CN104211383A - Method for sintering Zn2SiO4 microwave medium ceramic at low temperature - Google Patents
Method for sintering Zn2SiO4 microwave medium ceramic at low temperature Download PDFInfo
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- CN104211383A CN104211383A CN201410422743.8A CN201410422743A CN104211383A CN 104211383 A CN104211383 A CN 104211383A CN 201410422743 A CN201410422743 A CN 201410422743A CN 104211383 A CN104211383 A CN 104211383A
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Abstract
The invention discloses a method for sintering Zn2SiO4 microwave medium ceramic at a low temperature. The method comprises the following steps: taking Zn2SiO4 microwave medium ceramic powder, adding polyethylene glycol, carrying out ultrasonic dispersion, then, adding saturated CuSO4 and reducing metal powder, mechanically stirring, carrying out suction filtration, drying, calcining, sieving, sintering for forming to obtain the Zn2SiO4 microwave medium ceramic. The method is pollution-free in process, capable of lowering the sintering temperature by about 350 DEG C from 1350 DEG C under the condition that a dielectric constant is almost unchanged, can ensure that Q.f is higher than 60000 GHz and a resonant frequency temperature coefficient moves towards a positive direction, and can realize cofiring with a Cu electrode.
Description
Technical field
The present invention relates to the microwave-medium ceramics field in Materials science, relate to a kind of chemical replacement method specifically and introduce oxide compound sintering agent reduction Zn
2siO
4the method of microwave-medium ceramics sintering temperature.
Background technology
Zn
2siO
4be a kind of important compound, there is its distinctive physics and chemical property, applied to widely manufacture biomaterial, fluorescent material and microwave-medium ceramics.Zn
2siO
4owing to there are excellent dielectric properties, lower dielectric loss (desirable quality factor is 219000GHz), stable specific inductivity (ε
r=6.6) and higher thermal conductivity, in low temperature co-fired (LTCC) technology, potentiality are had a wide range of applications.But Zn
2siO
4pottery intrinsic sintering temperature more than 1300 DEG C, for LTCC technology, Zn
2siO
4the higher sintering temperature of pottery can not meet and the metal A g(961 DEG C compared with low melting point), Cu(1064 DEG C) burns altogether, so reduction sintering temperature seems extremely important.
The method of the most frequently used reduction sintering temperature mixes appropriate low melting point oxide or low softening point glass, but traditional solid phase method can worsen the dielectric properties of pottery while being added on and reducing sintering temperature, this is because adopt traditional solid phase to add, by mechanical process hybrid ceramic powder and sintering agent, it is uneven that this makes sintering agent mix, thus increase the consumption of sintering agent; Moreover, the dielectric properties of sintering agent are poor, so too much sintering agent can worsen the dielectric properties of pottery: between the principal crystalline phase of (1) material and glassy phase, chemical reaction occurs, produce second-phase, cause principal crystalline phase content to reduce, or have impurity phase to generate; (2) material internal exists because there being glassy phase, and its intrinsic loss is increased; (3) generation of lattice imperfection.Therefore, the mode of existing introducing sintering agent must be optimized, or seek a kind of new mode, to reduce the negative impact of sintering agent to ceramic dielectric performance.
Summary of the invention
The present invention, in order to solve the problems of the technologies described above, provides a kind of low-temperature sintering Zn
2siO
4the method of microwave-medium ceramics, it can not only reduce Zn
2siO
4microwave-medium ceramics sintering temperature and maintain the dielectric properties of this microwave-medium ceramics excellence, achieves the common burning of microwave-medium ceramics and Cu electrode.
