CN1693280A - Microwave medium ceramics and its preparation process - Google Patents

Microwave medium ceramics and its preparation process Download PDF

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Publication number
CN1693280A
CN1693280A CN 200510011860 CN200510011860A CN1693280A CN 1693280 A CN1693280 A CN 1693280A CN 200510011860 CN200510011860 CN 200510011860 CN 200510011860 A CN200510011860 A CN 200510011860A CN 1693280 A CN1693280 A CN 1693280A
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microwave
nitrate
medium ceramics
powder
citric acid
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岳振星
赵飞
李龙土
桂治轮
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Tsinghua University
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Tsinghua University
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Abstract

A ceramics as microwave medium has a chemical formula: CaO-2MO-xTiO2, where M is chosen from Zn, Cu, Ni and Mg and x=5-10. It is prepared through proportionally dissolving nitrate, butyl titanate and citric acid in deionized water, adding ammonia water to become sol, heating to become gel, calcining to become activated powder, wet grinding, die pressing and sintering at 1000-1100 deg.C.

Description

A kind of microwave-medium ceramics and preparation method thereof
Technical field
The present invention relates to a kind of is the complex phase ceramic compound and preparation method thereof of foundation characteristic with the oxide compound, and definite says, is to be complex phase ceramic of principal phase and preparation method thereof with a kind of many titanates with lower sintering temperature, belongs to the microwave dielectric material manufacturing
Technical field.
Background technology
Microwave-medium ceramics is the core material of microwave device.Recently for over ten years, because microwave technology equipment to miniaturization and integrated, especially develops rapidly to civilian in enormous quantities, low price direction, large quantities of microwave dielectric ceramic materials that are applicable to various microwave frequency bands have been developed at present.Be applied to the media ceramic of microwave circuit, should satisfy the requirement of following dielectric characterization: the relative permittivity ε that (1) is high rTo reduce device size, general requirement ε r〉=20; (2) high quality factor q is to improve selecting frequency characteristic, general requirement Q * f 〉=3000GHz; (3) near zero frequency-temperature coefficient τ fTo guarantee that device has good temperature stability.The microwave-medium ceramics of being used widely at present mainly contains high-dielectric constant microwave pottery and high quality factor microwave ceramics two classes.In recent years, along with the development of LTCC Technology (LTCC) and the requirement of microwave multilayer device development, domestic and international research personnel have carried out exploring widely and studying to some low fever's system materials, at present to the research and development of this field material still among positive the development.But still more limited for the system that is used for low fever's microwave-medium ceramics, this has limited the development of low temperature co-fired technology and microwave multilayer device to a great extent.
In the preparation process of microwave-medium ceramics, adopt the solid phase reaction process synthesizing ceramic powder usually, there is the sintering temperature height, react shortcoming such as incomplete.Particularly be difficult to the synthetic compound for some, common electronic ceramics synthetic method is difficult to obtain single thing phase, and adopts sol-gel method just can overcome above-mentioned deficiency, reaches the purpose that reduces sintering temperature and increase reactive behavior.
Summary of the invention
