Glass powder, resistance paste, preparation method and application

Abstract

The invention provides glass powder, resistance paste, a preparation method and application. The preparation method of the glass powder comprises the following steps: carrying out first smelting, quenching and first grinding on a first mixture to prepare a first intermediate with the particle size D50 not greater than 2 microns; grinding and mixing a modifier and the first intermediate to obtain a second mixture; the second mixture is subjected to second smelting, first stirring, water quenching and second grinding, and powder with the particle size D50 not larger than 2 micrometers is prepared; freezing and warming the powder to prepare a second intermediate; and carrying out ball-milling mixing on manganese dioxide and the second intermediate to obtain a third mixture, and carrying out third smelting and third grinding to make the manganese dioxide melt infiltrate into the surface layer of the second intermediate to prepare the glass powder. The resistance paste prepared from the prepared glass powder not only has good high-voltage pulse resistance, but also can greatly reduce the positive and negative temperature coefficients of the resistance paste.

Description

Technical Field

[0001] The present invention relates to the technical field of glass powder, and in particular to glass powder, resistor slurry, preparation method and application. Background Art

[0002] Resistor paste is an important material for manufacturing thick film resistors, resistor networks, hybrid integrated circuits, and special-purpose resistors and converter valves. Glass powder is an important component of resistor paste and is often used as a binder phase. The interaction between the binder phase and the conductive phase in the resistor paste affects the electrical properties of the paste, such as resistance value, resistance temperature coefficient, and high-voltage pulse resistance. The current resistor paste is highly sensitive to temperature and has poor high-voltage pulse resistance, which cannot meet market demand. Summary of the invention

[0003] In view of the problems existing in the prior art, a glass powder, a resistor slurry, a preparation method and an application are provided.

[0004] In some embodiments, a method for preparing glass powder is provided, the method for preparing glass powder comprising the following steps:

[0005] The first mixed material is first smelted, quenched, and first ground to prepare a particle size D 50 A first intermediate no larger than 2 μm;

[0006] Grinding and mixing the modifier and the first intermediate to prepare a second mixture;

[0007] The second mixed material is subjected to a second smelting, a first stirring, a water quenching, and a second grinding to prepare a particle size D 50 Powders no larger than 2μm;

[0008] Freezing the powder and returning it to the temperature to prepare a second intermediate;

[0009] ball-milling manganese dioxide and the second intermediate to prepare a third mixed material;

[0010] The third mixed material is subjected to a third smelting to allow the manganese dioxide melt to infiltrate the surface layer of the second intermediate, and the third grinding is performed to prepare the glass powder;

[0011] Calculated by feed amount, the first mixed material contains 10wt% to 40wt% of SiO2, 20wt% to 80wt% of PbO, and 2wt% to 25wt% of metal oxide.

[0012] In some embodiments, the preparation method meets one or more of the following characteristics:

[0013] (1) The modifier contains Al2O3, CaO and SnO, and the mass ratio of Al2O3, CaO and SnO is (1-15): (1-15): (0.01-15);

[0014] (2) Based on the amount of materials added, the second mixed material contains 1wt% to 15wt% of Al2O3, 1wt% to 15wt% of CaO, 0.01wt% to 15wt% of SnO and 75wt% to 95wt% of the first intermediate;

[0015] (3) Based on the amount of materials added, the third mixed material contains 0.1wt% to 10wt% of manganese dioxide and 90wt% to 99.9wt% of the second intermediate.

[0016] In some embodiments, the preparation method meets one or more of the following characteristics:

[0017] (1) Based on the amount of materials added, the first mixed material contains 15wt% to 35wt% of SiO2, 50wt% to 80wt% of PbO, and 2wt% to 25wt% of metal oxides;

[0018] (2) The mass ratio of Al2O3, CaO and SnO in the modifier is (1-15): (1-15): (0.01-8.5);

[0019] (3) Based on the amount of materials added, the second mixed material contains 1wt% to 15wt% of Al2O3, 1wt% to 15wt% of CaO, 0.01wt% to 8.5wt% of SnO and 75wt% to 95wt% of the first intermediate;

[0020] (4) Based on the amount of materials added, the third mixed material contains 0.1 wt% to 2 wt% of MnO2 and 98 wt% to 99.9 wt% of the second intermediate.

[0021] In some embodiments, the preparation method meets one or more of the following characteristics:

[0022] (1) The metal oxide in the first mixed material includes at least one of Bi2O3 and BaO;

[0023] (2) The temperature for performing the first smelting is 1300° C. to 1600° C.;

[0024] (3) The holding time for the first smelting is 30 min to 60 min;

[0025] (4) using a roller cooling device to perform the quenching;

[0026] (5) The temperature for the second smelting is 1200° C. to 1400° C.;

[0027] (6) The holding time for the second smelting is 30 min to 60 min.

