CN101851091B - Temperature change resistance composite high-dielectric electronic material and preparation method thereof - Google Patents

Abstract

The invention relates to a temperature change resistance composite high-dielectric electronic material and a preparation method thereof. The electronic material comprises the components by weight percent: 42-45% of BaTiO3, 19-26% of (Na 0.5, Bi 0.5) TiO3, 28-38% of Pb (Sn0.6, Ti0.4) O3, 0.6-1% of MgO and 0.2-2% of Sm2O3, wherein the Pb (Sn0.6, Ti0.4) O3 is prepared by PbO, SnO2 and TiO2, and the molar ratio of the PbO, the SnO2 and the TiO2 is 5: 3: 2; and the (Na 0.5, Bi 0.5) TiO3 is prepared by NaCO3, Bi2O3 and TiO2, and the molar ratio of the NaCO3, the Bi2O3 and the TiO2 is 2: 1: 4. The preparation method comprises: prefabricating the Pb (Sn0.6, Ti0.4) O3, prefabricating the (Na, Bi) TiO3, forming blank and sintering. The invention has low manufacturing cost, and is applicable to electron devices such as a capacitor, a filter and the like.

Description

Temperature change resistant composite high dielectric material and preparation method thereof

technical field

The invention relates to a composite high dielectric material characterized by composition, in particular, a composite high dielectric material capable of resisting temperature changes and a preparation method thereof.

Background technique

The dielectric material should have a high dielectric constant and have as wide a working temperature range as possible under the premise of ensuring a small temperature change rate of the dielectric constant. Although research institutions around the world have conducted a lot of research on dielectric materials for half a century, and their performance parameters have been greatly improved in many aspects, the operating temperature range of existing materials is still narrow. When the ambient temperature When the temperature rises above 150°C, its dielectric constant will change abruptly, which may cause the device and even the whole machine circuit to fail, so it cannot meet the increasingly high requirements of radar, aircraft and other special equipment.

Contents of the invention

The invention purpose of the present invention is aimed at the defective of prior art, one is to provide a kind of high reliability requirement that can satisfy electronic device, meet the increasingly higher requirement of radar, aircraft and other special equipment and be suitable for being suitable in bad environment temperature ( -55～+200℃), the second is to provide a BaTiO ₃ -(Na _0.5 , Bi _0.5 )TiO ₃ -Pb(Sn _0.6 , Ti _0.4 )O ₃ system material medium and its preparation method.

Realize above-mentioned invention object and adopt following technical scheme:

A composite high dielectric material with resistance to temperature change, the composition and weight percentage of raw materials are as follows: BaTiO ₃ is 42-45%, (Na _0.5 , Bi _0.5 )TiO ₃ is 19-26%, Pb(Sn _0.6 , Ti _0.4 )O ₃ is 28-38%, MgO is 0.6-1%, and Sm ₂ O ₃ is 0.2-2%. Among them, Pb(Sn _0.6 , Ti _0.4 )O ₃ is prepared by PbO, SnO ₂ and TiO ₂ , PbO, The molar ratio of SnO ₂ to TiO ₂ is 5:3:2; (Na _0.5 , Bi _0.5 )TiO ₃ is prepared using NaCO ₃ , Bi ₂ O ₃ and TiO ₂ , and the molar ratio of NaCO ₃ , Bi ₂ O ₃ to TiO ₂ It is 2:1:4.

A method for preparing a temperature-change-resistant composite high-dielectric material, comprising the following steps:

(1) Prefabrication of Pb(Sn _0.6 , Ti _0.4 )O ₃ : According to the molar ratio of PbO, SnO ₂ and TiO ₂ is 5:3:2, put the ingredients into a ball mill, add 1 to 3 times the volume of deionized water for ball milling Dry at 105°C for 1 to 12 hours to obtain powder, pass the powder through a 200-mesh sieve, heat the sieved powder to 980°C to 990°C for 3 to 5 hours, and cool at room temperature to obtain Pb (Sn _0.6 , Ti _0.4 )O ₃ ;

