CN114188067A - Thick-film resistor paste for glass glaze potentiometer and preparation method thereof - Google Patents

Thick-film resistor paste for glass glaze potentiometer and preparation method thereof Download PDF

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Publication number
CN114188067A
CN114188067A CN202111445816.1A CN202111445816A CN114188067A CN 114188067 A CN114188067 A CN 114188067A CN 202111445816 A CN202111445816 A CN 202111445816A CN 114188067 A CN114188067 A CN 114188067A
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film resistor
resistor paste
silver
glass
containing conductive
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杨长印
赵波
荣伟
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Xi'an Xinbei Electronic Technology Co ltd
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Xi'an Xinbei Electronic Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/003—Thick film resistors
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides

Abstract

The invention discloses a thick film resistor paste for a glass glaze potentiometer and a preparation method thereof, and relates to the technical field of thick film resistor pastes, wherein the thick film resistor paste comprises the following components in percentage by weight: 20-50 wt% of silver-containing conductive glass powder and 5-30 wt% of RuO2Or 15 to 30 wt% of Pb2Ru2O625-30 wt% of organic binder, 0.5-20 wt% of TCR regulator; the TCR modulator consists of ZrO2、Al2O3SnO is mixed according to any proportion; the total amount of the TCR regulator does not exceed the silver-containing conductive glass powder and RuO2Or Pb2Ru2O615 wt% of the total weight of the organic binder. The preparation method comprises the following steps: firstly preparing silver-containing conductive glass powder, then uniformly stirring and mixing the silver-containing conductive glass powder with other raw materials, and fully dispersing and processing the mixture by a three-roller machine to obtain the thick film resistor paste for the glass glaze potentiometer. The contradiction between the wear resistance and the contact resistance index of the traditional resistance paste for the glass glaze potentiometer is overcome; the sintered resistor film layer of the potential device has good wear resistance, excellent contact resistance and lower TCR characteristics.

Description

Thick-film resistor paste for glass glaze potentiometer and preparation method thereof
Technical Field
The invention relates to the technical field of thick film resistor paste, in particular to the technical field of thick film resistor paste for a glass glaze potentiometer and a preparation method thereof.
Background
The thick film resistance paste is a technical product integrating electronics, chemical engineering and metallurgy, and is one of the most basic electronic materials in the electronic information industry at present. At present, the thick film resistor paste mainly takes ruthenium resistor paste as a main component, the main conductive component of the paste is ruthenium oxide or ruthenate, such as lead ruthenate, bismuth ruthenate and the like, the resistor paste contains a certain amount of glass powder, and the resistor paste with different resistance values can be formed by different proportions of the glass powder and the conductive component.
In the past, numerous inventions have been introduced relating to the production of resistor pastes, mainly from 2 to 50 wt% RuO2Or 15 to 50 wt% of Pb2Ru2O6And 30-50 wt% of glass powder and 2-10 wt% of additive. RuO as a conductive phase2Or Pb2Ru2O6And glass frit as an inorganic binder, and then redispersed in an organic binder. The glass phase is matched with the conductive phase to adjust the resistance value, and simultaneously, the glass phase plays a role in bonding and can also ensure the strength of the resistance paste sintering film layer. The glass phase also plays a key role in the wear resistance of a resistor film layer of the potentiometer when the glass phase is used as a glass glaze potentiometer.
However, the existing prepared resistance paste can greatly improve the contact resistance between the surface of the resistance film layer of the glass glaze potentiometer and the electric brush due to the existence of the resistance body sintering film layer glass, and the two indexes of the contact resistance Change (CRV), the wear resistance and the contact resistance in the sliding process of the electric brush are a contradiction. The film strength and the wear-resistant property of the film are improved due to the fact that the content of the glass is large, but the contact resistance between the surface of the film and the electric brush is increased due to the insulating property of the glass; the glass content is small, the contact resistance is reduced, but the wear resistance is deteriorated. Therefore, the existing product is difficult to simultaneously take two indexes into consideration, and the overall performance of the glass glaze potentiometer product is low.
Disclosure of Invention
The invention aims to solve the problem of low overall performance of a glass glaze potentiometer product in the prior art, and provides thick film resistor paste for a glass glaze potentiometer and a preparation method thereof.