[0028] In some embodiments, in the preparation method, the temperature for performing the third smelting is 550° C. to 650° C., and the insulation time for performing the third smelting is 60 min to 120 min.

[0029] In some embodiments, the preparation method meets one or more of the following characteristics:

[0030] (1) The quenching temperature is 15°C to 30°C;

[0031] (2) The first stirring speed is 40 r / min to 60 r / min;

[0032] (3) The water quenching temperature is 15°C to 30°C;

[0033] (4) The volume of water during the water quenching process is 50 to 100 times the volume of the smelted powder;

[0034] (5) freezing the powder in a sealed environment;

[0035] (6) The freezing temperature is -100°C to -20°C;

[0036] (7) The freezing time is 3h to 5h;

[0037] (8) The temperature recovery rate is 1.5°C / h to 5°C / h.

[0038] In some embodiments, a glass powder is provided, and the glass powder is prepared according to the preparation method of the glass powder.

[0039] In some embodiments, the glass powder satisfies at least one of the following characteristics:

[0040] (1) The particle size of the glass powder is 500nm to 5μm;

[0041] (2) The softening point of the glass powder is 600°C to 800°C;

[0042] (3) The system of the glass powder is Si-Pb-Bi-Al system glass powder, Si-Pb-Bi-Ca system glass powder, or Si-Pb-Ba-Al system glass powder.

[0043] In some embodiments, there is provided application of the glass powder in preparing resistor paste or electronic products.

[0044] In some embodiments, a resistor paste is provided, which includes the glass powder.

[0045] In some embodiments, an electronic product is provided, which contains the glass powder or the resistor paste.

[0046] In some embodiments, the electronic product is at least one of a thick film resistor, a resistor network, a hybrid integrated circuit, and a converter valve.

[0047] The preparation method provided in the above application adopts the method of batch melting and infiltration of oxides to prepare and modify glass powder. Batch melting can accurately control the chemical composition and distribution uniformity of each component in the glass powder. The prepared high softening point glass powder has good batch stability and high pressure resistance. Manganese dioxide has the function of adjusting the temperature coefficient in the slurry. In the process of batch melting, the manganese dioxide is infiltrated into the surface of the glass powder by the infiltration method, which can maximize the role of manganese dioxide. In the process of slurry sintering, because manganese dioxide is infiltrated into the surface of the glass powder, it can effectively avoid the reaction of manganese dioxide with other components in the slurry, thereby affecting the performance of the slurry. The preparation method is simple to operate and can prepare high softening point glass powders such as Si-Pb-Bi-Al system glass powder, Si-Pb-Bi-Ca system glass powder, and Si-Pb-Ba-Al system glass powder. The glass powder prepared by the above-mentioned method is used to prepare resistor paste. The obtained resistor paste not only has good high-voltage pulse resistance performance, but also can greatly shorten the positive and negative temperature coefficients of the resistor paste, reducing the paste's sensitivity to temperature. BRIEF DESCRIPTION OF THE DRAWINGS

[0048] In order to more clearly illustrate the technical solutions in the implementation methods and examples of the present application and to more completely understand the present application and its beneficial effects, the following is a brief introduction to the drawings required for use in the description of the implementation methods or examples. Obviously, the drawings described below are only some embodiments of the present application, and those skilled in the art can obtain other drawings based on these drawings without creative work.

[0049] Figure 1 is a flow chart of a method for preparing glass powder in one embodiment;

[0050] Figure 2 This is a SEM photo of the glass powder sample of Example 1;

[0051] Figure 3 This is a SEM photo of the glass powder sample of Example 2;

[0052] Figure 4 This is the SEM photo of the glass powder sample of Example 3. DETAILED DESCRIPTION

[0053] In order to facilitate the understanding of the present invention, the present invention will be described more fully below with reference to the relevant drawings. The preferred embodiments of the present invention are given in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0054] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which the present invention belongs. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0055] Unless otherwise specified or incompatible herewith, the terms and phrases used herein shall have the following meanings:

[0056] The terms "and / or", "or / and", and "and / or" used in this application include any one of two or more related listed items, and also include any and all combinations of related listed items, and the arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or", "or / and", and "and / or", it should be understood that in this application, the technical solution undoubtedly includes technical solutions that are all connected by "logical and", and undoubtedly includes technical solutions that are all connected by "logical or". For example, "A and / or B" includes three parallel solutions of A, B and "a combination of A and B".

