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CN109694249A - A kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain - Google Patents

A kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain Download PDF

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CN109694249A
CN109694249A CN201910078210.5A CN201910078210A CN109694249A CN 109694249 A CN109694249 A CN 109694249A CN 201910078210 A CN201910078210 A CN 201910078210A CN 109694249 A CN109694249 A CN 109694249A
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temperature
preparation
sintering
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milling
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汪泽维
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Anqing Zye New Material Technology Extension Service Co Ltd
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Anqing Zye New Material Technology Extension Service Co Ltd
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Abstract

The present invention discloses a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain, belongs to technical field of functional ceramics, includes the following steps: to take Pb3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing dries after ball milling;The pre-burning in air atmosphere by mixed-powder after ball milling;Pre-burning product and PbO are taken, wet ball-milling is mixed and dried, and binder is added in mixed-powder, compression moulding after mixing;Be sintered in air atmosphere after compression moulding, 880~920 DEG C of sintering temperature, keep the temperature 3~5 hours to get.Preparation method of the present invention makes the firing temperature of porcelain be down to 900 DEG C or so, reduces the sintering temperature of porcelain, and porcelain body densified sintering product, and stomata is few, improves the anti-aging property of capacitor.Excessive PbO is added after pre-burning to reburn into, single Perovskite Phase can be synthesized, eliminates the influence of Jiao Lvshi relative dielectric constant.

Description

A kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain
Technical field
The present invention relates to technical field of functional ceramics, in particular to a kind of system of low-temperature sintering II type monolithic capacitor porcelain Preparation Method.
Background technique
Monolithic ceramic capacitor is to adapt to electronic technology high speed development to propose that geometric dimension is small, performance to electronic component Height, service life length, reliability height etc. require and one of the element that have developed rapidly.It is that will be coated with metal electrode slurry in technologic feature The ceramic dielectric green body of material, is superimposed ceramic material with electrode multilayer and electrode is burnt into an entirety simultaneously, formed it is multiple by Capacitor is in parallel and the capacitor that constitutes.
Low-temperature sintering monolithic capacitor porcelain is divided into I type monolithic capacitor porcelain and II type monolithic capacitor porcelain, and I type is only Stone capacitor ceramics mainly use the systems such as niobium bismuth zinc, niobium bismuth magnesium, Phospho-tungstic acid to carry out the other production of different temperature coefficients group.II Type monolithic capacitor porcelain will be produced with lead magnesio-niobate porcelain porcelain system by the group of different capabilities change rate.Pb(Mg1/3Nb2/3) O3For the principal crystalline phase of the system, Pb (Mg1/3Nb2/3)O3Dielectric constant with higher, tan δ is also smaller, meanwhile, at porcelain temperature Also the burning infiltration temperature (900~910 DEG C) of silver electrode, but Pb (Mg are connected to1/3Nb2/3)O3Shortcoming be Curie temperature it is lower and Subzero temperature loss is larger.Within the temperature range of curie point immigration is commonly used, usually using PbTiO3It, can as peak agent is moved Change the porcelain to take the lead in to obtain the high dielectric constant of room temperature and low temperature.But introduce PbTiO3Afterwards, firing temperature is still 1100 DEG C, it cannot cooperate with silver electrode.In addition, due to Pb (Mg1/3Nb2/3)O3Due to material characteristic be mutually distributed it is non-to sintering process It is often sensitive, it is also easy to produce Jiao Lvshi phase during sintering, influences the size of dielectric constant.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of preparation sides of low-temperature sintering II type monolithic capacitor porcelain Method solves Pb (Mg1/3Nb2/3)O3Use PbTiO3The problem of cannot cooperating with silver electrode as firing temperature after shifting peak agent.
In order to solve the above technical problems, the technical solution of the present invention is as follows:
A kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain, includes the following steps:
(1) Pb is taken3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing 10~15 hours, ball-milling medium For distilled water, dried after ball milling;
(2) pre-burning in air atmosphere by mixed-powder after ball milling, 750~800 DEG C of pre-sintering temperature, heat preservation 3~5 is small When;
(3) pre-burning product and PbO are taken, wet ball-milling mixes 2~4 hours, drying, the mixed-powder after drying is added viscous Agent, after mixing compression moulding are tied, the pressure of compression moulding is 90~100MPa;
(4) be sintered in air atmosphere after compression moulding, 880~920 DEG C of sintering temperature, keep the temperature 3~5 hours to get.
