temperature even above 2000 ℃.Sintering time was generally several hours to tens hours.
(2) liquid phase sintering: liquid phase sintering is to carry out sintering by the blank (generally having the 50-60% relative density) that at least two kinds of pressed powders are made more than the common product temperature of two kinds of materials, can produce the liquid phase of 1-20% during sintering.
(3) reaction sintering: reaction sintering is that the reaction by two or more different chemical materials makes stupalith be coupled to holistic sintering method.
Although the application of high-performance ceramics constantly enlarges, there is unsatisfactory place.Mainly show and cost an arm and a leg and fragility is big and heat-shock resistance is poor.This has limited its use range, particularly is very limited as structured material.
High-performance ceramics costs an arm and a leg and is mainly caused by two aspects.First raw material powder price height is because raw material powder is very pure compound; It two is that its manufacture method is consuming time expensive.In above-mentioned manufacture method, raw material powder needs further broken and carries out uniform mixing up to 50-100 hour with various additives and other ceramic powder in ball mill, in addition, need the cycle to grow the High Temperature High Pressure sintering of (several hours to tens hours) during sintering.
Big and the heat-shock resistance difference of the fragility of high-performance ceramics is caused by himself chemical property and structure.The molecular structure of stupalith is covalent linkage and ionic linkage, and its knot contains can be big, again because the dislocation in the ceramic crystal is difficult to motion, thereby the plastic deformation ability extreme difference of stupalith.And the outward appearance distortion does not normally take place and fracture suddenly, it is big promptly to show as fragility, poor toughness.Closely-related with fragility is that heat-shock resistance is poor, and promptly cold-resistant thermal change voltinism is poor.Cold and hot variation makes the inequality of expanding with heat and contract with cold of stupalith, causes the generation and the expansion of crackle, in case crackle unstable propagation then cause sudden fracture.
Therefore, reduce the price of high-performance ceramics, improving its fragility and heat-shock resistance is that the present technique field is urgent required, and this becomes the key of high-performance ceramics broadened application.
In recent years, by the composition of selection hexagonal boron nitride, thereby fragility, thermal conductivity and heat-shock resistance have been improved as the hi-tech composite ceramic material.For example, people such as K.S.Mazdiyasni adopts high temperature and high pressure method to make Si
3N
4-BN pottery temperature: 1800 ℃, pressure: 34.5MPa) (J.of Am.Ceram.Soc., V 64, n7,1981, P415-419) and the AlN-BN pottery (sintering temperature: 1800-2000 ℃, pressure: 11.5MPa) (Am.ceram.Soc.Bull., V64, n8,1985, P1149-54); Human hot pressing (sintering temperatures: 1800 ℃ such as Takao kanai, pressure: 40MPa) make BN-AlN pottery (Japanese J.of Applied Physics, v31, n5A, 1992, P1426-1427), people such as W.S.Coblenz have proposed to use the chemical reaction sintering method, utilize boron oxide (B
2O
3) aluminium nitride (AlN) and/or silicon nitride (Si
3N
4), at compacting blank below 1000 ℃, in temperature compressive reaction more than 1600 ℃, make hexagonal boron nitride and aluminum oxide and/or silicon oxide ceramics (J.Am.Ceram.Soc., V71, n12,1988, P1080-85).
But above-mentioned art methods all adopts the sintering method of High Temperature High Pressure, and production cost is reduced, and promptly still can't obtain required not only reducing production costs but also improve these two kinds of effects of performance simultaneously.In addition, because the crystalline structure of hexagonal boron nitride is very similar to graphite, promptly the atom on its six sides plane is combined closely by covalent linkage, and is to be connect by Robert Van de Walle power between each plane more weakly.This structure has been improved fragility on the one hand, but shows very strong anisotropy.More than ten times, intensity difference is more than three times in the poor thermal conductivity on the both direction for the BN-AlN pottery of people such as for example above-mentioned Tokao Kanai preparation.Fracture toughness property difference 4-6 on the stupalith both direction of people such as above-mentioned W.S.Coblenz preparation doubly.
Therefore, need the traditional High Temperature High Pressure sintering method of high-performance ceramics is made improvements,, improve its fragility and heat-shock resistance simultaneously again to reduce cost.