[0057] In the present application, "plurality", "multiple", "multiple times", "multiples", etc., unless otherwise specified, refer to a number greater than 2 or equal to 2. For example, "one or more" means one or greater than or equal to two.

[0058] The terms "combination thereof", "any combination thereof", "any combination thereof" and the like used in this application include all suitable combinations of any two or more of the listed items.

[0059] In this application, the "suitable" mentioned in "suitable combination", "suitable method", "any suitable method", etc. is based on the ability to implement the technical solution of this application, solve the technical problems of this application, and achieve the expected technical effects of this application.

[0060] In the present application, "preferred", "better", "more preferred" and "suitable" are only used to describe implementation methods or examples with better effects. It should be understood that they do not constitute limitations on the scope of protection of the present application.

[0061] In the present application, "further", "further", "particularly" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present application.

[0062] In this application, "optionally", "optional", and "optional" mean optional or dispensable, that is, any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0063] In the present invention, in the "first aspect", "second aspect", "third aspect", "fourth aspect", etc., the terms "first", "second", "third", "fourth", etc. are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", "third", "fourth", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0064] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0065] In the present application, when it comes to numerical intervals (i.e., numerical ranges), unless otherwise specified, the optional numerical distribution is considered continuous within the above numerical interval, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical range, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to the integers within the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints. In this article, it is equivalent to directly listing each integer, such as t is an integer selected from 1 to 10, indicating that t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. In addition, when multiple ranges are provided to describe features or characteristics, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all subranges included therein.

[0066] The temperature parameters in this application, unless otherwise specified, are allowed to be either constant temperature treatment or to vary within a certain temperature range. It should be understood that the constant temperature treatment allows the temperature to fluctuate within the accuracy range controlled by the instrument. Fluctuations within the range of ±5°C, ±4°C, ±3°C, ±2°C, and ±1°C are allowed.

[0067] In the present application, % (w / w) and wt% both represent weight percentage, % (v / v) refers to volume percentage, and % (w / v) refers to mass volume percentage.

[0068] The "room temperature" in this application generally refers to 5°C to 30°C, preferably 25±5°C.

[0069] The performance of resistor paste is crucial to the reliability and stability of electronic products in complex environments. With the development trend of customized and low-cost resistor paste market, the technical requirements and product demand of resistor paste are rapidly increasing. Therefore, glass powder that can stably control the performance of resistor paste in terms of temperature coefficient and high-voltage pulse resistance is needed.

[0070] In one embodiment, a method for preparing glass powder is provided, comprising the following steps:

[0071] The first mixed material is first smelted, quenched, and first ground to prepare a particle size D 50 A first intermediate no larger than 2 μm;

[0072] Grinding and mixing the modifier and the first intermediate to prepare a second mixture;

[0073] The second mixed material is subjected to a second smelting, a first stirring, a water quenching, and a second grinding to prepare a particle size D 50 Powders no larger than 2μm;

[0074] Freezing the powder and returning it to the temperature to prepare a second intermediate;

[0075] ball-milling the manganese dioxide and the second intermediate to prepare a third mixed material;

[0076] The third mixed material is subjected to a third smelting to allow the manganese dioxide melt to infiltrate the surface layer of the second intermediate, and then subjected to a third grinding to prepare glass powder.

[0077] In one embodiment, a method for preparing glass powder comprises the following steps:

[0078] S100: The first mixed material is first smelted, quenched, and first ground to prepare a particle size D 50 A first intermediate no larger than 2 μm;

[0079] S200: grinding and mixing the modifier and the first intermediate to prepare a second mixed material;

[0080] S300: The second mixed material is subjected to a second smelting, a first stirring, a water quenching, and a second grinding to prepare a particle size D 50 Powders no larger than 2μm;

[0081] S400: freezing the powder in a sealed environment and returning the temperature to obtain a second intermediate;

[0082] S500: ball-milling manganese dioxide and the second intermediate to prepare a third mixed material;

[0083] S600: The third mixed material is subjected to a third smelting process to allow the manganese dioxide melt to infiltrate the surface layer of the second intermediate, and then subjected to a third grinding process to prepare glass powder. Figure 1 .

[0084] In one embodiment, in step S100, based on the amount of materials added, the first mixed material contains 10 wt% to 40 wt% of SiO2, 20 wt% to 80 wt% of PbO, and 2 wt% to 25 wt% of metal oxides. The first mixed material may also contain 15 wt% to 35 wt% of SiO2, 50 wt% to 80 wt% of PbO, and 2 wt% to 25 wt% of metal oxides.