Wherein it is preferred to by mass percentage, Pb3O4For 61~63%, MgCO3For 9.4~10.3%, Nb2O5For 19.5~20.3%, TiO2For 2.4~2.8%, BiO3For 4.3~4.8%, Ce2O3It is 0.8~1.1%.
Wherein it is preferred to which the additional amount of PbO is the 5~7% of pre-burning products weight in the step (3).
Wherein it is preferred to which the binder is polyvinyl alcohol water solution, the weight ratio of the polyethylene alcohol and water is 1:(3 ~5).
Wherein it is preferred to which the degree of polymerization of the polyvinyl alcohol is 1400~1500, alcoholysis degree is 80~90%.
Wherein it is preferred to which the polyvinyl alcohol water solution is made of following preparation methods: take polyvinyl alcohol to be added to the water, It is heated using stirring in water bath, until polyvinyl alcohol is completely dissolved, exclusion bubble, sieving removal impurity reaches transparent.
Wherein it is preferred to which the weight ratio of mixed-powder and the binder after the drying is 100:(20~30).
Beneficial effects of the present invention:
Compared with prior art, preparation method provided by the invention is with Pb (Mg1/3Nb2/3)O3For basic system, use PbTiO3As peak agent is moved, Bi is then added2O3And SiO2As fluxing agent, the firing temperature of porcelain is made to be down to 900 DEG C or so, Occur liquid phase at a lower temperature, reduces the porcelain sintering temperature of porcelain, and porcelain body densified sintering product, stomata is few, improves The anti-aging property of capacitor.Also, excessive PbO is added after pre-burning to reburn into, single Perovskite Phase can be synthesized, disappeared In addition to Jiao Lvshi phase, the influence of Jiao Lvshi relative dielectric constant is eliminated.The experimental results showed that the only stone of low-temperature sintering of the invention Capacitor ceramics Curie temperature is about 0 DEG C, and the dielectric constant of room temperature is about that 7500, tan δ is 50 × 10-4
In addition, preparation method simple process provided by the invention, sintering temperature is low, sintering time is short, short preparation period, fits Suitable large-scale industrialization, has very vast potential for future development.
Specific embodiment
Below in conjunction with the specific embodiment of the invention, technical solution of the present invention is clearly and completely described, is shown So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to In the scope of protection of the invention.
Embodiment 1
The present embodiment provides a kind of preparation methods of low-temperature sintering II type monolithic capacitor porcelain, include the following steps:
(1) Pb is taken3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing 12 hours, ball-milling medium is to steam Distilled water is dried after ball milling;By mass percentage, Pb3O4For 62%, MgCO3For 9.9%, Nb2O5For 20.0%, TiO2For 2.6%, BiO3For 4.5%, Ce2O3It is 1.0%;
(2) pre-burning in air atmosphere by mixed-powder after ball milling, keeps the temperature 4 hours by 780 DEG C of pre-sintering temperature;
(3) pre-burning product and PbO are taken, the additional amount of PbO is the 6% of pre-burning products weight, and wet ball-milling mixes 3 hours, Binder is added in mixed-powder after drying by drying, and the weight ratio of mixed-powder and the binder after drying is 100: 25, compression moulding after mixing, the pressure of compression moulding is 95MPa;
(4) be sintered in air atmosphere after compression moulding, 900 DEG C of sintering temperature, keep the temperature 4 hours to get.
Wherein, the binder is polyvinyl alcohol water solution, and the weight ratio of the polyethylene alcohol and water is 1:4, described poly- The degree of polymerization of vinyl alcohol is 1400~1500, and alcoholysis degree is 80~90%.
Wherein, the polyvinyl alcohol water solution is made of following preparation methods: taking polyvinyl alcohol to be added to the water, using water-bath Agitating and heating, until polyvinyl alcohol is completely dissolved, exclusion bubble, sieving removal impurity reaches transparent.