The invention specifically adopts the following technical scheme for realizing the purpose:
a thick film resistor paste for a glass glaze potentiometer comprises the following components in percentage by weight: 20-50 wt% of silver-containing conductive glass powder and 5-30 wt% of RuO2And/or 15 to 30 wt% of Pb2Ru2O625-30 wt% of organic binder, 0.5-20 wt% of TCR regulator;
the TCR regulator is formed by mixing ZrO2, Al2O3 and SnO according to any proportion;
the total amount of the TCR regulator does not exceed the silver-containing conductive glass powder and RuO2、Pb2Ru2O615 wt% of the total weight of the organic binder.
Further, the silver-containing conductive glass powder comprises the following components in percentage by weight: 10 to 35 wt% of AgNO340 to 75% of Bi2O310 to 30 wt% of SiO21 to 15 wt% of Al2O3。
Furthermore, the silver-containing conductive glass powder also comprises other inorganic oxides, and the weight percentage of the other inorganic oxides is 0-5 wt%.
Further, the other inorganic oxides include MgO, CaO, BaO, B2O3Any one or a mixture of two or more of SrO, SnO and PbO.
The addition of the above inorganic oxide to the conductive glass frit does not have any disadvantage, but rather, can significantly improve the resistance characteristics.
Further, the organic binder includes a mixed solution of ethyl cellulose and terpineol.
Further, the concentration of the mixed solution of the ethyl cellulose and the terpineol is 3-10 wt%.
In order to achieve the purpose, the application also provides a preparation method of the thick film resistor paste for the glass glaze potentiometer, which comprises the following steps:
step 1: adding 10-35 wt% of AgNO340 to 75% of Bi2O310 to 30 wt% of SiO21 to 15 wt% of Al2O3Mixing with 0-5 wt% of other inorganic oxides to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at high temperature to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: 5 to 30 wt% of RuO2Or 15 to 30 wt% of Pb2Ru2O620-50 wt% of silver-containing conductive glass powder, and then 1-10 wt% of ZrO is added21 to 15 wt% of Al2O30.5-20 wt% of SnO, 25-30 wt% of ethyl cellulose and terpineol, uniformly stirring and mixing all the raw materials, and fully dispersing and processing by a three-roll machine to obtain the thick film resistor paste for the glass glaze potentiometer.
Further, the smelting temperature in the step 2 is 1000-1350 ℃; the smelting time is not less than 30 minutes.
Further, the quenching cooling in step 3 is to cool the smelted product by pouring it into deionized water.
The smelting product is beneficial to grinding after quenching and cooling treatment.
Further, other inorganic oxides include MgO, CaO, BaO, B2O3Any one or a mixture of two or more of SrO, SnO and PbO.
The invention has the following beneficial effects:
(1) the invention overcomes the contradiction between the wear resistance and the contact resistance index of the resistance paste for the traditional glass glaze potentiometer by changing the glass powder adopted by the resistance paste, namely replacing the traditional glass powder with the conductive glass powder;
(2) the resistor paste for the glass glaze potentiometer, which is prepared by the preparation method, has the advantages that the sintered resistor film layer of the potentiometer has good wear-resisting property, excellent contact resistance property and lower TCR property.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments.
Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of thick film resistor paste for a glass glaze potentiometer, which specifically comprises the following steps:
step 1: mixing 10 wt% of AgNO355% of Bi2O325% by weight of SiO25 wt% of Al2O3And 5 wt% of B2O3Mixing to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at 1350 ℃ for 30 minutes to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: mixing 30 wt% of Pb2Ru2O635 wt% of silver-containing conductive glass powder, then adding 5 wt% of TCR regulator, 30 wt% of mixed solution of ethyl cellulose and terpineol, and mixing all the raw materialsStirring and mixing uniformly, and fully dispersing and processing by a three-roller machine to obtain the thick film resistor paste for the glass glaze potentiometer.
Comparative example 1
Unlike example 1, the conductive glass frit of example 1 was replaced with the conventional glass frit of comparative example 1.