The objective of the invention is to solve existing problem in the above-mentioned prior art, a kind of manufacture method that contains isotropic hi-tech composite ceramics of hexagonal boron nitride is provided, and reaches the effect that reduces production costs and improve its fragility and thermal shock resistance.
The manufacture method that contains the hi-tech composite ceramics of hexagonal boron nitride of the present invention may further comprise the steps:
(1) raw material mixes: with boron oxide, boric acid and/or other boracic raw material and other stupalith are even by required mixed;
(2) moulding: adopting compression molding or casting, is blank with the material forming that mixes;
(3) nitriding treatment: 450-950 ℃ of temperature, feed ammonia and carry out nitriding treatment, the time is 0.5-24 hour, and making boron oxide and/or other boracic feedstock conversion is boron nitride, ammonia decomposition is 10-60%, and nitridation time is for to be converted into the boron nitride required time with boron oxide.
The stupalith that the present invention relates to comprises various ceramic powder and/or ceramic fiber.
At the aforesaid method mesoboric acid is the source of boron oxide, is boron oxide after dehydration.This dehydrating step can be carried out when mixing, moulding or nitrogenize.
Can mix with mechanically mixing or solution in the mixing described in the aforesaid method.Wherein mechanically mixing is by traditional method boron oxide and/or other boracic raw material to be placed on stupalith in the devices such as ball mill to mix; It is to use solvent (as water, alcohol or other solvent) with boron oxide and/or other boracic material dissolution wiring solution-forming that solution wherein mixes, and mixes with stupalith again, places moisture eliminator to stir afterwards and drying, then obtains the powder that mixes.
In aforesaid method, described compression molding is for the stupalith that contains boron oxide, can in below 450 ℃ or more than carry out, these two kinds of temperature correspond respectively to solid-state and liquid oxidatively boron.The cost of formed solid is low, but density is lower.And the cost height of liquid condition shaping, but density height.For boronic acid containing (H
3BO
3) ceramic mixture, then mold temperature can be divided into five scopes according to degree of dehydration: room temperature to 170 ℃, boric acid does not have dehydration, cost is low, hole is maximum; 170 ℃-273 ℃, boric acid is decomposed into solid-state metaboric acid (HBO
2), partial dehydration, hole reduces to some extent; 273 ℃-300 ℃, metaboric acid is by the solid-state liquid state that transfers to, and most of dehydration just can obtain higher density in low pressure (being lower than 1.0MPa); 300 ℃-450 ℃, liquid metaboric acid dewaters fully and changes into solid oxide boron; More than 450 ℃: solid oxide boron changes into liquid state.The arrangement of the temperature of moulding, pressure and dewatering process is depended on the density of goods and performance demands.
At the casting described in the aforesaid method is the flowability of utilizing liquid oxidatively boron or metaboric acid, makes ceramic mixing raw material be cast as required shape in mould.Part for some shape can adopt compression casting.Can further dehydration after casting for the mixing raw material that contains metaboric acid.
The most outstanding characteristics of the inventive method are to adopt the low temperature nitriding treatment, promptly are in liquid state and other ceramic powder is still solid-state temperature province and carries out nitriding treatment at boron oxide.Promptly, decompose generation activated nitrogen atom and liquid oxidatively boron reaction generation boron nitride by ammonia in 450-950 ℃ of temperature.Do not react yet indiffusion and do not participate in as the pottery (powder and/or fiber) of another solid phase, even shape does not change yet, these hard particles are bound up on one by the engaged of corner angle each other on the one hand, and the boron nitride that generates by reaction is together bonding as boning on the other hand.Because no matter how much content of boron nitride has, all can think a kind of successive bonding phase, so the hi-tech composite ceramic material of this structure has fragility and thermal shock resistance that high toughness is promptly improved.
It should be noted, in the method for the invention, when carrying out nitriding treatment, volume will reduce about 42% when liquid oxidatively boron was transformed into the boron nitride of respective numbers, thereby reaction the time will inevitably stay hole, and this hole plays a very important role to method tool of the present invention.At first, this successive hole can provide ammonia to diffuse into the passage that the blank internal layer carries out nitrogenizing reaction, and this becomes nitrogenizing reaction prerequisite completely.Secondly, suitable porosity plays the effect that reduces fragility and improve heat-shock resistance.By suitable control composition and processing parameter, the porosity that may command is suitable.