(2) Prefabricated (Na _0.5 , Bi _0.5 )TiO ₃ : According to the molar ratio of NaCO ₃ , Bi ₂ O ₃ and TiO ₂ is 2:1:4, put the ingredients into a ball mill, add 1 to 3 times the volume of deionization Water ball milling for 1-12 hours, drying at 105°C to obtain powder, passing the powder through a 200-mesh sieve, heating the sieved powder to 900°C-920°C for 1.5-2.5 hours, cooling at room temperature Get (Na _0.5 , Bi _0.5 )TiO ₃ ;

(3) BaTiO ₃ is 42-45% by weight, (Na _0.5 , Bi _0.5 ) TiO ₃ frit is 19-26%, Pb(Sn _0.6 , Ti _0.4 )O ₃ frit is 28-38%, and MgO is 0.6~1%, Sm ₂ O ₃ is 0.2~2% to prepare raw materials, put the prepared raw materials into a ball mill, add 1~3 times the volume of deionized water to ball mill for 1~12 hours; then dry at 105°C to obtain Powder, pass the powder through a 500-mesh sieve, add 5% to 6% by weight of organic binder or paraffin to the sieved powder, add 90 to 120Mpa to press to form a green body, and then heat to 1180 ℃～1200℃ heat preservation for 4～9 hours, and cooling at room temperature to prepare composite high dielectric material with resistance to temperature change.

The beneficial effect of the invention is that it provides a temperature-change-resistant composite high-dielectric electronic material suitable for working at a harsh ambient temperature of -55 to +200°C, which can meet the high reliability requirements of electronic devices. Although research institutions around the world have conducted a lot of research on dielectric materials for half a century, and their performance parameters have been greatly improved in many aspects, the operating temperature range of existing materials is still narrow. When the ambient temperature When the temperature rises above 150°C, its dielectric constant will change abruptly, which may cause the device and even the whole machine circuit to fail, so it cannot meet the increasingly high requirements of radar, aircraft and other special equipment. The dielectric material provided by the invention can just meet this stringent requirement. In addition, the dielectric constant of the dielectric material proposed by the present invention is relatively high, which is higher than the room temperature dielectric constant of the existing similar thermally stable materials not higher than 2800.

Description of drawings

Fig. 1 is the test result of the dielectric material with excellent performance that can be realized by the present invention.

Detailed ways

This embodiment is a kind of anti-temperature change composite high dielectric material and its preparation method. The raw materials used are: chemically pure BaTiO ₃ , chemically pure PbO, chemically pure TiO ₂ , analytically pure SnO ₂ , chemically pure NaCO ₃ , chemically pure Bi ₂ O ₃ , chemically pure TiO ₂ , chemically pure MgO, and analytically pure Sm ₂ O ₃ .

Its components and weight percentages of raw materials are as follows: BaTiO ₃ is 42-45%, (Na _0.5 , Bi _0.5 )TiO ₃ frit is 19-26%, Pb(Sn _0.6 , Ti _0.4 )O ₃ frit is 28-28% 38%, MgO is O.6~1%, Sm ₂ O ₃ is 0.2~2%; where Pb(Sn _0.6 , Ti _0.4 )O ₃ is prepared by PbO, SnO ₂ and TiO ₂ , PbO, SnO ₂ and TiO ₂ The molar ratio is 5:3:2; (Na _0.5 , Bi _0.5 )TiO ₃ is prepared using NaCO ₃ , Bi ₂ O ₃ and TiO ₂ , and the molar ratio of NaCO ₃ , Bi ₂ O ₃ and TiO ₂ is 2:1: 4.

Specific examples are as follows:

Embodiment one:

(1) Prefabrication of Pb(Sn _0.6 , Ti _0.4 )O ₃ : According to the molar ratio of PbO, SnO ₂ and TiO ₂ as 5:3:2, put the ingredients into a ball mill, add 3 times the volume of deionized water and ball mill for 12 hours , dried at 105°C to obtain powder, passed the powder through a 200-mesh sieve, heated the sieved powder to 990°C for 5 hours, and cooled at room temperature to obtain Pb(Sn _0.6 , Ti _0.4 )O ₃ ;

