CN103058652B - Preparation method of calcium-borate-glass-modified strontium titanate-lanthanum aluminate composite ceramic - Google Patents

Preparation method of calcium-borate-glass-modified strontium titanate-lanthanum aluminate composite ceramic Download PDF

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CN103058652B
CN103058652B CN201310003909.8A CN201310003909A CN103058652B CN 103058652 B CN103058652 B CN 103058652B CN 201310003909 A CN201310003909 A CN 201310003909A CN 103058652 B CN103058652 B CN 103058652B
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CN103058652A (en
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樊慧庆
雷慎辉
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Dongguan Meitu Baoxin Material Co.,Ltd.
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Northwestern Polytechnical University
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Abstract

The invention discloses a preparation method of calcium-borate-glass-modified strontium titanate-lanthanum aluminate composite ceramic. The method is used for solving a technical problem of high preparation temperature of an existing STO-LAO ceramic material preparation method. According to a technical scheme provided by the invention, alumina, lanthanum oxide, titanium dioxide and strontium carbonate are adopted as raw materials, and are subjected to ball milling in a nylon tank with anhydrous ethanol as a grinding medium; bake-drying and grinding are carried out, and the material is sintered in a sintering reaction furnace; calcium borate glass is added, and secondary ball milling is carried out; bake-drying and grinding are carried out, and the material is pressed and molded by using a cold isostatic pressing machine; and sintering is carried out after molding, such that the calcium-borate-glass-modified strontium titanate-lanthanum aluminate composite ceramic is obtained. In a solid-phase sintering reaction, the added calcium borate glass sintering aid system produces a proper amount of an additive liquid phase, such that atom migration diffusion rate is accelerated, mass transfer process is enhanced, reaction process is accelerated, and reaction temperature and time are reduced. The preparation temperature is reduced from 1100-1250 DEG C of a background technology to 1550-1680 DEG C.