[0085] It can be understood that in step S100, based on the amount of material fed, the first mixture contains 10wt% to 40wt% SiO2, which means that the content of SiO2 in the first mixture can be but is not limited to 10wt%, 15wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, etc., or a range selected from any two of the aforementioned values.

[0086] It can be understood that in step S100, based on the amount of material fed, the first mixture contains 20wt% to 80wt% PbO, which means that the content of PbO in the first mixture can be but is not limited to 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, 80wt%, etc., or a range selected from any two of the aforementioned values.

[0087] It can be understood that in step S100, based on the amount of feed, the first mixture contains 2wt% to 25wt% of metal oxide, which means that the content of metal oxide in the first mixture can be but is not limited to 2wt%, 5wt%, 10wt%, 15wt%, 20wt%, 25wt%, etc., or a range selected from any two of the aforementioned values.

[0088] In one embodiment, in step S100, the metal oxide in the first mixed material includes at least one of Bi2O3 and BaO.

[0089] In one embodiment, in step S100, the temperature for the first smelting is 1300°C to 1600°C, for example, 1300°C, 1400°C, 1500°C, 1600°C or a range selected from any two of the foregoing values.

[0090] In one embodiment, in step S100, the holding time for the first smelting is 30 min to 60 min, for example, 30 min, 40 min, 50 min, 60 min or a range selected from any two of the foregoing values.

[0091] In one embodiment, in step S100, the quenching temperature is 15°C to 30°C.

[0092] In one embodiment, in step S100, quenching is performed using a roller cooling device;

[0093] In one embodiment, step S100 also includes the following steps:

[0094] S110: After the first grinding, the product is sieved, dried, and sieved a second time to prepare a first intermediate.

[0095] In one embodiment, in step S110, after first grinding to a particle size D50 not greater than 2 μm, the product is sieved through a 325-mesh sieve, dried at 100° C. to 150° C. for 24 h to 48 h, and sieved through an 80-mesh sieve after drying.

[0096] In one embodiment, in step S200, the modifier contains Al2O3, CaO and SnO, and the mass ratio of Al2O3, CaO and SnO is (1-15): (1-15): (0.01-15). The mass ratio of Al2O3, CaO and SnO in the modifier can also be (1-15): (1-15): (0.01-8.5).

[0097] In one embodiment, in step S200, based on the amount of materials fed, the second mixture contains 1 wt% to 15 wt% Al2O3, 1 wt% to 15 wt% CaO, 0.01 wt% to 15 wt% SnO and 75 wt% to 95 wt% of the first intermediate. The second mixture may also contain 1 wt% to 15 wt% Al2O3, 1 wt% to 15 wt% CaO, 0.01 wt% to 8.5 wt% SnO and 75 wt% to 95 wt% of the first intermediate.

[0098] It can be understood that in step S200, based on the amount of material fed, the second mixture contains 1wt% to 15wt% Al2O3, which means that the content of Al2O3 in the second mixture can be but is not limited to 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, etc., or a range selected from any two of the aforementioned values.

[0099] It can be understood that in step S200, based on the amount of material fed, the second mixture contains 1wt% to 15wt% CaO, which means that the content of CaO in the second mixture can be but is not limited to 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, etc., or a range selected from any two of the aforementioned values.

[0100] It can be understood that in step S200, based on the amount of material fed, the second mixture contains 0.01wt% to 15wt% SnO, which means that the content of SnO in the second mixture can be but is not limited to 0.01wt%, 0.05wt%, 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt%, 15wt%, etc., or a range selected from any two of the aforementioned values.

[0101] It can be understood that in step S200, based on the amount of feed, the second mixture contains 75wt% to 95wt% of the first intermediate, which means that the content of the first intermediate in the second mixture can be but is not limited to 75wt%, 80wt%, 85wt%, 90wt%, 95wt%, etc., or a range selected from any two of the aforementioned values.

[0102] In one embodiment, in step S300, the temperature for the second smelting is 1200°C to 1400°C, for example, 1200°C, 1300°C, 1400°C, 1500°C, 1600°C or a range selected from any two of the foregoing values.

[0103] In one embodiment, in step S300, the holding time for the second smelting is 30 min to 60 min, for example, 30 min, 40 min, 50 min, 60 min or a range selected from any two of the foregoing values.

[0104] In one embodiment, in step S300, the second mixed material is subjected to a second melting, and in the first stirring step, the second mixed material is stirred after it is completely melted.