Experimental verification 1
Respectively carrying out performance experiment verification on the slurry sample 1# prepared in the embodiment 1 and the resistance slurry sample 2# prepared in the comparative example 1, and adopting a 250-mesh stainless steel wire net; the samples were screen printed on a 96% ceramic (Al2O3) substrate, dried at 125 deg.C for 10 minutes, and then sintered at 850 deg.C for 10 minutes to produce resistors, and the results of measuring the properties of the samples are shown in Table 1.
The square resistance, TCR, wear resistance and contact resistance Change (CRV) are tested by a 1 x 10mm graph, the resistance change rate after 100 weeks of wear resistance test and the maximum value after 10 weeks of CRV test.
TABLE 1
Figure BDA0003381723230000041
Figure BDA0003381723230000051
From the results in table 1, it can be seen that, in the case that the conductive phases of the two samples have the same content of lead ruthenate and the sheet resistances are not different from each other, the TCR of sample 1 is small, and the wear resistance and the CRV synchronization are significantly improved compared with sample 2.
Example 2
The embodiment provides a preparation method of thick film resistor paste for a glass glaze potentiometer, which specifically comprises the following steps:
step 1: mixing 25 wt% of AgNO350% of Bi2O315% by weight of SiO25 wt% of Al2O3And 5 wt% of B2O3Mixing to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at 1300 ℃ for 30 minutes to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: 20 wt% of RuO240 wt% of silver-containing conductive glass powder, then 10 wt% of TCR regulator, 30 wt% of mixed solution of ethyl cellulose and terpineol are added, all the raw materials are stirred and mixed uniformly, and the thick film resistor paste for the glass glaze potentiometer is obtained by fully dispersing and processing through a three-roller machine.
Comparative example 2
Unlike example 2, the conventional glass frit was used in comparative example 2 instead of the conductive glass frit in example 2.
Experimental verification 2
Respectively carrying out performance experiment verification on the slurry sample 1# prepared in the embodiment 2 and the resistance slurry sample 2# prepared in the comparative example 2, and adopting a 250-mesh stainless steel wire net; the samples were screen printed on a 96% ceramic (Al2O3) substrate, dried at 125 deg.C for 10 minutes, and then sintered at 850 deg.C for 10 minutes to produce resistors, and the results of measuring the properties of the samples are shown in Table 2.
The square resistance, TCR, wear resistance and contact resistance Change (CRV) are tested by a 1 x 10mm graph, the resistance change rate after 100 weeks of wear resistance test and the maximum value after 10 weeks of CRV test.
TABLE 2
Figure BDA0003381723230000061
As can be seen from the results in table 2, in the case that the conductive phases of the two samples have the same content of lead ruthenate and the sheet resistances are not different from each other, the TCR of sample 1 is small, and the wear resistance and the CRV are significantly improved at the same time, compared with sample 2.
Example 3
The embodiment provides a preparation method of thick film resistor paste for a glass glaze potentiometer, which specifically comprises the following steps:
step 1: mixing 35 wt% of AgNO340% of Bi2O315% by weight of SiO25 wt% of Al2O3And 5 wt% of B2O3Mixing to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at 1300 ℃ for 30 minutes to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: adding 20 wt% of Pb2Ru2O645 wt% of silver-containing conductive glass powder, then adding 5 wt% of TCR regulator, 30 wt% of mixed solution of ethyl cellulose and terpineol, stirring and mixing all the raw materials uniformly, and fully dispersing and processing by a three-roller machine to obtain the thick film resistor paste for the glass glaze potentiometer.
Comparative example 3
Unlike example 3, the conventional glass frit was used in comparative example 3 instead of the conductive glass frit in example 3.
Experimental verification 3
Respectively carrying out performance experiment verification on the slurry sample 1# prepared in the embodiment 3 and the resistance slurry sample 2# prepared in the comparative example 3, and adopting a 250-mesh stainless steel wire net; the samples were screen printed on a 96% ceramic (Al2O3) substrate, dried at 125 deg.C for 10 minutes, and then sintered at 850 deg.C for 10 minutes to produce resistors, and the results of measuring the properties of the samples are shown in Table 3.
The square resistance, TCR, wear resistance and contact resistance Change (CRV) are tested by a 1 x 10mm graph, the resistance change rate after 100 weeks of wear resistance test and the maximum value after 10 weeks of CRV test.