Description

The preparation method of lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics
Technical field
The present invention relates to a kind of preparation method of strontium titanate-lanthanum aluminate composite ceramics, be specifically related to a kind of preparation method of lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics.
Background technology
Strontium titanate-lanthanum aluminate (hereinafter to be referred as STO-LAO) stupalith is important study hotspot material, and it is at super crystal lattice material, heterojunction material, and monocrystal material, substrate material and function film energy direction have large quantity research.And everybody has often ignored its microwave communication material applications.Because STO-LAO ceramic material microwave is functional, material as microwave devices such as resonator, wave filter, vibrator, clamper, polyrod antenna, medium guided wave loops, be widely used in mobile communication, high definition satellite communication and military commerical radar, the fields such as vehicle-mounted airborne wireless telecommunications system.
Document 1 " T.Shimada, K.Kura, S.Ohtsuki.Dielectric properties and far infrared reflectivity of lanthanum aluminate-strontium titanate ceramics.Journal of the European Ceramic Society, 2006, 26:2017-2021. " a kind of preparation method of STO-LAO stupalith disclosed, the method adopts the Strontium carbonate powder that purity is 99.9%, titanium dioxide, aluminum oxide, lanthanum oxide powder is raw material, raw material powder is dried to accurate weighing, lanthanum trioxide is 500 ℃ of oven dry in addition, after weighing, with deionized water, be grinding medium, after ball milling at 1400 ℃ of preburning powdered materials, with after 150MPa pressure forming, then adopt oxide compound mixed-sintering method to send out and prepared STO-LAO system pottery, sintering temperature is 1580～1680 ℃, concrete sintering process such as soaking time etc. does not provide detailed introduction.
Document 2 " Seo-Yong Cho, Kug Sun Hong, Kyung-Hyun Ko.Mixture-like behavior in the microwave dielectric properties of the (1-x) LaAlO 3xSrTiO 3system.Materials Research Bulletin, 3,1999,34 (4): 511～516. " disclose a kind of preparation method of STO-LAO stupalith, the method has been prepared (1-x) LaAlO with traditional solid sintering technology at 1550～1650 ° of C sintering 3xSrTiO 3(x=0.0～1.0) pottery.Its Strontium carbonate powder, titanium dioxide, aluminum oxide, lanthanum oxide powder that has adopted that purity is 99.9% is raw material, raw material powder is dried to accurate weighing, with zirconium dioxide abrading-ball ball milling 24h in ball grinder, after at 1300 ℃ of pre-burning 2h, after secondary ball milling 24h under air atmosphere, 1550～1650 ° of C sintering 2 hours.
The preparation method of the disclosed STO-LAO stupalith of above-mentioned document, its preparation temperature is all too high.
Summary of the invention
In order to overcome the high deficiency of preparation method's preparation temperature of existing STO-LAO stupalith, the invention provides a kind of preparation method of lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics.The method be take high-purity strontium carbonate, aluminum oxide, lanthanum trioxide, titanium dioxide and dehydrated alcohol as raw material, add sintering aid system lime borate oxide glass, by traditional solid reaction process, in lower temperature and shorter time, obtain high performance strontium titanate-lanthanum aluminate stupalith.Due in solid state sintering reaction, the lime borate oxide glass sintering aid system of interpolation produces appropriate additive liquid phase, can accelerate the diffusion mobility speed of atom, and then strengthens mass transfer process, and accelerated reaction process, reduces temperature of reaction and time.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics, is characterized in comprising the following steps:
(a) by stoichiometry mol ratio aluminum oxide: lanthanum trioxide: titanium dioxide: Strontium carbonate powder=x: x: (1-x): (1-x) [x=0～1] weighs purity higher than 99.5% aluminum oxide, lanthanum trioxide, titanium dioxide and Strontium carbonate powder raw material powder, and be poured in the nylon tank that zirconium oxide balls is housed, by compactedness, be that requirement below 60% adds analytical pure dehydrated alcohol as grinding medium, with ball milling 5～10h under the speed of 450～500r/min, oven dry is incubated 3～10h after grinding in the sintering reaction stove of 1300～1400 ° of C;
(b) take out powder after sintering and add 1～10wt%, purity higher than 99.5% lime borate glass, secondary ball milling 5～10h under the speed of 450～500r/min, dries after grinding and takes out;
(c) use cold isostatic press in 300～500Mpa compression moulding;
(d) after moulding at 1100～1250 ° of C sintering 3～4h, obtain strontium titanate-lanthanum aluminate composite ceramics of lime borate glass modification.
In described step (b), the preparation method of lime borate glass is that calcium oxide and boric acid oxide compound glass are according to CaO: B 2o 3mol ratio=2: 1～1: 2 batchings, 800～900 ° of C insulations were as cold as room temperature in deionized water middling speed after one hour, were ground to maximum particle diameter and were less than 30 μ m.
The invention has the beneficial effects as follows: owing to take high-purity strontium carbonate, aluminum oxide, lanthanum trioxide, titanium dioxide and dehydrated alcohol as raw material, add sintering aid system lime borate oxide glass, by traditional solid reaction process, in lower temperature and shorter time, obtain high performance strontium titanate-lanthanum aluminate stupalith.Due in solid state sintering reaction, the lime borate oxide glass sintering aid system of interpolation produces appropriate additive liquid phase, has accelerated the diffusion mobility speed of atom, and then has strengthened mass transfer process, has accelerated reaction process, has reduced temperature of reaction and time.Preparation temperature is reduced to 1550～1680 ° of C by 1100～1250 of background technology.
Below in conjunction with drawings and Examples, the present invention is elaborated.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of strontium titanate-lanthanum aluminate composite ceramics of the embodiment of the present invention 1～4 preparation.
Fig. 2 is the stereoscan photograph of strontium titanate-lanthanum aluminate composite ceramics of the embodiment of the present invention 1～4 preparation.
Fig. 3 is the performance curve of strontium titanate-lanthanum aluminate composite ceramics of the embodiment of the present invention 1～4 preparation.
Fig. 4 is strontium titanate-lanthanum aluminate composite ceramics of the embodiment of the present invention 1～4 preparation dielectric properties curve under microwave frequency band 7GHz.
Embodiment
With reference to Fig. 1～4.Preparation method's concrete steps of lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics of the present invention are as follows:
Embodiment 1,0.3: 0.3: 0.7 in molar ratio: 0.7 weighs purity higher than 99.5% alumina raw material powder 3.0588g, lanthanum trioxide 9.7743g, titanium dioxide 5.5906g and Strontium carbonate powder 10.3340g, and be poured in the nylon tank that zirconium oxide balls is housed, by compactedness, be that requirement below 60% adds analytical pure dehydrated alcohol as grinding medium, with the speed ball milling 10h of 450r/min, oven dry is incubated 10h after grinding in the sintering reaction stove of 1300 ° of C; Take out powder after sintering add high-purity (>=99.5%) calcium oxide of 1wt% (0.2876g) and boric acid oxide glass (hereinafter to be referred as BC, CaO: B 2o 3mol ratio is 2: 1, and 850 ° of C insulations are as cold as room temperature in deionized water middling speed after one hour and make glass, are ground to maximum particle diameter and are less than 30 μ m) at the speed secondary ball milling 10h of 450r/min, dry and grind rear taking-up; With cold isostatic press in 300Mpa compression moulding; After moulding, at 1250 ° of C sintering 3h, obtain strontium titanate-lanthanum aluminate composite ceramics of lime borate glass modification.
Embodiment 2,0.3: 0.3: 0.7 in molar ratio: 0.7 weighs purity higher than 99.5% alumina raw material powder 3.0588g, lanthanum trioxide 9.7743g, titanium dioxide 5.5906g and Strontium carbonate powder 10.3340g, and be poured in the nylon tank that agate abrading-ball is housed, by compactedness be requirement below 60% add deionized water as grinding medium the speed ball milling 9h with 470r/min, dry after grinding and be incubated 7h in the sintering reaction stove of 1330 ° of C; Take out powder after sintering add high-purity (>=99.5%) calcium oxide of 2wt% (0.5752g) and boric acid oxide glass (hereinafter to be referred as BC, CaO: B 2o 3mol ratio is 1: 2, and 900 ° of C insulations are as cold as room temperature in deionized water middling speed after one hour and make glass, are ground to maximum particle diameter and are less than 30 μ m) at the speed secondary ball milling 9h of 470r/min, dry and grind rear taking-up; With cold isostatic press in 370Mpa compression moulding; After moulding, at 1200 ° of C sintering 3.3h, obtain strontium titanate-lanthanum aluminate composite ceramics of lime borate glass modification.
Embodiment 3,0.6: 0.6: 0.4 in molar ratio: 0.4 weighs purity higher than 99.5% alumina raw material powder 6.1177g, lanthanum trioxide 19.5485g, titanium dioxide 3.1946g and Strontium carbonate powder 5.9052g, and be poured in the nylon tank that zirconium oxide balls is housed, by compactedness be requirement below 60% add analytical pure dehydrated alcohol as grinding medium the speed ball milling 7h with 490r/min, dry after grinding and be incubated 5h in the sintering reaction stove of 1360 ° of C; Take out powder after sintering add high-purity (>=99.5%) calcium oxide of 5wt% (1.7383g) and boric acid oxide glass (hereinafter to be referred as BC, CaO: B 2o 3mol ratio is 1: 1, and 800 ° of C insulations are as cold as room temperature in deionized water middling speed after one hour and make glass, are ground to maximum particle diameter and are less than 30 μ m) at the speed secondary ball milling 7h of 490r/min, dry and grind rear taking-up; With cold isostatic press in 430Mpa compression moulding; After moulding, at 1150 ° of C sintering 3.7h, obtain strontium titanate-lanthanum aluminate composite ceramics of lime borate glass modification.
Embodiment 4,0.4: 0.4: 0.6 in molar ratio: 0.6 weighs purity higher than 99.5% alumina raw material powder 4.0785g, lanthanum trioxide 13.0324g, titanium dioxide 4.7919g and Strontium carbonate powder 8.8577g, and be poured in the nylon tank that agate abrading-ball is housed, by compactedness be requirement below 60% add deionized water as grinding medium the speed ball milling 5h with 500r/min, dry after grinding and be incubated 3h in the sintering reaction stove of 1400 ° of C; Take out powder after sintering add high-purity (>=99.5%) calcium oxide of 10wt% (3.076g) and boric acid oxide glass (hereinafter to be referred as BC, CaO: B 2o 3mol ratio is 1: 1, and 900 ° of C insulations are as cold as room temperature in deionized water middling speed after one hour and make glass, are ground to maximum particle diameter and are less than 30 μ m) at the speed secondary ball milling 5h of 500r/min, dry and grind rear taking-up; With cold isostatic press in 500Mpa compression moulding; After moulding, at 1100 ° of C sintering 4h, obtain strontium titanate-lanthanum aluminate composite ceramics of lime borate glass modification.
Above concrete numerical value passes through summary of experience by great many of experiments and gropes out, for example: Ball-milling Time 5～10 hours, the uniform granularity degree of 5 hours following powders is not ideal enough, and more than 10 hours, performance is substantially unchanged, thereby cause waste.In like manner, in sintering reaction stove, being incubated 3～10h is also the optimized scope that test obtains.For example rotating speed is between 450～500r/min again, and the too low granularity of rotating speed is excessive, and the too high powder cohesiveness that causes of rotating speed increases, and is unfavorable for subsequent disposal.The addition of zinc oxide and boric acid oxide compound 1～10wt% has guaranteed the comprehensive excellent properties of strontium titanate-lanthanum aluminate composite ceramics, and performance is more excellent during few additive, and when addition strengthens, cooling-down effect is more obvious.
As can be seen from Figure 1, obtained lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics crystal property is intact, and phase composition is even, substantially without dephasign.
As can be seen from Figure 2, obtained lime borate glass modification strontium titanate-lanthanum aluminate composite ceramic particle is complete, well-crystallized, and crystal grain is evenly tiny, without separating out of second-phase and dephasign.
As can be seen from Figure 3, prepared different components and add the xSTO-1-x of the BC glass of 1～10wt%) LAO composite ceramics is under radio frequency, ceramic loss is very low, temperature stability is good.
As can be seen from Figure 4, matrix strontium titanate-lanthanum aluminate composite ceramics excellent performance under 7GHz, specific inductivity approaches 50, minimum the more than 30 of up-to-date domestic and international commercial applications that surpassed.Q f mechanical quality factor reach approach 50,000GHz(wherein minimum sintered ceramic as figure be about 42,000GHz), and reached nearly zero temperature coefficient of resonance frequency (≤± 40 * 10 -6), applicability is very high.Prepared lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics, the excellent properties that has kept matrix pottery, and sintering temperature is significantly reduced to 1100 ° below C by 1680 ° of C of background technology, being better than international current reported low-temperature sintering type microwave dielectric ceramic novel material 50%～100%(experiment gained is 10 as schemed minimum, 000GHz left and right, and international literature report is commonly 5 at present, 000～8, the integrated chip type technique burning of 000GHz) being convenient to product and metal is made, and has very large commercial application prospect and excellent practical performance.