Method of the present invention is not owing to adopt the High Temperature High Pressure sintering, thereby greatly reduce production cost, owing to adopt the composition of hexagonal boron nitride as ceramic, fragility and shock resistance have significantly been improved, because the boron nitride by boron oxide and/or other boracic raw material and ammonia react generation in the inventive method is free growing, so do not have anisotropy on macroscopic view.Be that the production cost that contains hexagonal boron nitride hi-tech composite ceramics that makes of the inventive method is low, fragility is low and good thermal shock and macroscopic view on show as isotropy.
The preparation method of hi-tech composite ceramics of the present invention breaks through the constraint of traditional ceramics production method, is a kind of new method, and prepared high-performance ceramics has the excellent ratio of performance to price, thereby has expanded range of application.
Further specify high-performance ceramics of the present invention and manufacture method thereof below in conjunction with embodiment.
Embodiment
Present embodiment prepares the ceramic composite of aluminium nitride and hexagonal boron nitride.
Select materials is the aluminum nitride powder and the chemical pure boric acid of diameter 4-6 micron.
Mix: adopt the solution blending means to carry out the uniform mixing of raw material powder, be about in the alcohol (chemical pure) that boric acid is dissolved in 50-60 ℃, each hundred ml ethanol dissolves in about 30-40 gram boric acid, then aluminium nitride powder is sneaked in this solution, and stirs drying.Afterwards with mixture heating up to 350 ℃ dehydration, dehydration back mixture has slight caking phenomenon, and it is ground to granule less than 0.2mm.
Make four kinds of mixture of ingredients altogether, promptly the effective content of boron oxide (weight percentage) is respectively Sample A in these mixtures: 6%, and sample B: 15%, sample C:22% and sample D:29%.
Moulding: the above-mentioned raw materials powder is pressed into the disk of 10mm in graphite jig, per sample (p.s.) weighs 0.64 gram, and the hot pressing furnace temperature is 560 ℃, is incubated 20 minutes, and used pressure is 22.5MPa, carries out in high pure nitrogen atmosphere during compacting.Obtain the sample that thickness is 2.5-3.0mm at last.
Nitriding treatment: use the iron and steel thermo-chemical treatment with nitriding furnace above-mentioned moulding sample to be carried out nitrogenize, temperature is 580 ± 10 ℃, and ammonia dissociation rate is approximately 60%, and nitridation time is 6 hours.Handle through this, obtain the ceramic composite of hexagonal boron nitride and aluminium nitride.
Obtained above-mentioned four kinds of BN-AlN ceramic samples are analyzed and performance test.
Sample is carried out the X-ray diffraction test, found sharp-pointed hexagonal boron nitride diffraction peak, do not find amorphous substance, also do not find the diffraction peak of boron oxide and boric acid.This illustrates that all boron oxides all have been converted into hexagonal boron nitride.
Four kinds of samples that present embodiment makes are 1.81g/cm by the proportion of liquid oxidatively boron
3(with reference to the vitreous state boron oxide), aluminium nitride proportion are 3.25g/cm
3, boron nitride proportion is 2.25g/cm
3Calculate liquid oxidatively boron in four kinds of samples and account for the weight percent of hexagonal boron nitride in matrix material after the volume percent of mixture and the nitrogenize, the results are shown in table 1.
Porosity with four kinds of samples of mercury infiltration method measurement the results are shown in table 1.
Four kinds of samples are carried out hardness test, test with 2 kilograms and 20 kilograms of loads respectively, wherein Sample A is very crisp, does not have hardness value.The results are shown in table 1.
The analysis and the performance of table 1 present embodiment ceramic sample
Find out that by table 1 volume of liquid oxidatively boron in mixture can make the high density ceramic matrix material greater than 30% o'clock.
In addition, the crack length when utilizing hardness test on four jiaos of the impressions calculates the fracture toughness property of sample D, and tests the performance number of its different directions.The results are shown in table 2.