The technical solution adopted in the present invention is: a kind of low-temperature sintering Zn
2siO
4the method of microwave-medium ceramics, comprises the following steps:
Step one: take Zn
2siO
4microwave dielectric ceramic powder, and add polyoxyethylene glycol and deionized water wherein, it is for subsequent use that magnetic agitation is made into suspension liquid;
Step 2, to step one prepare suspension liquid in add saturated CuSO simultaneously
4solution and for replacing saturated CuSO
4gOLD FROM PLATING SOLUTION belongs to the reducing metal powder of Cu, makes Zn
2+and Cu
2+mol ratio be 1:(0.04 ~ 0.09), after mechanical stirring 1h, for subsequent use;
Carry out suction filtration after step 3, the solution left standstill 12h that step 2 obtained, the powder after suction filtration is repeatedly washed with alcohol wash after for subsequent use;
Step 4, powder step 3 obtained put into loft drier, and under 60-80 DEG C of condition, dry 12h, for subsequent use;
Step 5, powder dried in step 4 is put into retort furnace be heated to 500 DEG C, insulation 1h, obtained CuO and Zn
2siO
4base matter composite granule, for subsequent use;
Step 6, add the binding agent accounting for its quality 5%-10% and carry out granulation in the powder after step 5 heating, after then crossing 60-80 mesh sieve, be pressed into green compact with tabletting machine, for subsequent use;
Step 7, the green compact of step 6 compression moulding are warmed up to 600 DEG C with 1-1.5 DEG C/min, binder removal 1.5-2h, then with 3-5 DEG C/min, are warming up to 950-1100 DEG C and sinter, after insulation 2-4h, obtained Zn
2siO
4microwave-medium ceramics.
The tackiness agent adopted in described step 6 is polyvinyl alcohol, and its concentration is 0.1g/ml.
In described step 6, tabletting machine adopts pressure to be 150-200MPa, and green compact are the right cylinder of Φ 10mm × 5mm.
In the present invention, guaranteed by the add-on controlling reducing metal powder, the final CuO generated accounts for Zn
2siO
43% ~ 6% of microwave-medium ceramics base-material gross weight.
Beneficial effect of the present invention:
(1) step one of the present invention by adding Aqueous Solutions of Polyethylene Glycol and carrying out magnetic agitation in ceramic powder, effectively reduces Zn
2siO
4the reunion of powder;
(2), in the present invention, introduce CuO by substitution method and make CuO at Zn compared with conventional solid-state method
2siO
4in matrix, distribution distribution is more even, advantageously in reduction sintering temperature;
(3) in the present invention green compact 950-1100 DEG C carry out sintering 2 ~ 4h, in sintering process, along with sintering temperature raise, CuO and Zn
2siO
4the base matter of pottery forms eutectic mixture (liquid phase), and liquid phase infiltrates solid particulate, and solid particulate is close to each other under liquid phase produces the effect of huge capillary force, slippage, rearrangement occurs simultaneously, effectively facilitates sintering.
Accompanying drawing explanation
Fig. 1 is the energy spectrum analysis figure utilizing chemical replacement method to introduce the different positions of the free surface of CuO;
Fig. 2 is the constituent content subordinate list of different positions in Fig. 1;
Fig. 3 is the specific embodiment of the invention;
Fig. 4 is the test result figure of microwave dielectric property in specific embodiment;
Fig. 5 is the effect diagram of sintering agent to experimental performance.
Embodiment
As shown in the figure, a kind of low-temperature sintering Zn
2siO
4the method of microwave-medium ceramics, comprises the following steps:
Step one: take Zn
2siO
4microwave dielectric ceramic powder, and add polyoxyethylene glycol and deionized water wherein, it is for subsequent use that magnetic agitation is made into suspension liquid;
Step 2, to step one prepare suspension liquid in add saturated CuSO simultaneously
4solution and for replacing saturated CuSO
4gOLD FROM PLATING SOLUTION belongs to the reducing metal powder of Cu, makes Zn
2+and Cu
2+mol ratio be 1:(0.04 ~ 0.09), after mechanical stirring 1h, for subsequent use;
Carry out suction filtration after step 3, the solution left standstill 12h that step 2 obtained, the powder after suction filtration is repeatedly washed with alcohol wash after for subsequent use;
Step 4, powder step 3 obtained put into loft drier, and under 60-80 DEG C of condition, dry 12h, for subsequent use;
Step 5, powder dried in step 4 is put into retort furnace be heated to 500 DEG C, insulation 1h, obtained CuO and Zn
2siO
4base matter composite granule, for subsequent use;
Step 6, add the binding agent accounting for its quality 5%-10% and carry out granulation in the powder after step 5 heating, after then crossing 60-80 mesh sieve, be pressed into green compact with tabletting machine, for subsequent use;
Step 7, the green compact of step 6 compression moulding are warmed up to 600 DEG C with 1-1.5 DEG C/min, binder removal 1.5-2h, then with 3-5 DEG C/min, are warming up to 950-1100 DEG C and sinter, after insulation 2-4h, obtained Zn
2siO
4microwave-medium ceramics.
