CN100436371C

CN100436371C - Method of lowering sinter temperature of (Zr0.8 Sn0.2) TiO4 ceramic

Info

Publication number: CN100436371C
Application number: CNB2006100883715A
Authority: CN
Inventors: 汤乐群; 李军; 金玉成; 黄新友
Original assignee: ZHENJIANG LANBAOSHI ELECTRONIC INDUSTRY Co Ltd
Current assignee: ZHENJIANG LANBAOSHI ELECTRONIC INDUSTRY Co Ltd
Priority date: 2006-07-14
Filing date: 2006-07-14
Publication date: 2008-11-26
Anticipated expiration: 2026-07-14
Also published as: CN1887792A

Abstract

The method of lowering sinter temperature of (Zr0.8Sn0.2)TiO4 ceramic belongs to the field of microwave dielectric material producing technology. The ceramic material is prepared with (Zr0.8Sn0.2)TiO4 as main material, ZnO 0.5 wt%, MnCO3 0.3 wt% and CeO2 0.5 wt%, and through pre-sintering at 1180 deg.c for 4 hr, crushing, 200-mesh sieving and subsequent conventional ceramic preparing process. The present invention features that during the crushing and mixing, lead borate glass in 2-6 wt% and fused Bi2O3/Li2O block in 1-5 wt% are added to lower the sintering temperature to 1230-1300 deg.c, and when lead borate glass in 4 wt% and fused Bi2O3/Li2O block in 3 wt% are added and the sintering temperature is 1250 deg.c, best performance of the ceramic may be obtained.

Description

A kind of reduction (Zr 0.8Sn 0.2) TiO 4The method of ceramic sintering temperature

Technical field

The invention belongs to microwave dielectric material manufacturing technology field, particularly a kind of solid solution ceramic material of low sintering high quality factor is exactly a kind of reduction (Zr concretely _0.8Sn _0.2) TiO ₄The method of ceramic sintering temperature.

Background technology

(Zr _1-xSn _x) TiO ₄The pottery source is wide, and the Q value is high, and temperature stability is good, is widely used in various dielectric resonators and the wave filter.(Zr _1-xSn _x) TiO ₄The principal crystalline phase of pottery is with iris ZrTiO ₄(Zr, Sn) sosoloid for the basis has good microwave property.When x＜0.3, formation be monocrystalline (Zr _1-xSn _x) TiO ₄, wherein especially with x=0.2, i.e. (Zr _0.8Sn _0.2) TiO ₄(being abbreviated as ZST) material microwave performance is best.But the ZST firing temperature is up to 1380～1400 ℃, and how to deal with problems is urgent problem.People want that by doping vario-property when reducing sintering temperature, material keeps original superior dielectric properties.Shi Yong etc. are at " University Of Tianjin's journal " ZnO-MoO that the 2nd phase delivered in 2004 ₃Add (Zr _0.8Sn _0.2) TiO ₄Dielectric properties one literary composition in mention, adds a small amount of ZnO separately and can reduce sintering temperature, but dielectric loss increases, Wu Jianqiang is in the 42nd the 3rd phase of volume of " Chinese pottery " March in 2006, doped-glass makes (Zr _0.8Sn _0.2) TiO ₄Sintering temperature reduce, but the glass ingredient complexity, complicated process of preparation, and sintering temperature is still about 1320 ℃.Can find a kind of effective reduction (Zr _0.8Sn _0.2) TiO ₄Can the method for ceramic sintering temperature just becomes make full use of (Zr _0.8Sn _0.2) TiO ₄The key of pottery excellent dielectric properties.

Summary of the invention

The invention provides and a kind ofly can effectively reduce (Zr _0.8Sn _0.2) TiO ₄The method of sintering temperature, and can keep original dielectric properties, sintering range is 1230 ℃～1300 ℃, method is simple.