[0105] In one embodiment, in step S300, the rotation speed of the first stirring is 40 r / min to 60 r / min.

[0106] In one embodiment, in step S300, the water quenching temperature is 15°C to 30°C.

[0107] In one embodiment, in step S300, the volume of water during the water quenching process is 50 to 100 times the volume of the smelting powder.

[0108] In one embodiment, step S300 also includes the following steps:

[0109] S310: After the second grinding, sieving, drying, and sieving again, a particle size D is obtained. 50 Powders not larger than 2μm.

[0110] In one embodiment, in step S310, after the second grinding to a particle size D50 of not more than 2 μm, the mixture is sieved through a 325-mesh sieve and dried at a temperature of 100° C. to 150° C. for 24 h to 48 h. After drying, the mixture is sieved through an 80-mesh sieve to obtain a particle size D 50 Powders not larger than 2μm.

[0111] In one embodiment, in step S400, the freezing temperature is -100°C to -20°C, for example, -100°C, -90°C, -80°C, -70°C, -60°C, -50°C, -40°C, -30°C, -20°C or a range selected from any two of the foregoing values.

[0112] In one embodiment, in step S400, the powder is placed in a sealed environment and frozen.

[0113] In one embodiment, in step S400, the freezing time is 3h to 5h, for example, 3h, 4h, 5h or a range selected from any two of the foregoing values. After freezing treatment, fine stress will be generated inside the glass powder, and these stresses will be partially released after warming up, thereby causing slight structural changes. These changes can increase the density of the material, improve its hardness and compressive strength, and freezing treatment can improve the uniformity of the chemical composition in the glass powder, especially when mixing multiple raw materials to prepare glass powder. In a low temperature environment, the diffusion rate of atoms or molecules slows down, which helps to mix more evenly. After warming up, this uniformity is maintained, thereby improving the chemical stability and durability of the glass powder.

[0114] In one embodiment, in step S400, the temperature recovery rate is 1.5°C / h to 5°C / h.

[0115] In one embodiment, in step S500, based on the amount of material added, the third mixture contains 0.1 wt% to 10 wt% of manganese dioxide and 90 wt% to 99.9 wt% of the second intermediate; the third mixture contains 0.1 wt% to 2 wt% of manganese dioxide and 98 wt% to 99.9 wt% of the second intermediate.

[0116] It can be understood that in step S500, based on the amount of material fed, the third mixture contains 0.1wt% to 10wt% manganese dioxide, which means that the content of manganese dioxide in the third mixture can be but is not limited to 0.1wt%, 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, etc., or a range selected from any two of the aforementioned values.

[0117] It can be understood that in step S500, based on the amount of feed, the third mixture contains 90wt% to 99.9wt% of the second intermediate, which means that the content of the second intermediate in the third mixture can be but is not limited to 90wt%, 91wt%, 92wt%, 93wt%, 94wt%, 95wt%, 96wt%, 97wt%, 98wt%, 99wt%, 99.9wt% and the like, or a range selected from any two of the aforementioned values.

[0118] In one embodiment, in step S500, manganese dioxide and the second intermediate are ball-milled under a second stirring condition so that manganese dioxide is adsorbed on the surface of the second intermediate.

[0119] In one embodiment, in step S600, the temperature for performing the third smelting is 550°C to 650°C, for example, 550°C, 600°C, 650°C or a range consisting of any two of the foregoing values.

[0120] In one embodiment, in step S600, the holding time for the third smelting is 60 min to 120 min, for example, 60 min, 70 min, 80 min, 90 min, 100 min, 110 min, 120 min or a range selected from any two of the foregoing values.

[0121] After the third smelting, the manganese dioxide melt can penetrate into the surface layer of the second intermediate.

[0122] In one implementation, step S600 also includes the following steps:

[0123] S610: After the third grinding, the mixture is sieved, dried, and sieved a second time to prepare glass powder.

[0124] In one embodiment, in step S610, after the third grinding to a particle size D50 not greater than 5 μm, the powder is sieved through a 325-mesh sieve and dried at 100° C. to 150° C. for 24 h to 48 h. After drying, the powder is sieved through an 80-mesh sieve to prepare glass powder.

[0125] In one embodiment, a glass powder is provided, which is prepared according to the above-mentioned method for preparing the glass powder.

[0126] In one embodiment, the particle size of the provided glass powder is 500nm to 5μm, for example, 500nm, 1μm, 1.5μm, 2μm, 2.5μm, 3μm, 3.5μm, 4μm, 4.5μm, 5μm or a range selected from any two of the foregoing values.