(2) Prefabricated (Na _0.5 , Bi _0.5 )TiO ₃ : According to the molar ratio of NaCO ₃ , Bi ₂ O ₃ and TiO ₂ as 2:1:4, put the ingredients into a ball mill, add 3 times the volume of deionized water for ball milling Dry the powder at 105°C for 12 hours, pass the powder through a 200-mesh sieve, heat the sieved powder to 900°C for 2.5 hours, and cool at room temperature to obtain (Na _0.5 , Bi _0.5 ) TiO ₃ ;

(3) BaTiO ₃ is 42% by weight, (Na _0.5 , Bi _0.5 ) TiO ₃ frit is 19%, Pb(Sn _0.6 , Ti _0.4 )O ₃ frit is 38%, MgO is O.6%, Sm ₂ O ₃ is 0.4% to prepare raw materials, put the prepared raw materials into a ball mill, add 3 times the volume of deionized water and ball mill for 9 hours; then dry at 105°C to obtain powder, pass the powder through a 500-mesh sieve, Add 5% by weight organic binder or paraffin to the sieved powder, add 120Mpa to press to form a green body, then heat to 1200°C for 7 hours, and cool at room temperature to obtain a temperature-change-resistant composite high-k dielectric material .

Embodiment two:

(1) Prefabrication of Pb(Sn _0.6 , Ti _0.4 )O ₃ : According to the molar ratio of PbO, SnO ₂ and TiO ₂ as 5:3:2, put the ingredients into a ball mill, add 3 times the volume of deionized water and ball mill for 8 hours , dried at 105°C to obtain powder, passed the powder through a 200-mesh sieve, heated the sieved powder to 990°C for 5 hours, and cooled at room temperature to obtain Pb(Sn _0.6 , Ti _0.4 )O ₃ ;

(2) Prefabricated (Na _0.5 , Bi _0.5 )TiO ₃ : According to the molar ratio of NaCO ₃ , Bi ₂ O ₃ and TiO ₂ as 2:1:4, put the ingredients into a ball mill, add 3 times the volume of deionized water for ball milling For 8 hours, dry at 105°C to obtain powder, pass the powder through a 200-mesh sieve, heat the sieved powder to 920°C for 2 hours, and cool at room temperature to obtain (Na _0.5 , Bi _0.5 )TiO ₃ ;

(3) By weight BaTiO ₃ is 43%, (Na _0.5 , Bi _0.5 )TiO ₃ frit is 21%, Pb(Sn _0.6 , Ti _0.4 )O ₃ frit is 34%, MgO is 0.8%, Sm ₂ O ₃ is to prepare raw materials at 1.2%, put the prepared raw materials into a ball mill, add 3 times the volume of deionized water and ball mill for 12 hours; then dry the powder at 105°C, pass the powder through a 500-mesh sieve, and Add 6% by weight organic binder or paraffin to the sieved powder, add 120Mpa to press to form a green body, then heat to 1190°C for 8 hours, and cool at room temperature to obtain a temperature-change-resistant composite high-k dielectric material.

Embodiment three:

(1) Prefabrication of Pb(Sn _0.6 , Ti _0.4 )O ₃ : According to the molar ratio of PbO, SnO ₂ and TiO ₂ as 5:3:2, put the ingredients into a ball mill, add 3 times the volume of deionized water and ball mill for 12 hours , dried at 105°C to obtain powder, passed the powder through a 200-mesh sieve, heated the sieved powder to 990°C for 5 hours, and cooled at room temperature to obtain Pb(Sn _0.6 , Ti _0.4 )O ₃ ;

(2) Prefabricated (Na _0.5 , Bi _0.5 )TiO ₃ : According to the molar ratio of NaCO ₃ , Bi ₂ O ₃ and TiO ₂ as 2:1:4, put the ingredients into a ball mill, add 3 times the volume of deionized water for ball milling Dry at 105°C for 12 hours to obtain powder, pass the powder through a 200-mesh sieve, heat the sieved powder to 920°C for 1.5 hours, and cool at room temperature to obtain (Na _0.5 , Bi _0.5 )TiO ₃ ;

(3) By weight BaTiO ₃ is 45%, (Na _0.5 , Bi _0.5 )TiO ₃ frit is 23%, Pb(Sn _0.6 , Ti _0.4 )O ₃ frit is 29%, MgO is 1%, Sm ₂ O ₃ is to prepare raw materials at 2%, put the prepared raw materials into a ball mill, add 3 times the volume of deionized water and ball mill for 12 hours; then dry at 105°C to obtain powder, pass the powder through a 500-mesh sieve, Add 6% by weight organic binder or paraffin to the sieved powder, add 120Mpa to press to form a green body, then heat to 1200°C for 9 hours, and cool at room temperature to obtain a temperature-change-resistant composite high-k dielectric material.