The objective of the invention is to develop a kind of low fever's microwave-medium ceramics low temperature co-fired microwave dielectric ceramic field, that have medium specific inductivity that is expected to be applied to, promptly the technological line by the sol-gel combustion method obtains a kind of microwave-medium ceramics with lower sintering temperature, medium specific inductivity and higher figure of merit.
The invention provides the method for compositing formula and this media ceramic product of preparation of this low fever's media ceramic.
Low fever's microwave-medium ceramics of medium specific inductivity of the present invention is made up of the oxide compound of Ca and Ti and one or both oxide compounds among Zn, Cu, Ni and the Mg, and its chemical constitution is: CaO-2MO-xTiO 2(M represents Zn, Cu, Ni, Mg).
Described media ceramic, its component mole deal ratio is: GaO 1: MO 2: TiO 25～10.
The preparation method of described microwave-medium ceramics of the present invention is characterized in that, described CaO-2MO-xTiO 2(M represents Zn, Cu, Ni, Mg), x=5～10 potteries wherein are that nitrocalcite, zinc nitrate, cupric nitrate, nickelous nitrate, magnesium nitrate, butyl (tetra) titanate and citric acid more than 99% is starting raw material with purity, are made up of following steps:
(1) a certain proportion of nitrocalcite, zinc nitrate (or cupric nitrate, nickelous nitrate, magnesium nitrate), citric acid and butyl (tetra) titanate are dissolved in a certain amount of deionized water, form solution, wherein the amount of the citric acid of Jia Ruing is 1～2: 1 with the ratio of metal ion total mole number;
(2) ammoniacal liquor is slowly added in the solution of step (1) preparation, reach 6,, form transparence colloidal sol 50～80 ℃ of heating and lasting the stirring until the pH value;
(3) colloidal sol with step (2) preparation places 100～120 ℃ baking oven to dry, until forming filemot xerogel;
(4) xerogel that step (3) is obtained ignites in air, and xerogel burning back forms fluffy black powder;
(5) powder that step (4) is made synthesizes the single-phase powder of high reactivity at 950～1000 ℃ of temperature lower calcinations;
(6) step (5) synthetic powder is added polyvinyl alcohol (PVA) aqueous solution, granulation, compression moulding through wet-milling, oven dry back; In High Temperature Furnaces Heating Apparatus, burn till then, promptly make microwave-medium ceramics in 1000～1100 ℃ of temperature.
The present invention adopts a kind of new softening synthetic method-gel combustion method, can form homogeneous in the pre-burning process, reunite less and the high powder of chemically reactive; Than ordinary electronic pottery preparation technology, can obtain more vast scale even monophasic many titanates: Ca 2Zn 4Ti 15O 36Or Ca 2Zn 4Ti 16O 38(as shown in Figure 1); Adopt method synthetic powder provided by the invention, have higher sintering activity, can obtain fine and close stupalith (seeing accompanying drawing 2) by sintering down in lower temperature (1000～1100 ℃); Microwave-medium ceramics of the present invention has following feature: sintering temperature low (between 1000～1100 ℃), has medium specific inductivity (between 45～50), high quality factor (Q * f value is between 18000～29000GHz), temperature coefficient of resonance frequency less than+40～+ 75ppm/ ℃.Microwave-medium ceramics provided by the present invention belongs to the microwave dielectric ceramic materials of the medium specific inductivity that can burn till under lower sintering temperature, this type of material is also relatively more rare in the world at present.Microwave-medium ceramics of the present invention is the possibility that provides more choices that manufactures and designs of the development and use of novel low temperature co-fired microwave dielectric ceramic systems and microwave multilayer device, industrial very big value is arranged.
Description of drawings
Fig. 1 is the XRD spectrum of powder after differing temps (600 ℃, 800 ℃, 900 ℃, 1000 ℃) is handled after the sol-gel burning.