A kind of reduction (Zr _0.8Sn _0.2) TiO ₄The method of ceramic sintering temperature, major ingredient are (Zr _0.8Sn _0.2) TiO ₄, ZnO, the 0.3wt%MnCO of the 0.5wt% of adding major ingredient weight ₃, 0.5wt%CeO ₂, synthetic in 1180 ℃ of insulations pre-burning in 4 hours, pulverize, cross 200 mesh sieves, stand-by, adopt common process to prepare stupalith then, it is characterized in that: in pulverizing mixing process, added the nonex of 2～6wt% of major ingredient weight and the Bi of 1～5wt% ₂O ₃/ Li ₂O frit, sintering temperature are got 1230 ℃～1300 ℃, wherein get the Bi of 4wt% nonex and 3wt% ₂O ₃/ Li ₂The O frit is at 1250 ℃ of sintering, and ceramic performance is best.

The nonex preparation process is as follows: with Pb ₃O ₄And B ₂O ₃With (4/3): 1 molar ratio mixed grinding mixing, compound be 1000 ℃ of fusions, and be incubated 50 minutes, pours into subsequently and carry out quenching in the cold water.Solidified glass drying is ground later on up to sieving 200 mesh sieve, stays with stand-by.

Bi ₂O ₃/ Li ₂O frit preparation process is as follows: with Bi ₂O ₃And Li ₂CO ₃Grind mixing with 92: 11 mixed in molar ratio, compound is placed in the corundum crucible and forms Solid solution down at 830 ℃, is incubated 40 minutes, pours into subsequently and carries out quenching in the cold water, grinds up to sieving 200 mesh sieves after the drying, stays with standby.

It is low that the present invention has sintering temperature, and according to the difference of forming proportioning, sintering temperature does not reduce the dielectric properties of stupalith simultaneously at 1230 ℃～1300 ℃.The simple cost of preparation technology is low.

Description of drawings

Fig. 1 is for adopting the microstructure of the present invention's agglomerated material in the time of 1250 ℃

The process flow sheet of Fig. 2 specimen preparation

Embodiment

Embodiment	The hotchpotch add-on	Sintering temperature ℃	DIELECTRIC CONSTANT _r	Q(f＝7GHZ)
Embodiment	The hotchpotch add-on	Sintering temperature ℃	DIELECTRIC CONSTANT _r	Q(f＝7GHZ)	Embodiment 1	The Bi of 2wt% nonex and 1wt% ₂O ₃/Li ₂The O frit	1300	42	6600
Embodiment 2	The Bi of 2wt% nonex and 1wt% ₂O ₃/Li ₂The O frit	1280	39	6350	Embodiment 1	The Bi of 2wt% nonex and 1wt% ₂O ₃/Li ₂The O frit	1300	42	6600
Embodiment 2	The Bi of 2wt% nonex and 1wt% ₂O ₃/Li ₂The O frit	1280	39	6350	Embodiment 3	The Bi of 4wt% nonex and 3wt% ₂O ₃/Li ₂The O frit	1280	44	6930
Embodiment 4	The Bi of 4wt% nonex and 3wt% ₂O ₃/Li ₂The O frit	1250	44	6900	Embodiment 3	The Bi of 4wt% nonex and 3wt% ₂O ₃/Li ₂The O frit	1280	44	6930
Embodiment 4	The Bi of 4wt% nonex and 3wt% ₂O ₃/Li ₂The O frit	1250	44	6900	Embodiment 5	The Bi of 4wt% nonex and 3wt% ₂O ₃/Li ₂The O frit	1230	35	6250
Embodiment 6	The Bi of 6wt% nonex and 5wt% ₂O ₃/Li ₂The O frit	1230	31	6100	Embodiment 5	The Bi of 4wt% nonex and 3wt% ₂O ₃/Li ₂The O frit	1230	35	6250