The above-mentioned examples give three different formulations respectively, and obtain composite high-k dielectric materials satisfying different sintering temperatures and different dielectric constants. The obtained electronic material is coated with a metal electrode, and the capacitance is measured and the relative permittivity ε is calculated under a low-frequency electric field with a frequency of 1KHz and in different constant temperature environments.

Accompanying drawing 1 is the test result of the dielectric material of excellent performance that the present invention can realize, as Fig. 1, room temperature dielectric constant is 2950, and the absolute value of dielectric constant change rate remains on 15% under-55～+200 ℃ It can meet the increasingly high requirements of radar, aircraft and other special equipment.

The dielectric material of the invention is suitable for commonly used electronic devices such as filters and capacitors, especially for electronic systems that require high reliability under severe conditions of -55 to +200°C.

The above disclosures are only specific embodiments of the present invention. Although the present invention is disclosed above with preferred embodiments, the present invention is not limited thereto. Any changes that those skilled in the art can conceive without departing from the scope of the present invention Within the design concept and scope, various changes and modifications to the present invention should fall within the protection scope of the present invention.

Claims (1)

1. the preparation method of a temperature change resistance composite high-dielectric electronic material is characterized in that, the component of formation temperature change resistance composite high-dielectric electronic material and the percentage by weight of raw material thereof are following: BaTiO ₃Be 42～45%, (Na _0.5, Bi _0.5) TiO ₃Be 19～26%, Pb (Sn _0.6, Ti _0.4) O ₃Be 28～38%, MgO is 0.6～1%, Sm ₂O ₃Be 0.2～2%, its preparation method comprises the steps:

(1) prefabricated Pb (Sn _0.6, Ti _0.4) O ₃: press PbO, SnO ₂With TiO ₂Mol ratio be 5: 3: 2 the batching; Batching is inserted ball mill; Add 1～3 times of volumes of deionized water ball milling 1～12 hour, oven dry obtains powder under 105 ℃ of environment, and powder is passed through 200 purpose screen clothes; Powder after sieving is heated to 980 ℃～990 ℃ insulations 3～5 hours, and the room temperature cooling makes Pb (Sn _0.6, Ti _0.4) O ₃

(2) prefabricated (Na _0.5, Bi _0.5) TiO ₃: press NaCO ₃, Bi ₂O ₃With TiO ₂Mol ratio be 2: 1: 4 the batching; Batching is inserted ball mill; Add 1～3 times of volumes of deionized water ball milling 1～12 hour, oven dry obtains powder under 105 ℃ of environment, and powder is passed through 200 purpose screen clothes; Powder after sieving is heated to 900 ℃～920 ℃ insulations 1.5～2.5 hours, and the room temperature cooling makes (Na _0.5, Bi _0.5) TiO ₃

(3) according to weight BaTiO ₃Be 42～45%, (Na _0.5, Bi _0.5) TiO ₃Frit is 19～26%, Pb (Sn _0.6, Ti _0.4) O ₃Frit is 28～38%, and MgO is 0.6～1%, Sm ₂O ₃Be 0.2～2% preparation raw material, with joining raw material insert ball mill, add the deionized water ball milling 1～12 hour of 1～3 times of volume; Oven dry obtains powder under 105 ℃ of environment then; Powder is passed through 500 purpose screen clothes; The organic bond that adds 5%～6% weight ratio in the powder after sieving; Add 90～120Mpa pressure and process green compact, be heated to 1180 ℃～1200 ℃ insulations 4～9 hours afterwards, the room temperature cooling makes temperature change resistance composite high-dielectric electronic material.

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