According to the rule of mixture performance, with the data of data reduction one-tenth in the above-mentioned document and sample D identical component sample and compare.The sample of K.S.Mazdiyasni is converted into control sample 1.The sample of TakaoKanai is converted into control sample 2.List these data in table 2.
Table 2: the performance of the BN-AlN pottery that different methods is made
The data of control sample 2 are two groups of data in the table 2, show that the anisotropy of this sample is obvious.
As seen from Table 2, sample D of the present invention has identical density and the intensity with control sample 1, and is suitable with the hardness of control sample 2, but toughness is apparently higher than control sample 2.Should point out that control sample 2 has been owing to used 1.3% carbide of calcium additive, thereby have higher-strength and density.In addition, sample D of the present invention has isotropic performance, obviously is better than control sample.
The hi-tech composite ceramics manufacture method that contains hexagonal boron nitride of the present invention, owing to do not adopt the High Temperature High Pressure sintering, and do not add additive, thereby low cost of manufacture, the low price of obtained ceramic.In addition, owing to adopt hexagonal boron nitride as ceramics component, and adopt the technology of boron oxide nitriding treatment generation boron nitride, thereby finished product have good toughness and heat-shock resistance and isotropic performance.So just having obtained simultaneously reduces cost improves two kinds of effects of performance.For bright prospects have been opened up in the further widespread use of high-performance ceramics.
Though the present invention is illustrated by BN-AlN pottery and this specific embodiment of manufacture method thereof, present technique field personnel clearly realize that the present invention is not limited to this, method of the present invention generally is applicable to the manufacturing of the high-performance ceramics that contains hexagonal boron nitride, as BN-Si
3N
4Deng.What in addition, participate in nitrogenizing reaction in the present embodiment is boron oxide.And any material that can provide boron to originate all can be used as the raw material of nitriding treatment, and this is not limited to boron oxide or boric acid.
Claims (4)
1, a kind of preparation method who contains the composite ceramics of hexagonal boron nitride is characterized in that this method comprises the following steps:
(1) raw material mixes: with boron oxide or boric acid and ceramic powder and/or fiber uniform mixing, and boron oxide or be 6-29wt% wherein by the content of boric acid institute reduced boron oxide in mixture;
(2) moulding: adopt compression molding or casting, will mix raw material powder and be shaped to blank;
(3) nitriding treatment: 450-950 ℃ of temperature, feed ammonia and carry out nitriding treatment, the treatment time is 0.5-24 hour, afterwards cooling.
2, according to the process of claim 1 wherein described be mixed into mechanically mixing or solution mixing.
3, according to the process of claim 1 wherein described compression molding, carrying out solid-state compression molding below 450 ℃ for the ceramic mixture that contains boron oxide.
4, according to the process of claim 1 wherein described compression molding, carrying out liquid compression molding more than 450 ℃ for the ceramic mixture that contains boron oxide.
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| CN97100379A CN1060457C (en) | 1997-02-03 | 1997-02-03 | Composite porcelain containing hexagonal boron nitride and preparation method thereof |
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| CN97100379A CN1060457C (en) | 1997-02-03 | 1997-02-03 | Composite porcelain containing hexagonal boron nitride and preparation method thereof |
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Cited By (1)
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| CN100402465C (en) * | 2006-09-12 | 2008-07-16 | 吉林大学 | Method for preparing dielectric ceramic from wollastonite |
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| CN101973767A (en) * | 2010-11-17 | 2011-02-16 | 珲春先进陶瓷工程有限公司 | Preparation method of boron nitride |
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| CN108947587A (en) * | 2018-07-16 | 2018-12-07 | 西北工业大学 | A kind of preparation method at boron nitride interface |
| KR20210058855A (en) * | 2018-09-27 | 2021-05-24 | 스미또모 덴꼬오 하드메탈 가부시끼가이샤 | Cubic boron nitride polycrystal and method for producing same |
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| CN85104097A (en) * | 1985-05-24 | 1986-11-19 | 中国科学院上海硅酸盐研究所 | Boron nitride fiber reinforced reactively sintered silicon nitride ceramics |
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