Embodiment 7	The Bi of 6wt% nonex and 5wt% ₂O ₃/Li ₂The O frit	1250	33	6250
Embodiment 7	The Bi of 6wt% nonex and 5wt% ₂O ₃/Li ₂The O frit	1250	33	6250	Embodiment 8	The Bi of 2wt% nonex and 5wt% ₂O ₃/Li ₂The O frit	1250	39	6500
Embodiment 9	The Bi of 2wt% nonex and 5wt% ₂O ₃/Li ₂The O frit	1280	40	6550	Embodiment 8	The Bi of 2wt% nonex and 5wt% ₂O ₃/Li ₂The O frit	1250	39	6500
Embodiment 9	The Bi of 2wt% nonex and 5wt% ₂O ₃/Li ₂The O frit	1280	40	6550	Embodiment 10	The Bi of 6wt% nonex and 1wt% ₂O ₃/Li ₂The O frit	1260	37	6300
Embodiment 11	The Bi of 6wt% nonex and 1wt% ₂O ₃/Li ₂The O frit	1300	39	6370	Embodiment 10	The Bi of 6wt% nonex and 1wt% ₂O ₃/Li ₂The O frit	1260	37	6300

The present invention adopts common process to prepare stupalith, detailed process such as Fig. 2, the Bi of doping 4wt% nonex and 3wt% in major ingredient as can be seen ₂O ₃/ Li ₂The O frit, sintering temperature is in the time of 1250 ℃, the dielectric properties of pottery are best, Fig. 1 is for adopting the microstructure of the present invention's agglomerated material 1250 ℃ the time, the ceramic crystalline grain even compact, this is because the low melting point additive forms earlier the liquid phase acceleration of sintering in sintering process, goes into principal crystalline phase as last phase resorption and plays the doping vario-property effect and arrived the sintering later stage.This " double effect " of low melting point additive can make sintering temperature reduce, and property retention is constant or raising.

Claims

1, a kind of reduction (Zr _0.8Sn _0.2) TiO ₄The method of ceramic sintering temperature, major ingredient are (Zr _0.8Sn _0.2) TiO ₄, ZnO, the 0.3wt%MnCO of the 0.5wt% of adding major ingredient weight ₃, 0.5wt%CeO ₂, synthetic in 1180 ℃ of insulations pre-burning in 4 hours, pulverize, cross 200 mesh sieves, stand-by, adopt common process to prepare stupalith then, it is characterized in that: in pulverizing mixing process, added the nonex of 2～6wt% of major ingredient weight and the Bi of 1～5wt% ₂O ₃/ Li ₂O frit, sintering temperature are got 1230 ℃～1300 ℃.

2, a kind of reduction (Zr according to claim 1 _0.8Sn _0.2) TiO ₄The method of ceramic sintering temperature is characterized in that: the Bi that gets major ingredient weight 4wt% nonex and 3wt% ₂O ₃/ Li ₂The O frit is at 1250 ℃ of sintering.

3, a kind of reduction (Zr according to claim 1 _0.8Sn _0.2) TiO ₄The method of ceramic sintering temperature is characterized in that: the nonex preparation process is as follows: with Pb ₃O ₄And B ₂O ₃With (4/3): 1 molar ratio mixed grinding mixing, compound be 1000 ℃ of fusions, and be incubated 50 minutes, pours into subsequently and carry out quenching in the cold water, and solidified glass drying is ground later on up to sieving 200 mesh sieve.

4, a kind of reduction (Zr according to claim 1 _0.8Sn _0.2) TiO ₄The method of ceramic sintering temperature is characterized in that: Bi ₂O ₃/ Li ₂The preparation process of O frit is as follows: with Bi ₂O ₃And Li ₂CO ₃Grind mixing with 92: 11 mixed in molar ratio, compound forms Solid solution down at 830 ℃, is incubated 40 minutes, pours into subsequently and carries out quenching in the cold water, grinds up to sieving 200 mesh sieves after the drying.