CN101139168B - Method for preparing microwave dielectric glass ceramics - Google Patents
Method for preparing microwave dielectric glass ceramics Download PDFInfo
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- CN101139168B CN101139168B CN2007100165381A CN200710016538A CN101139168B CN 101139168 B CN101139168 B CN 101139168B CN 2007100165381 A CN2007100165381 A CN 2007100165381A CN 200710016538 A CN200710016538 A CN 200710016538A CN 101139168 B CN101139168 B CN 101139168B
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Abstract
The present invention relates to a preparation technique technology for glass ceramic materials, in particular to a preparation method for microwave dielectric glass ceramics in which the temperature feature of the materials can be effectively controlled. The preparation method comprises the steps such as raw material preparation, material mixing, glass melting, nuclearization heat treatment, crystallization treatment, etc. The same formula is adopted for products of different temperature drift parameters and the processes before the melting in the process of preparation are the same and the time for applying the heat treatment to products of different temperature drifts is different. The nucleation time of the glass ceramic is utilized to control the positive-negative of the dielectric constant and the magnitude of the temperature coefficient and change the temperature drift of the glass ceramic. Comparing the present invention with the prior art, the formula of the raw materials is optimized, the preparation technique is simple, the operation and control are convenient, the parameters of the prepared glass ceramics products are reliable and the glass ceramics can be widely applied in multiple fields of microwave dielectric materials.
Description
Technical field:
The present invention relates to a kind of fabricating technology field of glass ceramic material, particularly a kind of in heat treatment process the effective preparation method of the microwave dielectric glass ceramics of control material temperature profile.
Background technology:
Although glass-ceramic has been widely used in various dielectric materialss, be not a kind of ideal microwave dielectric material, three indexs of its reflection dielectric properties are not ideal.At first, specific inductivity is little, generally is no more than 10.Secondly, dielectric loss is excessive, and the Q value has only 200～500.Also having the important point, is exactly that temperature coefficient of permittivity is very high, instability.So practical glass-ceramic is few as microwave dielectric material, also is at present and inquires into and conceptual phase.Studying more is the glass-ceramic substrate material of low-k, and directly purpose is to reduce sintering temperature, realizes the common burning with integrated circuit, especially in the research and development of multi layer substrate.The research focus of this class material concentrated on reduce loss and promptly improve Q value aspect to reduce its heating, less demanding for temperature coefficient of permittivity (temperature is floated).And for capacitor material resonator material, temperature is floated but very important.The temperature coefficient of resonance frequency of a resonator is ± during 10ppm/ ℃.If resonant frequency is I0GHz when 30 ℃ of summers, ℃ be that its frequency will reach 10.55GHz or 9.45GHz in winter-25 so.To the frequency of facing mutually, the temperature that this material is described is floated excessive, is difficult to use.
The adjustment that existing microwave ceramics dielectric materials temperature is floated is by changing Chemical Composition, and positive temperature characteristics and subzero temperature characteristic two-phase proportion realize thereby change.This method is come directly, still, and the corresponding prescription of determining of each temperature factor of determining.In the time will producing the product of a plurality of temperature factor, need a plurality of prescriptions, sometimes, the product lot quantity that a certain temperature is floated is little, and its preparation cost is too big, is difficult to be suitable for the marketization and produces.In addition, glass-ceramic is considered to the material of low-k, and it is suitable to circuit substrate that people think always, makes the electrical condenser resonator and be unsuitable for.But,, add stronger ion such as the La of ionic polarization when its composition is transformed
3+, and Zn
2+The time, the polarization under the microwave condition will significantly strengthen.So, can improve the micro-wave dielectric constant greatly, just can be competent at being suitable for of electrical condenser resonator.
Summary of the invention:
The objective of the invention is to deficiency at existing microwave dielectric glass ceramics and preparation method thereof existence, propose a kind of preparation technology's method that can overcome the microwave dielectric glass ceramics of its prior art shortcoming, this method can effectively be controlled temperature by the control device in the heat treatment process and float; Can increase the specific inductivity of material under the microwave by control preparation technology parameter and prescription.
To achieve these goals, the inventive method comprises steps such as preparation raw material, batch mixing, glass smelting, coring thermal treatment, crystallization and thermal treatment; The product that equality of temperature is not floated parameter adopts same prescription, operation in its preparation process before the fusion is identical, the asynchronism(-nization) that the product that equality of temperature is not floated is heat-treated, positive and negative and big or small with glass-ceramic nucleation time control temperature coefficient of permittivity, and change its temperature drift.