TABLE 3
Figure BDA0003381723230000071
From the results in table 3, it can be seen that in the case that the conductive phases of the two samples have the same content of lead ruthenate and the sheet resistances are not different from each other, the TCR of sample 1 is small, and the wear resistance and CRV synchronization are significantly improved compared with sample 2.
Example 4
The embodiment provides a preparation method of thick film resistor paste for a glass glaze potentiometer, which specifically comprises the following steps:
step 1: mixing 15 wt% of AgNO365% of Bi2O310% by weight of SiO25 wt% of Al2O3And 5 wt% of B2O3Mixing to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at 1350 ℃ for 30 minutes to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: mixing 30 wt% of Pb2Ru2O640 wt% of silver-containing conductive glass powder, then adding 5 wt% of TCR regulator, 25 wt% of mixed solution of ethyl cellulose and terpineol, stirring and mixing all the raw materials uniformly, and fully dispersing and processing by a three-roller machine to obtain the thick film resistor paste for the glass glaze potentiometer.
Comparative example 4
Unlike example 4, the conventional glass frit was used in comparative example 4 instead of the conductive glass frit in example 4.
Experimental verification 4
Respectively carrying out performance experiment verification on the slurry sample 1# prepared in the embodiment 4 and the resistance slurry sample 2# prepared in the comparative example 4, and adopting a 250-mesh stainless steel wire net; the samples were screen printed on a 96% ceramic (Al2O3) substrate, dried at 125 deg.C for 10 minutes, and then sintered at 850 deg.C for 10 minutes to produce resistors, and the results of measuring the properties of the samples are shown in Table 4.
The square resistance, TCR, wear resistance and contact resistance Change (CRV) are tested by a 1 x 10mm graph, the resistance change rate after 100 weeks of wear resistance test and the maximum value after 10 weeks of CRV test.
TABLE 4
Figure BDA0003381723230000081
From the results in table 4, it can be seen that, in the case that the conductive phases of the two samples have the same content of lead ruthenate and the sheet resistances are not different from each other, the TCR of sample 1 is small, and the wear resistance and the CRV synchronization are significantly improved compared with sample 2.
Example 5
The embodiment provides a preparation method of thick film resistor paste for a glass glaze potentiometer, which specifically comprises the following steps:
step 1: mixing 10 wt% of AgNO375% of Bi2O310% by weight of SiO21 wt% of Al2O34% by weight of B2O3Mixing to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at 1350 ℃ for 30 minutes to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: mixing 15 wt% of Pb2Ru2O6And mixing 50 wt% of silver-containing conductive glass powder, adding 5 wt% of TCR regulator and 30 wt% of mixed solution of ethyl cellulose and terpineol, stirring and mixing all the raw materials uniformly, and fully dispersing and processing by a three-roller machine to obtain the thick film resistor paste for the glass glaze potentiometer.
Comparative example 5
Unlike example 5, the conventional glass frit was used in comparative example 5 instead of the conductive glass frit in example 5.
Experimental verification 5
Respectively carrying out performance experiment verification on the slurry sample 1# prepared in the embodiment 5 and the resistance slurry sample 2# prepared in the comparative example 5, and adopting a 250-mesh stainless steel wire net; the samples were screen printed on a 96% ceramic (Al2O3) substrate, dried at 125 deg.C for 10 minutes, and then sintered at 850 deg.C for 10 minutes to produce resistors, and the results of measuring the properties of the samples are shown in Table 5.
The square resistance, TCR, wear resistance and contact resistance Change (CRV) are tested by a 1 x 10mm graph, the resistance change rate after 100 weeks of wear resistance test and the maximum value after 10 weeks of CRV test.
TABLE 5
Figure BDA0003381723230000091
From the results in table 5, it can be seen that in the case that the conductive phases of the two samples have the same content of lead ruthenate and the sheet resistances are not different from each other, the TCR of sample 1 is small, and the wear resistance and CRV synchronization are significantly improved compared with sample 2.
Example 6
The embodiment provides a preparation method of thick film resistor paste for a glass glaze potentiometer, which specifically comprises the following steps:
step 1: mixing 15 wt% of AgNO360% of Bi2O315% by weight of SiO25 wt% of Al2O3And 5 wt% of B2O3Mixing to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at 1350 ℃ for 30 minutes to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: mixing 5 wt% of RuO2And mixing 50 wt% of silver-containing conductive glass powder, adding 20 wt% of TCR regulator and 25 wt% of mixed solution of ethyl cellulose and terpineol, stirring and mixing all the raw materials uniformly, and fully dispersing and processing by a three-roller machine to obtain the thick film resistor paste for the glass glaze potentiometer.