[0127] In one embodiment, the softening point of the provided glass powder is 600°C to 800°C, for example, 600°C, 650°C, 700°C, 750°C, 800°C or a range selected from any two of the foregoing values.

[0128] In one embodiment, the system of the provided glass powder can be Si-Pb-Bi-Al system glass powder, Si-Pb-Bi-Ca system glass powder, or Si-Pb-Ba-Al system glass powder.

[0129] The glass powder provided can stably control the temperature coefficient and high voltage pulse resistance of the resistor paste.

[0130] In one embodiment, a use of glass powder in preparing a resistor paste is provided.

[0131] The glass powder prepared by the provided preparation method is used to prepare resistor paste. The prepared resistor paste not only has good high-voltage pulse resistance performance, but also can greatly shorten the positive and negative temperature coefficients of the resistor paste, thereby reducing the paste's sensitivity to temperature.

[0132] In one embodiment, a resistor paste is provided, which includes the aforementioned glass powder.

[0133] In one embodiment, the provided resistor paste contains 40 wt % to 50 wt % of glass powder, 40 wt % to 60 wt % of organic vehicle, and 3 wt % to 10 wt % of conductive phase.

[0134] In one embodiment, the organic vehicle in the resistor paste contains 70 wt % to 90 wt % of terpineol and 10 wt % to 30 wt % of ethyl cellulose.

[0135] In one embodiment, the conductive phase in the resistor paste contains 80 wt % to 90 wt % of lead ruthenate and 10 wt % to 20 wt % of silver powder.

[0136] In one embodiment, an electronic product is provided, which contains the aforementioned glass powder or the aforementioned resistor paste.

[0137] In one embodiment, the provided electronic product is at least one of a thick film resistor, a resistor network, a hybrid integrated circuit, and a converter valve.

[0138] The embodiments of the present application will be described in detail below in conjunction with some examples. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which the conditions are not specified in the following examples are preferably referred to the guidance given in the present application, and can also be based on the experimental manual or normal conditions in the art, or can also be based on the conditions recommended by the manufacturer, or with reference to experimental methods known in the art.

[0139] Example 1

[0140] (1) Preparation of the first intermediate

[0141] The first intermediate raw materials are weighed according to the formula, and the weight percentage composition is: SiO2 30.78%, PbO 58.01%, BaO 11.21%, and mixed to obtain a first mixed material; the first mixed material is smelted at a smelting temperature of 1500°C and a heat preservation time of 60 minutes; and the main system glass slag is obtained after quenching using a roller cooling device, and the water temperature of the roller cooling device during quenching is 25°C. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve to obtain a first intermediate;

[0142] (2) Preparation of the second intermediate

[0143] The raw materials of the second intermediate and the first intermediate prepared in step (1) are weighed according to the formula, and the weight percentage composition is: Al2O3 2.58%, CaO 4.12%, SnO 8.49% and the first intermediate 84.81%, and the materials are ground and mixed to obtain a second mixed material; the second mixed material is melted by a stirring and melting method to improve the uniformity and stability of the glass powder, and the second mixed material is stirred after it is completely melted, the melting temperature is: 1200°C, the stirring speed is 50r / min, and the stirring and heat preservation time is 60min. The obtained glass liquid is water quenched to obtain modified glass slag, the water quenching temperature is 25°C, the volume of water during water quenching is 80 times the volume of the smelted powder, the glass slag is dry-milled to a particle size D50 less than 2μm, passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve, and finally the glass powder is sealed and placed under low temperature conditions of -50°C for refrigeration for 5 hours, and then naturally warmed to obtain a second intermediate;

[0144] (3) Preparation of finished glass powder by melt infiltration method

[0145] According to the formula, manganese dioxide and the second intermediate prepared in step (2) are weighed, and the weight percentage composition is: MnO2 6.70%, and the second intermediate 93.3%. The materials are mixed by ball milling and stirring, so that the manganese dioxide can be adsorbed on the surface of the second intermediate to obtain a third mixed material. The third mixed material is slightly melted at a relatively low melting temperature, so that the surface of the second intermediate is in a slightly melted state, and the manganese dioxide melt can penetrate into the surface layer of the second intermediate. The melting temperature is: 600°C, and the holding time is 120 minutes to obtain a finished glass slag. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel screen and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel screen to obtain a finished glass powder.

[0146] The glass powder was observed using a scanning electron microscope. The results can be found in Figure 2 ,Depend on Figure 2 It can be seen that the maximum particle size of the glass powder is less than 5um, the particle size distribution is relatively concentrated, the dispersibility and anti-settling effect are good, and it has a conical microcrystalline structure.