(1) weight percent of listing by table 1 formulated raw material when
Table 1: composition of raw materials (wt/%)
| SiO 2 | Al 2O 3 | La 2O 3 | ZnO? | MgO? | B 2O 3 | TiO 2 |
| 30.8? | 10.3? | 12.7? | 14? | 12.2? | 5? | 15? |
(2) batch mixing and glass smelting
1. take by weighing the chemical pure powder of each composition according to prescription in the table, wherein Al
2O
3And SiO
2The powder median size is poured ball mill into less than 10 μ m, adds water for ball milling 4 hours, and the ratio of its raw material, ball, water is 30: 30: 40; It is standby to be dried into mixed powder then under 110～130 ℃;
2. with the mixed powder of oven dry at 40MPa pressure lower lock block, put into the pure alumina crucible, bubble is eliminated in 1200～1300 ℃ of fusions more than 1 hour in stove, forms the clarification liquation;
3. will clarify liquation and pour in 550～650 ℃ the mould, mould is put into 550～650 ℃ stove with frit, furnace cooling obtains translucent vitreum.
(3) coring thermal treatment
Require difference according to temperature coefficient of permittivity, vitreum is put into 600～700 ℃ retort furnace, be incubated 3～10 hours; When requiring temperature to float to be zero, be about 7 hours, when positive temperature is floated less than 7 hours, when subzero temperature floats greater than 7 hours; After the coring thermal treatment, the glass block becomes opaque, the whitening look, and a large amount of nucleus produce, and have the residual glass phase.
(4) crystallization and thermal treatment
With the glass block after the coring thermal treatment, under 750～850 ℃, handle and made residual glass phase crystallization in 30 hours, obtain finished product; Finished product its characteristic under 10GHz is: relative permittivity
〉=14.5, the inverse 〉=12600GHz of test frequency f * Q loss tangent value, drift temperature factor τ
fFor+125～-110ppm/ ℃.
Soaking time difference under the coring thermal treatment of the present invention in thermal treatment, τ
fCan in very broad scope, regulate, to satisfy various use needs.
The present invention compared with prior art, its composition of raw materials is optimized, preparation technology is simple, convenient operation and control, the and reliable in parameters of prepared glass-ceramic product can be widely used in multiple microwave dielectric material field.
Embodiment:
Enforcement of the present invention comprises preparation raw material, batch mixing, glass smelting, coring thermal treatment, five steps of crystallization and thermal treatment:
The weight percent prescription of preparation raw material is: SiO
2: 30.8; Al
2O
3: 10.3; La
2O
3: 12.7; ZnO:14; MgO:12.2; B
2O
3: 5; TiO
2: 15.
Take by weighing the chemical pure powder of each composition earlier according to prescription, require Al
2O
3And SiO
2The powder median size is poured ball mill into less than 10 μ m, adds water for ball milling 4 hours, and wherein, the ratio of raw material, ball, water is 30:30:40; Then 110～130 ℃ of following dry for standby;
Again with the mixed powder of oven dry at 40MPa pressure lower lock block, put into the pure alumina crucible, bubble is eliminated in 1200～1300 ℃ of fusions more than 1 hour in stove, forms the clarification liquation;
To clarify liquation then and pour in the mould about 550～650 ℃, mould is put into 550～650 ℃ stove with frit, furnace cooling obtains translucent vitreum;
Require difference according to temperature coefficient of permittivity, vitreum is put into 600～700 ℃ retort furnace, be incubated 3～10 hours; When requiring temperature to float to be zero, be 6～8 hours, when positive temperature is floated 6 hours, when subzero temperature floats 8 hours; After the coring thermal treatment, it is opaque fully that vitreum becomes, the whitening look, and a large amount of nucleus produce, but also have the residual glass phase.
With the glass block after the coring thermal treatment, made residual glass phase crystallization in 30 hours at last, obtain finished product 800 ℃ of following crystallization and thermal treatment.
Embodiment 1:
Produce a collection of drift temperature factor τ according to above-mentioned implementation step
fBe 0 product, the having the call of this series products, requiring has very stable operating frequency, desirable lower value between the parameter region in its process, the coring heat treatment time is 7 hours.