Fig. 2 is at the SEM of 1100 ℃ of ceramics samples that burn till surface topography.
Embodiment
A kind of microwave-medium ceramics of the present invention is made up of the oxide compound of Ca and Ti and one or both oxide compounds among Zn, Cu, Ni and the Mg, and its chemical constitution is: CaO-2MO-xTiO 2(M represents Zn, Cu, Ni, Mg); Described media ceramic, its component mole deal ratio is: CaO 1: MO 2: TiO 25～10.The preparation method of described microwave-medium ceramics is that nitrocalcite, zinc nitrate, cupric nitrate, nickelous nitrate, magnesium nitrate, butyl (tetra) titanate and citric acid more than 99% is starting raw material with purity, is made up of following steps:
(1) a certain proportion of nitrocalcite, zinc nitrate (or cupric nitrate, nickelous nitrate, magnesium nitrate), citric acid and butyl (tetra) titanate are dissolved in a certain amount of deionized water, form solution, wherein the amount of the citric acid of Jia Ruing is 1～2: 1 with the ratio of metal ion total mole number;
(2) ammoniacal liquor is slowly added in the solution of step (1) preparation, reach 6,, form transparence colloidal sol 50～80 ℃ of heating and lasting the stirring until the pH value;
(3) colloidal sol with step (2) preparation places 100～120 ℃ baking oven to dry, until forming filemot xerogel;
(4) xerogel that step (3) is obtained ignites in air, and xerogel burning back forms fluffy black powder;
(5) powder that step (4) is made synthesizes the single-phase powder of high reactivity at 950～1000 ℃ of temperature lower calcinations;
(6) step (5) synthetic powder is added polyvinyl alcohol (PVA) aqueous solution, granulation, compression moulding through wet-milling, oven dry back; In High Temperature Furnaces Heating Apparatus, burn till then, promptly make microwave-medium ceramics in 1000～1100 ℃ of temperature.
Only the present invention is further specified for following embodiment, but not in order to limit protection scope of the present invention.
Embodiment 1 (CaO-2ZnO-xTiO 2, x=5～10)
Present embodiment is Ca (NO more than 99% with purity 3) 24H 2O, Zn (NO 3) 26H 2O, butyl (tetra) titanate ((C 4H 9O) 4Ti) and citric acid (C 6H 8O 7H 2O) be starting raw material, and realize by following each step:
(1) with a certain proportion of Ca (NO 3) 24H 2O, Zn (NO 3) 26H 2O and citric acid are dissolved in a certain amount of deionized water, stir, and form colourless transparent solution, and wherein the amount of the citric acid of Jia Ruing is 1～2: 1 with the ratio of metal ion total mole number;
(2) incite somebody to action both butyl (tetra) titanate ((C of certainty ratio 4H 9O) 4Ti) slowly pour in the solution of step (1) preparation, heat 50～80 ℃ and lasting the stirring, have floss to exist in the solution;
(3) with ammoniacal liquor (NH 3H 2O) slowly add in the solution of step (2) preparation, arrive 6 until the pH value.Continuation is 50～80 ℃ of heating and continue stirring, is faint yellow clear shape again until solution;
(4) solution that step (3) is prepared is as for drying in 100～120 ℃ the baking oven, until forming filemot xerogel;
(5) pour a small amount of dehydrated alcohol in the xerogel that obtains toward step (4) and ignite, xerogel burning back forms fluffy black powder;
(6) powder that step (5) is made is synthetic 1000 ℃ of calcinings, adds polyvinyl alcohol (PVA) aqueous solution, granulation, compression moulding through wet-milling, oven dry back again; And then with the ceramic idiosome of the gained high temperature kiln roasting at 1070～1100 ℃, firing time is 3～6 hours, promptly makes microwave-medium ceramics.
The composition of table 1 embodiment 1 described microwave-medium ceramics
Form numbering ??Ca(NO 3) 2·4H 2O (mole) ??Zn(NO 3) 2·6H 2O (mole) ??(C 4H 9O) 4Ti (mole) ??C 6H 8O 7·H 2O (mole) Sintering temperature (℃)
??1 ??0.03 ??0.06 ??0.15 ??0.24-0.48 ??1100
??2 ??0.03 ??0.06 ??0.18 ??0.27-0.54 ??1100