[0147] Example 2

[0148] (1) Preparation of the first intermediate

[0149] Weigh the raw materials of the first intermediate according to the formula, and the weight percentage composition is: SiO2 19.19%, PbO 60.42%, Bi2O3 20.39%, and mix them to obtain a first mixed material; melt the first mixed material at a melting temperature of 1500°C and a holding time of 60 minutes; and quench it using a roller cooling device to obtain a main system glass slag, and the water temperature of the roller cooling device during quenching is 25°C. After the glass slag is dry-milled to a particle size D50 less than 2μm, it is passed through a 325-mesh stainless steel screen and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel screen to obtain a first intermediate;

[0150] (2) Preparation of the second intermediate

[0151] The raw materials of the second intermediate and the first intermediate prepared in step (1) are weighed according to the formula, and the weight percentage composition is: Al2O3 5.63%, CaO 5.32%, SnO 0.31% and the first intermediate 88.74%, and the raw materials are ground and mixed to obtain a second mixed material; the second mixed material is melted by a stirring and melting method to improve the uniformity and stability of the glass powder, and the second mixed material is stirred after it is completely melted, the melting temperature is: 1200°C, the stirring speed is 50r / min, and the stirring and heat preservation time is 60min. The obtained glass liquid is water quenched to obtain modified glass slag, the water quenching temperature is 25°C, the volume of water during water quenching is 80 times the volume of the smelted powder, the glass slag is dry-milled to a particle size D50 less than 2μm, passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve, and finally the glass powder is sealed and placed under low temperature conditions of -50°C for refrigeration for 5 hours, and then naturally warmed to obtain a second intermediate;

[0152] (3) Preparation of finished glass powder by melt infiltration method

[0153] According to the formula, manganese dioxide and the second intermediate prepared in step (2) are weighed, and the weight percentage composition is: MnO2 0.56%, and the second intermediate 99.44%. The materials are mixed by ball milling and stirring, so that the manganese dioxide can be adsorbed on the surface of the second intermediate to obtain a third mixed material. The third mixed material is slightly melted at a relatively low melting temperature, so that the surface of the second intermediate is in a slightly melted state, and the manganese dioxide melt can penetrate into the surface layer of the second intermediate. The melting temperature is: 600°C, and the holding time is 120 minutes to obtain a finished glass slag. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel screen and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel screen to obtain a finished glass powder.

[0154] The glass powder was observed using a scanning electron microscope. The results can be found in Figure 3 ,Depend on Figure 3 It can be seen that the maximum particle size of the glass powder is less than 5um, the particle size distribution is relatively concentrated, the dispersibility and anti-settling effect are good, and it has a conical microcrystalline structure.

[0155] Example 3

[0156] (1) Preparation of the first intermediate

[0157] The first intermediate raw materials are weighed according to the formula, and the weight percentage composition is: SiO2 20.57%, PbO 74.30%, Bi2O35.12%, and mixed to obtain a first mixed material; the first mixed material is smelted at a smelting temperature of 1500°C and a heat preservation time of 60 minutes; and the main system glass slag is obtained after quenching using a roller cooling device, and the water temperature of the roller cooling device during quenching is 25°C. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve to obtain the first intermediate;

[0158] (2) Preparation of the second intermediate

[0159] The raw materials of the second intermediate and the first intermediate prepared in step (1) are weighed according to the formula, and the weight percentage composition is: Al2O3 4.6%, CaO 3.12%, SnO 0.09% and the first intermediate 92.19%, and the materials are ground and mixed to obtain a second mixed material; the second mixed material is melted by a stirring and melting method to improve the uniformity and stability of the glass powder, and the second mixed material is stirred after it is completely melted, the melting temperature is: 1200°C, the stirring speed is 50r / min, and the stirring and heat preservation time is 60min. The obtained glass liquid is water quenched to obtain modified glass slag, the water quenching temperature is 25°C, the volume of water during water quenching is 80 times the volume of the smelted powder, the glass slag is dry-milled to a particle size D50 less than 2μm, passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve, and finally the glass powder is sealed and placed under low temperature conditions of -50°C for refrigeration for 5 hours, and then naturally warmed to obtain a second intermediate;

[0160] (3) Preparation of finished glass powder by melt infiltration method

[0161] According to the formula, manganese dioxide and the second intermediate prepared in step (2) are weighed, and the weight percentage composition is: MnO2 0.54%, and the second intermediate 99.46%. The materials are mixed by ball milling and stirring, so that the manganese dioxide can be adsorbed on the surface of the second intermediate to obtain a third mixed material. The third mixed material is slightly melted at a relatively low melting temperature, so that the surface of the second intermediate is in a slightly melted state, and the manganese dioxide melt can penetrate into the surface layer of the second intermediate. The melting temperature is: 600°C, and the holding time is 120 minutes to obtain a finished glass slag. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve to obtain a finished glass powder.