The tackiness agent adopted in described step 6 is polyvinyl alcohol, and its concentration is 0.1g/ml.
In described step 6, tabletting machine adopts pressure to be 150-200MPa, and green compact are the right cylinder of Φ 10mm × 5mm.
The present invention is elaborated below in conjunction with embodiment.
A kind of low-temperature sintering Zn
2siO
4the method of microwave-medium ceramics, comprises the following steps:
Step one: take 20g Zn
2siO
4microwave dielectric ceramic powder, and add 500-1000mL to it, massfraction is the Aqueous Solutions of Polyethylene Glycol of 0.5-1wt%, magnetic agitation 15-30min, is made into suspension liquid for subsequent use;
Add the saturated CuSO of 0.008-0.02mol in step 2, the suspension liquid prepared to step one simultaneously
4solution and for replacing saturated CuSO
4gOLD FROM PLATING SOLUTION belongs to the reducing metal powder of Cu, after mechanical stirring 1h, for subsequent use;
Carry out suction filtration after step 3, the solution left standstill 12h that step 2 obtained, the powder after suction filtration is repeatedly washed with alcohol wash after for subsequent use;
Step 4, powder step 3 obtained put into loft drier, and under 60-80 DEG C of condition, dry 12h, for subsequent use;
Step 5, powder dried in step 4 is put into retort furnace be heated to 500 DEG C, insulation 1h, obtained CuO and Zn
2siO
4the eutectic mixture of base matter, for subsequent use;
Step 6, add the binding agent accounting for its quality 5%-10% and carry out granulation in the powder after step 5 heating, after then crossing 60-80 mesh sieve, be pressed into green compact with tabletting machine, for subsequent use;
Step 7, the green compact of step 6 compression moulding are warmed up to 600 DEG C with 1-1.5 DEG C/min, binder removal 1.5-2h, then with 3-5 DEG C/min, are warming up to 950-1100 DEG C and sinter, after insulation 2-4h, obtained Zn
2siO
4microwave-medium ceramics.
The tackiness agent adopted in described step 6 is polyvinyl alcohol, and its concentration is 0.1g/ml.
In described step 6, tabletting machine adopts pressure to be 150-200MPa, and green compact are the right cylinder of Φ 10mm × 5mm.
In the present invention testing method and test set as follows:
1, the diameter of sample and thickness use milscale to measure;
2, resonant frequency and the quality factor of 20 ~ 80 DEG C are measured by Agilent N5230C-220 vector network analyzer and DWB2-6 high/low temperature experimental box;
3, adopt enclosed cell method to measure the quality factor of prepared cylindrical ceramic sample, survey frequency scope is within the scope of 13-14GHz.
In the present invention, the growing amount of CuO is 5wt%, at 1000 DEG C, sinter 3h, and pottery obtains optimum microwave dielectric property: dielectric constant=6.5, Qf=67342GHz, τ=-23ppm/ DEG C.By this kind of method, not only reduce the sintering temperature of Zn2SiO4 pottery, reduce the negative impact of sintering agent to ceramic dielectric performance simultaneously.
The present invention by adding Aqueous Solutions of Polyethylene Glycol and magnetic agitation obtains Zn in microwave dielectric ceramic powder
2siO
4suspension liquid, alleviate Zn to a certain extent
2siO
4the reunion of powder, then passes through chemical replacement method from saturated CuSO
4displace Cu in solution, obtain Cu-Zn
2siO
4presoma, reacted by heated oxide and finally obtain CuO-Zn
2siO
4composite granule.Substitution method is introduced CuO and is introduced than solid phase method more even (see accompanying drawing 1, accompanying drawing 2) that CuO is distributed in matrix powder, and adding of CuO does not affect Zn
2siO
4the generation of phase.In sintering process, along with sintering temperature raises, CuO and Zn
2siO
4the base matter of pottery forms eutectic mixture (liquid phase), and liquid phase infiltrates solid particulate, and solid particulate is close to each other under liquid phase produces the effect of huge capillary force, slippage, rearrangement occurs simultaneously, thus facilitates sintering.Compared with solid phase method, when reducing same sintering temperature, its dielectric properties will be far superior to solid phase method, as shown in Figure 5.