Comparative example 6
Unlike example 6, the conventional glass frit was used in comparative example 6 instead of the conductive glass frit in example 6.
Experimental verification 6
Respectively carrying out performance experiment verification on the slurry sample 1# prepared in the embodiment 6 and the resistance slurry sample 2# prepared in the comparative example 6, and adopting a 250-mesh stainless steel wire net; the samples were screen printed on a 96% ceramic (Al2O3) substrate, dried at 125 deg.C for 10 minutes, and then sintered at 850 deg.C for 10 minutes to produce resistors, and the results of measuring the properties of the samples are shown in Table 6.
The square resistance, TCR, wear resistance and contact resistance Change (CRV) are tested by a 1 x 10mm graph, the resistance change rate after 100 weeks of wear resistance test and the maximum value after 10 weeks of CRV test.
TABLE 6
Figure BDA0003381723230000101
As can be seen from the results in table 6, in the case that the conductive phases of the two samples have the same content of lead ruthenate and the sheet resistances are not different from each other, the TCR of sample 1 is small, and the wear resistance and the CRV synchronization are significantly improved as compared with sample 2.
Example 7
The embodiment provides a preparation method of thick film resistor paste for a glass glaze potentiometer, which specifically comprises the following steps:
step 1: mixing 15 wt% of AgNO365% of Bi2O315% by weight of SiO25 wt% of Al2O3Mixing to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at 1350 ℃ for 30 minutes to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: mixing 30 wt% of RuO239.5 wt% of silver-containing conductive glass powder, then 0.5 wt% of TCR regulator, 30 wt% of mixed solution of ethyl cellulose and terpineol are added, all the raw materials are stirred and mixed uniformly, and the thick film resistor paste for the glass glaze potentiometer is obtained by fully dispersing and processing through a three-roller machine.
Comparative example 7
Unlike example 7, the conductive glass frit of example 7 was replaced with the conventional glass frit of comparative example 7.
Experimental verification 7
Respectively carrying out performance experiment verification on the slurry sample 1# prepared in the embodiment 7 and the resistance slurry sample 2# prepared in the comparative example 7, and adopting a 250-mesh stainless steel wire net; the samples were screen printed on a 96% ceramic (Al2O3) substrate, dried at 125 deg.C for 10 minutes, and then sintered at 850 deg.C for 10 minutes to produce resistors, and the results of measuring the properties of the samples are shown in Table 7.
The square resistance, TCR, wear resistance and contact resistance Change (CRV) are tested by a 1 x 10mm graph, the resistance change rate after 100 weeks of wear resistance test and the maximum value after 10 weeks of CRV test.
TABLE 7
Figure BDA0003381723230000111
From the results in table 7, it can be seen that, in the case that the conductive phases of the two samples have the same content of lead ruthenate and the sheet resistances are not different, the TCR of sample 1 is small, and the wear resistance and CRV synchronization are obviously improved compared with sample 2.
Example 8
Determining the dosage interval of each component in the conductive glass powder:
if in the conductive glass frit, AgNO3If the content ratio is less than 5%, the contact resistance of the conductive glass powder to the resistor body is not obviously improved; conversely, if AgNO3When the ratio is more than 35 wt%, indexes such as film layer structure and resistance value dispersibility of the resistance paste are deteriorated, and AgNO of 10-35 wt% is used3The obtained conductive glass powder not only obviously improves the contact resistance, but also has excellent indexes such as film layer structure, resistance value dispersibility and the like of the resistance slurry, so the AgNO is applied3The content is determined to be 10-35 wt%.
When Bi is present2O3When the proportion of (B) is less than 40 wt%, the softening point of the glass becomes too high, so that the sintering temperature is increased and the stability of the electric resistance is lowered, but when Bi is contained2O3Above 75 wt%, a stable glass phase cannot be obtained, so that Bi is incorporated herein2O3The content of (B) is determined to be 40 to 75 wt%.