Embodiment 2:
Produce a collection of drift temperature factor τ according to above-mentioned implementation step
fProduct for+5ppm/ ℃ temperature factor for the negative temperature characteristic of compensation integral circuit, needs resonator that positive temperature characteristics is arranged sometimes; Capping value between the parameter region in its process, coring heat treatment time are 6.5 hours.
The product that above-mentioned two embodiment make records its characteristic parameter value under the 10GHz condition: relative permittivity ε
rBe 14.8, f * Q is 12800GHz.
Claims (3)
1. the preparation method of a microwave dielectric glass ceramics is characterized in that comprising preparation raw material, batch mixing, glass smelting, coring thermal treatment, crystallization and thermal treatment step; The product that equality of temperature is not floated parameter adopts same prescription, operation in its preparation process before the fusion is identical, the asynchronism(-nization) that the product that equality of temperature is not floated is heat-treated, positive and negative and big or small with glass-ceramic nucleation time control temperature coefficient of permittivity, and change its temperature drift; When requiring temperature to float to be zero, be 7 hours, when positive temperature is floated less than 7 hours, when subzero temperature floats greater than 7 hours; The weight percent prescription of its preparation raw material is: SiO
2: 30.8; Al
2O
3: 10.3; La
2O
3: 12.7; ZnO: 14; MgO: 12.2; B
2O
3: 5; TiO
2: 15.
2. the preparation method of microwave dielectric glass ceramics according to claim 1 is characterized in that batch mixing and glass smelting take by weighing the chemical pure powder of each composition, wherein Al by prescription
2O
3And SiO
2The powder median size is poured ball mill into less than 10 μ m, adds water for ball milling 4 hours, and the ratio of its raw material, ball, water is 30: 30: 40; It is standby to be dried into mixed powder then under 110～130 ℃; The mixed powder of oven dry at 40MPa pressure lower lock block, is put into the pure alumina crucible, and bubble is eliminated in 1200～1300 ℃ of fusions more than 1 hour in stove, forms the clarification liquation; Pour in 550～650 ℃ the mould clarifying liquation, mould is put into 550～650 ℃ stove with frit, furnace cooling obtains translucent vitreum.
3. the preparation method of microwave dielectric glass ceramics according to claim 1 is characterized in that coring thermal treatment according to temperature coefficient of permittivity, puts into 600～700 ℃ retort furnace with vitreum, is incubated 3～10 hours; After the coring thermal treatment, the glass block becomes opaque, the whitening look, and nucleus produces, and has glassy phase.
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|---|---|---|---|
| CN2007100165381A CN101139168B (en) | 2007-08-18 | 2007-08-18 | Method for preparing microwave dielectric glass ceramics |
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|---|---|---|---|
| CN2007100165381A CN101139168B (en) | 2007-08-18 | 2007-08-18 | Method for preparing microwave dielectric glass ceramics |
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|---|---|
| CN101139168A CN101139168A (en) | 2008-03-12 |
| CN101139168B true CN101139168B (en) | 2010-12-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103771711B (en) * | 2013-12-24 | 2016-05-18 | 中国科学院上海硅酸盐研究所 | Devitrified glass of high quality factor and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1662463A (en) * | 2000-09-01 | 2005-08-31 | W·C·贺利氏股份有限两合公司 | Glass ceramic mass and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1662463A (en) * | 2000-09-01 | 2005-08-31 | W·C·贺利氏股份有限两合公司 | Glass ceramic mass and use thereof |
Non-Patent Citations (5)
| Title |
|---|
| JP特开2006-248801A 2006.09.21 |
| 刘建安等.钛酸铅微晶玻璃介电性能研究.玻璃与搪瓷33 1.2005,33(1),11-14. |
| 刘建安等.钛酸铅微晶玻璃介电性能研究.玻璃与搪瓷33 1.2005,33(1),11-14. * |
| 刘浩等.MgO-Al_2O_3-SiO_2系统微晶玻璃的热处理工艺对其介电性能的影响.佛山陶瓷14 8.2004,14(8),12-14. |
| 刘浩等.MgO-Al_2O_3-SiO_2系统微晶玻璃的热处理工艺对其介电性能的影响.佛山陶瓷14 8.2004,14(8),12-14. * |
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