Low-temperature sintering monolithic capacitor porcelain Curie temperature manufactured in the present embodiment is 0 DEG C, and the dielectric constant of room temperature is 7500, tan δ are 50 × 10-4, insulation resistance 1011Ω。
Embodiment 2
The present embodiment provides a kind of preparation methods of low-temperature sintering II type monolithic capacitor porcelain, include the following steps:
(1) Pb is taken3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing 10 hours, ball-milling medium is to steam Distilled water is dried after ball milling;By mass percentage, Pb3O4For 62%, MgCO3For 10.3%, Nb2O5For 19.5%, TiO2For 2.8%, BiO3For 4.3%, Ce2O3It is 1.1%;
(2) pre-burning in air atmosphere by mixed-powder after ball milling, keeps the temperature 5 hours by 750 DEG C of pre-sintering temperature;
(3) pre-burning product and PbO are taken, the additional amount of PbO is the 5% of pre-burning products weight, and wet ball-milling mixes 4 hours, Binder is added in mixed-powder after drying by drying, and the weight ratio of mixed-powder and the binder after drying is 100: 20, compression moulding after mixing, the pressure of compression moulding is 100MPa;
(4) be sintered in air atmosphere after compression moulding, 880 DEG C of sintering temperature, keep the temperature 5 hours to get.
Wherein, the binder is polyvinyl alcohol water solution, and the weight ratio of the polyethylene alcohol and water is 1:4, described poly- The degree of polymerization of vinyl alcohol is 1400~1500, and alcoholysis degree is 80~90%.
Wherein, the polyvinyl alcohol water solution is made of following preparation methods: taking polyvinyl alcohol to be added to the water, using water-bath Agitating and heating, until polyvinyl alcohol is completely dissolved, exclusion bubble, sieving removal impurity reaches transparent.
Low-temperature sintering monolithic capacitor porcelain Curie temperature manufactured in the present embodiment is 1 DEG C, and the dielectric constant of room temperature is 7400, tan δ are 50 × 10-4, insulation resistance 1011Ω。
Embodiment 3
The present embodiment provides a kind of preparation methods of low-temperature sintering II type monolithic capacitor porcelain, include the following steps:
(1) Pb is taken3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing 15 hours, ball-milling medium is to steam Distilled water is dried after ball milling;By mass percentage, Pb3O4For 62.3%, MgCO3For 9.4%, Nb2O5For 20.3%, TiO2For 2.4%, BiO3For 4.8%, Ce2O3It is 0.8%;
(2) pre-burning in air atmosphere by mixed-powder after ball milling, keeps the temperature 3 hours by 800 DEG C of pre-sintering temperature;
(3) pre-burning product and PbO are taken, the additional amount of PbO is the 7% of pre-burning products weight, and wet ball-milling mixes 2 hours, Binder is added in mixed-powder after drying by drying, and the weight ratio of mixed-powder and the binder after drying is 100: 30, compression moulding after mixing, the pressure of compression moulding is 90MPa;
(4) be sintered in air atmosphere after compression moulding, 920 DEG C of sintering temperature, keep the temperature 3 hours to get.
Wherein, the binder is polyvinyl alcohol water solution, and the weight ratio of the polyethylene alcohol and water is 1:5, described poly- The degree of polymerization of vinyl alcohol is 1400~1500, and alcoholysis degree is 80~90%.
Wherein, the polyvinyl alcohol water solution is made of following preparation methods: taking polyvinyl alcohol to be added to the water, using water-bath Agitating and heating, until polyvinyl alcohol is completely dissolved, exclusion bubble, sieving removal impurity reaches transparent.
Low-temperature sintering monolithic capacitor porcelain Curie temperature manufactured in the present embodiment is 2 DEG C, and the dielectric constant of room temperature is 7400, tan δ are 50 × 10-4, insulation resistance 1011Ω。
Embodiment 4
The present embodiment provides a kind of preparation methods of low-temperature sintering II type monolithic capacitor porcelain, include the following steps:
(1) Pb is taken3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing 14 hours, ball-milling medium is to steam Distilled water is dried after ball milling;By mass percentage, Pb3O4For 61%, MgCO3For 10.2%, Nb2O5For 20.3%, TiO2For 2.8%, BiO3For 4.7%, Ce2O3It is 1.0%;
(2) pre-burning in air atmosphere by mixed-powder after ball milling, keeps the temperature 4 hours by 780 DEG C of pre-sintering temperature;
(3) pre-burning product and PbO are taken, the additional amount of PbO is the 6% of pre-burning products weight, and wet ball-milling mixes 3 hours, Binder is added in mixed-powder after drying by drying, and the weight ratio of mixed-powder and the binder after drying is 100: 24, compression moulding after mixing, the pressure of compression moulding is 90MPa;
(4) be sintered in air atmosphere after compression moulding, 900 DEG C of sintering temperature, keep the temperature 4 hours to get.
Wherein, the binder is polyvinyl alcohol water solution, and the weight ratio of the polyethylene alcohol and water is 1:5, described poly- The degree of polymerization of vinyl alcohol is 1400~1500, and alcoholysis degree is 80~90%.