Claims (1)

1. a preparation method for lime borate glass modification strontium titanate-lanthanum aluminate composite ceramics, is characterized in that comprising the following steps:
(a) by stoichiometry mol ratio aluminum oxide: lanthanum trioxide: titanium dioxide: Strontium carbonate powder=x: x: (1-x): (1-x) [x=0～1] weighs purity higher than 99.5% aluminum oxide, lanthanum trioxide, titanium dioxide and Strontium carbonate powder raw material powder, and be poured in the nylon tank that zirconium oxide balls is housed, by compactedness, be that requirement below 60% adds analytical pure dehydrated alcohol as grinding medium, with ball milling 5～10h under the speed of 450～500r/min, oven dry is incubated 3～10h after grinding in the sintering reaction stove of 1300～1400 ° of C;
(b) take out powder after sintering and add 1～10wt%, purity higher than 99.5% lime borate glass, secondary ball milling 5～10h under the speed of 450～500r/min, dries after grinding and takes out;
(c) use cold isostatic press in 300～500Mpa compression moulding;
(d) after moulding at 1100～1250 ° of C sintering 3～4h, obtain strontium titanate-lanthanum aluminate composite ceramics of lime borate glass modification;
In described step (b), the preparation method of lime borate glass is that calcium oxide and boric acid oxide compound glass are according to CaO: B 2o 3mol ratio=2: 1～1: 2 batchings, 800～900 ° of C insulations were as cold as room temperature in deionized water middling speed after one hour, were ground to maximum particle diameter and were less than 30 μ m.
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