Claims (3)
1. a low-temperature sintering Zn
2siO
4the method of microwave-medium ceramics, is characterized in that: comprise the following steps:
Step one: take Zn
2siO
4microwave dielectric ceramic powder, and add polyoxyethylene glycol and deionized water wherein, it is for subsequent use that magnetic agitation is made into suspension liquid;
Step 2, to step one prepare suspension liquid in add saturated CuSO simultaneously
4solution and for replacing saturated CuSO
4gOLD FROM PLATING SOLUTION belongs to the reducing metal powder of Cu, makes Zn
2+and Cu
2+mol ratio be 1:(0.04 ~ 0.09), after mechanical stirring 1h, for subsequent use;
Carry out suction filtration after step 3, the solution left standstill 12h that step 2 obtained, the powder after suction filtration is repeatedly washed with alcohol wash after for subsequent use;
Step 4, powder step 3 obtained put into loft drier, and under 60-80 DEG C of condition, dry 12h, for subsequent use;
Step 5, powder dried in step 4 is put into retort furnace be heated to 500 DEG C, insulation 1h, obtained CuO and Zn
2siO
4composite granule, for subsequent use;
Step 6, add the binding agent accounting for its quality 5%-10% and carry out granulation in the powder after step 5 heating, after then crossing 60-80 mesh sieve, be pressed into green compact with tabletting machine, for subsequent use;
Step 7, the green compact of step 6 compression moulding are warmed up to 600 DEG C with 1-1.5 DEG C/min, binder removal 1.5-2h, then with 3-5 DEG C/min, are warming up to 950-1100 DEG C and sinter, after insulation 2-4h, obtained Zn
2siO
4microwave-medium ceramics.
2. a kind of low-temperature sintering Zn as claimed in claim 1
2siO
4the method of microwave-medium ceramics, is characterized in that: the tackiness agent adopted in described step 6 is polyvinyl alcohol, and its concentration is 0.1g/ml.
3. a kind of low-temperature sintering Zn as claimed in claim 1
2siO
4the method of microwave-medium ceramics, is characterized in that: in described step 6, tabletting machine adopts pressure to be 150-200MPa, and green compact are the right cylinder of Φ 10mm × 5mm.
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|---|---|---|---|
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|---|---|---|---|
| CN201410422743.8A CN104211383B (en) | 2014-08-26 | 2014-08-26 | A kind of low-temperature sintering Zn 2siO 4the method of microwave-medium ceramics |
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| CN104211383A true CN104211383A (en) | 2014-12-17 |
| CN104211383B CN104211383B (en) | 2016-01-20 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198479A (en) * | 2015-10-12 | 2015-12-30 | 北京东泰富博新材料科技股份有限公司 | Method for preparing starch-containing ceramic slurry from diatomite |
| CN111377721A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | Low-temperature co-fired ceramic material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2683432C1 (en) * | 2018-03-20 | 2019-03-28 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Zinc silicate-based material for production of dielectric material |
-
2014
- 2014-08-26 CN CN201410422743.8A patent/CN104211383B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 李谦等: "CuSO4溶液包覆Ba2Ti9O20陶瓷介电性能的研究", 《功能材料与器件学报》, vol. 18, no. 1, 29 February 2012 (2012-02-29), pages 70 - 74 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198479A (en) * | 2015-10-12 | 2015-12-30 | 北京东泰富博新材料科技股份有限公司 | Method for preparing starch-containing ceramic slurry from diatomite |
| CN105198479B (en) * | 2015-10-12 | 2016-05-11 | 北京东泰富博新材料科技股份有限公司 | A kind of method of utilizing diatomite to prepare starch-containing ceramic size |
| CN111377721A (en) * | 2018-12-27 | 2020-07-07 | 中国科学院上海硅酸盐研究所 | Low-temperature co-fired ceramic material and preparation method thereof |
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