Wherein, the polyvinyl alcohol water solution is made of following preparation methods: taking polyvinyl alcohol to be added to the water, using water-bath Agitating and heating, until polyvinyl alcohol is completely dissolved, exclusion bubble, sieving removal impurity reaches transparent.
Low-temperature sintering monolithic capacitor porcelain Curie temperature manufactured in the present embodiment is -1 DEG C, and the dielectric constant of room temperature is 7200, tan δ are 50 × 10-4, insulation resistance 1011Ω。
Embodiment 5
The present embodiment provides a kind of preparation methods of low-temperature sintering II type monolithic capacitor porcelain, include the following steps:
(1) Pb is taken3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing 12 hours, ball-milling medium is to steam Distilled water is dried after ball milling;By mass percentage, Pb3O4 is 63%, MgCO3For 9.5%, Nb2O5For 19.6%, TiO2For 2.5%, BiO3For 4.5%, Ce2O3It is 0.9%;
(2) pre-burning in air atmosphere by mixed-powder after ball milling, keeps the temperature 5 hours by 790 DEG C of pre-sintering temperature;
(3) pre-burning product and PbO are taken, the additional amount of PbO is the 7% of pre-burning products weight, and wet ball-milling mixes 2 hours, Binder is added in mixed-powder after drying by drying, and the weight ratio of mixed-powder and the binder after drying is 100: 26, compression moulding after mixing, the pressure of compression moulding is 90MPa;
(4) be sintered in air atmosphere after compression moulding, 910 DEG C of sintering temperature, keep the temperature 4 hours to get.
Wherein, the binder is polyvinyl alcohol water solution, and the weight ratio of the polyethylene alcohol and water is 1:5, described poly- The degree of polymerization of vinyl alcohol is 1400~1500, and alcoholysis degree is 80~90%.
Wherein, the polyvinyl alcohol water solution is made of following preparation methods: taking polyvinyl alcohol to be added to the water, using water-bath Agitating and heating, until polyvinyl alcohol is completely dissolved, exclusion bubble, sieving removal impurity reaches transparent.
Low-temperature sintering monolithic capacitor porcelain Curie temperature manufactured in the present embodiment is 0 DEG C, and the dielectric constant of room temperature is 7450, tan δ are 50 × 10-4, insulation resistance 1011Ω。
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (7)

1. a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain, it is characterised in that include the following steps:
(1) Pb is taken3O4、MgCO3、Nb2O5、TiO2、Bi2O3And Ce2O3, wet ball-milling mixing 10~15 hours, ball-milling medium is to steam Distilled water is dried after ball milling;
(2) pre-burning in air atmosphere by mixed-powder after ball milling, keeps the temperature 3~5 hours by 750~800 DEG C of pre-sintering temperature;
(3) pre-burning product and PbO are taken, wet ball-milling mixes 2~4 hours, drying, and bonding is added in the mixed-powder after drying Agent, after mixing compression moulding, the pressure of compression moulding are 90~100MPa;
(4) be sintered in air atmosphere after compression moulding, 880~920 DEG C of sintering temperature, keep the temperature 3~5 hours to get.
2. a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain according to claim 1, it is characterised in that: By mass percentage, Pb3O4For 61~63%, MgCO3For 9.4~10.3%, Nb2O5For 19.5~20.3%, TiO2It is 2.4 ~2.8%, BiO3For 4.3~4.8%, Ce2O3It is 0.8~1.1%.
3. a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain according to claim 1, it is characterised in that: The additional amount of PbO is the 5~7% of pre-burning products weight in the step (3).
4. a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain according to claim 1, it is characterised in that: The binder is polyvinyl alcohol water solution, and the weight ratio of the polyethylene alcohol and water is 1:(3~5).
5. a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain according to claim 4, it is characterised in that: The degree of polymerization of the polyvinyl alcohol is 1400~1500, and alcoholysis degree is 80~90%.
6. a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain according to claim 5, it is characterised in that: The polyvinyl alcohol water solution is made of following preparation methods: it takes polyvinyl alcohol to be added to the water, is heated using stirring in water bath, until Polyvinyl alcohol is completely dissolved, and excludes bubble, and sieving removal impurity reaches transparent.
7. a kind of preparation method of low-temperature sintering II type monolithic capacitor porcelain according to claim 1, it is characterised in that: The weight ratio of mixed-powder and the binder after the drying is 100:(20~30).
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