When SiO is present2At contents below 10 wt%, the glass phase is unstable, conversely, when SiO2Above 30 wt%, the softening point temperature of the glass is increased too much, so that SiO is applied to the present invention2The content of (B) is determined to be 10 to 30 wt%.
When Al is present2O3When the content is 1 wt%, the moisture resistance of the resistor body and the chemical stability of the glass are reduced; when Al is present2O3Above 15 wt%, the glass will rapidly super-crystallize to an unstable state, and therefore Al is claimed herein2O3The content of (B) is determined to be 1 to 15 wt%.

Claims (10)

1. The thick-film resistor paste for the glass glaze potentiometer is characterized by comprising the following components in percentage by weight: 20-50 wt% of silver-containing conductive glass powder and 5-30 wt% of RuO2Or 15 to 30 wt% of Pb2Ru2O625-30 wt% of organic binder, 0.5-20 wt% of TCR regulator;
the TCR modulator consists of ZrO2、Al2O3SnO is mixed according to any proportion;
the total amount of the TCR regulator does not exceed the silver-containing conductive glass powder and RuO215 wt% of the total weight of the organic binder; or the total amount of the TCR modulator does not exceed silver-containing conductive glass powder and Pb2Ru2O615 wt% of the total weight of the organic binder.
2. The thick-film resistor paste for the glass glaze potentiometer as claimed in claim 1, wherein the silver-containing conductive glass powder comprises the following components in percentage by weight: 10 to 35 wt% of AgNO340 to 75% of Bi2O310 to 30 wt% of SiO21 to 15 wt% of Al2O3。
3. The thick-film resistor paste for a glass glaze potentiometer according to claim 2, wherein the silver-containing conductive glass powder further comprises other inorganic oxides in an amount of 0-5 wt%.
4. A thick film resistor paste for a glass-glaze potentiometer according to claim 3, wherein the other inorganic oxides include MgO, CaO, BaO, B2O3Any one or a mixture of two or more of SrO, SnO and PbO.
5. A thick film resistor paste for a glass-glaze potentiometer according to claim 1, wherein the organic binder comprises a mixed solution of ethyl cellulose and terpineol.
6. The thick-film resistor paste for a glass-glaze potentiometer according to claim 5, wherein the concentration of the mixed solution of ethyl cellulose and terpineol is 3-10 wt%.
7. The preparation method of the thick film resistor paste for the glass glaze potentiometer as claimed in any one of the claims 1 to 5, which is characterized by comprising the following steps:
step 1: adding 10-35 wt% of AgNO340 to 75% of Bi2O310 to 30 wt% of SiO21 to 15 wt% of Al2O3Mixing with 0-5 wt% of other inorganic oxides to obtain a mixed product;
step 2: smelting the mixed product obtained in the step 1 at high temperature to obtain a smelting product;
and step 3: quenching, cooling and grinding the smelting product obtained in the step 2 to prepare silver-containing conductive glass powder;
and 4, step 4: 5 to 30 wt% of RuO2Or 15 to 30 wt% of Pb2Ru2O620-50 wt% of silver-containing conductive glass powder, and then 1-10 wt% of ZrO is added21 to 15 wt% of Al2O30.5-20 wt% of SnO, 25-30 wt% of ethyl cellulose and terpineol, stirring and mixing all the raw materials uniformly, fully dispersing by a three-roller machine, and addingObtaining the thick film resistor paste for the glass glaze potentiometer.
8. The method for preparing the thick-film resistor paste for the glass glaze potentiometer according to claim 7, wherein the melting temperature in the step 2 is 1000-1350 ℃; the smelting time is not less than 30 minutes.
9. The method for preparing a thick-film resistor paste for a glass-glaze potentiometer according to claim 7, wherein the quenching cooling in step 3 is performed by pouring the melted product into deionized water for cooling.
10. The method for preparing thick film resistor paste for glass-glaze potentiometers according to claim 7, wherein 5 wt% of other inorganic oxides are added in step 1, and the other inorganic oxides include MgO, CaO, BaO, B2O3Any one or a mixture of two or more of SrO, SnO and PbO.
CN202111445816.1A 2021-11-29 2021-11-29 Thick-film resistor paste for glass glaze potentiometer and preparation method thereof Pending CN114188067A (en)

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