??3 ??0.03 ??0.06 ??0.225 ??0.315-0.63 ??1100
??4 ??0.03 ??0.06 ??0.24 ??0.33-0.66 ??1100
??5 ??0.03 ??0.06 ??0.27 ??0.36-0.72 ??1100
??6 ??0.03 ??0.06 ??0.30 ??0.39-0.78 ??1100
The dielectric properties of table 2 embodiment 1 described microwave-medium ceramics under 6.5GHz
Form Specific inductivity, ε r Quality factor, Q * f (GHz) Frequency-temperature coefficient, τ f(ppm/℃)
??1 ??50.1 ??18000 ??+75.0
??2 ??49.4 ??19500 ??+71.5
??3 ??49.3 ??24000 ??+63.5
??4 ??48.1 ??29000 ??+44.1
??5 ??49.7 ??28000 ??+55.2
??6 ??50.2 ??26500 ??+59.5
Embodiment 2 (CaO-(2-y) ZnO-yCuO-8TiO 2, y=0～1)
Present embodiment is Ca (NO more than 99% with purity 3) 24H 2O, Zn (NO 3) 26H 2O, Cu (NO 3) 23H 2O, butyl (tetra) titanate ((C 4H 9O) 4Ti) and citric acid (C 6H 8O 7H 2O) be starting raw material, and realize by following each step:
(1) with a certain proportion of Ca (NO 3) 24H 2O, Zn (NO 3) 26H 2O, Cu (NO 3) 23H 2O and citric acid are dissolved in a certain amount of deionized water, stir, and form light blue clear solution, and wherein the amount of the citric acid of Jia Ruing is 1～2: 1 with the ratio of metal ion total mole number;
(2) incite somebody to action both butyl (tetra) titanate ((C of certainty ratio 4H 9O) 4Ti) slowly pour in the solution of step (1) preparation, heat 50～80 ℃ and lasting the stirring, have floss to exist in the solution;
(3) with ammoniacal liquor (NH 3H 2O) slowly add in the solution of step (2) preparation, arrive 6 until the pH value.Continuation is 50～80 ℃ of heating and continue stirring, is the clear shape again until solution;
(4) solution that step (3) is prepared is as for drying in 100-120 ℃ the baking oven, until forming filemot xerogel;
(5) pour a small amount of dehydrated alcohol in the xerogel that obtains toward step (4) and ignite, xerogel burning back forms fluffy black powder;
(6) powder that step (5) is made is synthetic 950 ℃ of calcinings, adds polyvinyl alcohol (PVA) aqueous solution, granulation, compression moulding through wet-milling, oven dry back again; And then with the ceramic idiosome of the gained high temperature kiln roasting at 1000-1050 ℃, firing time is 3～6 hours, promptly makes microwave-medium ceramics.
The composition of table 3 embodiment 2 described microwave-medium ceramics
Form numbering ?Ca(NO 3) 2·4H 2O (mole) ?Zn(NO 3) 2·6H 2O (mole) ?Cu(NO 3) 2·3H 2O (mole) ?(C 4H 9O) 4Ti (mole) ??C 6H 8O 7·H 2O (mole) Sintering temperature (℃)
??1 ??0.03 ??0.057 ??0.003 ??0.24 ??0.33-0.66 ??1050
??2 ??0.03 ??0.05 ??0.01 ??0.24 ??0.33-0.66 ??1025
??3 ??0.03 ??0.04 ??0.02 ??0.24 ??0.33-0.66 ??1000
The dielectric properties of table 4 embodiment 2 described microwave-medium ceramics under 6.5GHz
Form Specific inductivity, ε r Quality factor, Q * f (GHz) Frequency-temperature coefficient, τ f(ppm/℃)
??1 ??47.3 ??24000 ??+51.0
??2 ??46.2 ??20000 ??+45.0
??3 ??45.5 ??18000 ??+40.0
Accompanying drawing 1 is depicted as among the embodiment 1 the XRD spectrum of powder after differing temps (600 ℃, 800 ℃, 900 ℃, 1000 ℃) is handled after the sol-gels burning of forming 3 prescriptions.As seen can form desirable thing phase composite through incinerating powder more than 900 ℃.And form and keep stable.
Accompanying drawing 2 is depicted as to be formed 3 (left figure) and forms 4 (right figure) at the SEM of 1100 ℃ of ceramics samples that burn till surface topography among the embodiment 1.Can see that the ceramic structure behind the sintering is very fine and close.
The present invention is expected to the base-material as new low fever's microwave ceramics, and then development of new low-temperature co-burning ceramic material, can be widely used in the manufacturing of various microwave multilayer devices, can satisfy systems such as mobile communication, satellite communications to device miniaturization, multiple stratification, integrated demand, increase the kind of the low fired microwave dielectric ceramic material system of medium specific inductivity.

Claims (4)

1, a kind of microwave-medium ceramics is characterized in that, this microwave-medium ceramics is made up of the oxide compound of Ca and Ti and one or both oxide compounds among Zn, Cu, Ni and the Mg, and its chemical constitution is: CaO-2MO-xTiO 2, M represents Zn, Cu, Ni, Mg.
2, a kind of microwave-medium ceramics according to claim 1 is characterized in that, this microwave-medium ceramics component mole deal ratio is: CaO: MO: TiO 2=1: 2: x, wherein, M represents Zn, Cu, Ni, Mg, x=5～10.
3, the preparation method of a kind of microwave-medium ceramics according to claim 1 is characterized in that, described CaO-2MO-xTiO 2, x=5～10 potteries is that nitrocalcite, zinc nitrate, cupric nitrate, nickelous nitrate, magnesium nitrate, butyl (tetra) titanate and citric acid more than 99% is starting raw material with purity, and is made up of following each step:
(1) a certain proportion of nitrate, citric acid and butyl (tetra) titanate are dissolved in a certain amount of deionized water, form solution, wherein the amount of the citric acid of Jia Ruing is 1～2: 1 with the ratio of metal ion total mole number;
Described nitrate is any one or two kinds of among nitrocalcite, zinc nitrate, cupric nitrate, nickelous nitrate, the magnesium nitrate;
(2) ammoniacal liquor is slowly added in the solution that step (1) prepared, reach 6,50～80 ℃ of heating and continue to stir, form transparence colloidal sol until the pH value;
(3) colloidal sol with step (2) preparation places 100～120 ℃ baking oven to dry, until forming filemot xerogel;
(4) xerogel that step (3) is obtained ignites in air, and xerogel burning back forms fluffy black powder;
(5) powder that step (4) is made synthesizes the single-phase powder of high reactivity at 950～1000 ℃ of temperature lower calcinations;
(6) step (5) synthetic powder is added polyvinyl alcohol (PVA) aqueous solution, granulation, compression moulding through wet-milling, oven dry back; At the high temperature kiln roasting, promptly make microwave-medium ceramics then.
4, the preparation method of a kind of microwave-medium ceramics according to claim 3 is characterized in that, is 1000～1100 ℃ at the firing temperature of high temperature kiln roasting.
CN 200510011860 2005-06-03 2005-06-03 Microwave medium ceramics and its preparation process Pending CN1693280A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613205B (en) * 2009-07-20 2012-03-28 浙江大学 Method for preparing (Ca, Nd) TiO3 microwave dielectric ceramic by adopting sol-gel method
CN102534284A (en) * 2011-12-12 2012-07-04 南昌航空大学 Method for preparing medical porous NiTi shape memory alloy by microwave sintering
CN110734285A (en) * 2019-11-06 2020-01-31 常州大学 liquid phase combustion for preparing multi-principal-element ABO3Method for producing perovskite-structured ceramic
CN111377709A (en) * 2018-12-31 2020-07-07 深圳市大富科技股份有限公司 Microwave dielectric ceramic material, dielectric ceramic block and microwave communication equipment
CN112390644A (en) * 2020-11-23 2021-02-23 中国振华集团云科电子有限公司 Method for improving quality of MCT ceramic once ball-milling mixed material

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613205B (en) * 2009-07-20 2012-03-28 浙江大学 Method for preparing (Ca, Nd) TiO3 microwave dielectric ceramic by adopting sol-gel method
CN102534284A (en) * 2011-12-12 2012-07-04 南昌航空大学 Method for preparing medical porous NiTi shape memory alloy by microwave sintering
CN102534284B (en) * 2011-12-12 2013-04-17 南昌航空大学 Method for preparing medical porous NiTi shape memory alloy by microwave sintering
CN111377709A (en) * 2018-12-31 2020-07-07 深圳市大富科技股份有限公司 Microwave dielectric ceramic material, dielectric ceramic block and microwave communication equipment
CN110734285A (en) * 2019-11-06 2020-01-31 常州大学 liquid phase combustion for preparing multi-principal-element ABO3Method for producing perovskite-structured ceramic
CN110734285B (en) * 2019-11-06 2022-03-01 常州大学 Liquid phase combustion preparation multi-principal-element ABO3Method for producing perovskite-structured ceramic
CN112390644A (en) * 2020-11-23 2021-02-23 中国振华集团云科电子有限公司 Method for improving quality of MCT ceramic once ball-milling mixed material

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