[0162] The glass powder was observed using a scanning electron microscope. The results can be found in Figure 4 ,Depend on Figure 4 It can be seen that the maximum particle size of the glass powder is less than 5um, the glass appearance is close to spherical, and the hardness is high. This type of glass powder has good dispersibility and stability in the slurry.

[0163] Comparative Example 1

[0164] The first intermediate raw material is weighed according to the formula, and the weight percentage composition is: MnO2 0.54%, Al2O3 4.58%, CaO3.10%, SnO 0.09%, SiO2 18.86%, PbO 68.13%, Bi2O34.70%, and mixed to obtain a first mixed material; the first mixed material is smelted at a smelting temperature of 1500°C and a holding time of 60 min; and the main system glass slag is obtained after quenching using a roller cooling device, and the water temperature of the roller cooling device during quenching is 25°C. The glass slag is dry-milled to a particle size D50 less than 2μm, and then passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve to obtain a finished glass powder.

[0165] Comparative Example 2

[0166] (1) Preparation of the first intermediate

[0167] The first intermediate raw materials are weighed according to the formula, and the weight percentage composition is: SiO2 20.57%, PbO 74.30%, Bi2O35.12%, and mixed to obtain a first mixed material; the first mixed material is smelted at a smelting temperature of 1500°C and a heat preservation time of 60 minutes; and the main system glass slag is obtained after quenching using a roller cooling device, and the water temperature of the roller cooling device during quenching is 25°C. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve to obtain the first intermediate;

[0168] (2) Preparation of the second intermediate

[0169] According to the formula, the raw materials of the second intermediate and the first intermediate prepared in step (1) are weighed, and the weight percentage composition is: Al2O3 4.6%, CaO 3.12%, SnO 0.09% and the first intermediate 92.19%, and the mixture is ground and mixed to obtain a second mixture; the second mixture is melted by a stirring and melting method to improve the uniformity and stability of the glass powder, and the second mixture is stirred after it is completely melted. The melting temperature is: 1200°C, the stirring speed is 50r / min, and the stirring and heat preservation time is 60min. The obtained glass liquid is water quenched to obtain modified glass slag. The water quenching temperature is 25°C, and the volume of water during water quenching is 80 times the volume of the smelted powder. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel screen and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel screen to obtain a second intermediate;

[0170] (3) Preparation of finished glass powder by melt infiltration method

[0171] According to the formula, manganese dioxide and the second intermediate prepared in step (2) are weighed, and the weight percentage composition is: MnO2 0.54%, and the second intermediate 99.46%. The materials are mixed by ball milling and stirring, so that the manganese dioxide can be adsorbed on the surface of the second intermediate to obtain a third mixed material. The third mixed material is slightly melted at a relatively low melting temperature, so that the surface of the second intermediate is in a slightly melted state, and the manganese dioxide melt can penetrate into the surface layer of the second intermediate. The melting temperature is: 600°C, and the holding time is 120 minutes to obtain a finished glass slag. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve to obtain a finished glass powder.

[0172] Comparative Example 3

[0173] (1) Preparation of the first intermediate

[0174] The first intermediate raw materials are weighed according to the formula, and the weight percentage composition is: SiO2 20.57%, PbO 74.30%, Bi2O35.12%, and mixed to obtain a first mixed material; the first mixed material is smelted at a smelting temperature of 1500°C and a heat preservation time of 60 minutes; and the main system glass slag is obtained after quenching using a roller cooling device, and the water temperature of the roller cooling device during quenching is 25°C. The glass slag is dry-milled to a particle size D50 of less than 2μm, and then passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve to obtain the first intermediate;

[0175] (2) Preparation of the second intermediate

[0176] The raw materials of the second intermediate and the first intermediate prepared in step (1) are weighed according to the formula, and the weight percentage composition is: Al2O3 4.6%, CaO 3.12%, SnO 0.09% and the first intermediate 92.19%, and the materials are ground and mixed to obtain a second mixed material; the second mixed material is melted by a stirring and melting method to improve the uniformity and stability of the glass powder, and the second mixed material is stirred after it is completely melted, the melting temperature is: 1200°C, the stirring speed is 50r / min, and the stirring and heat preservation time is 60min. The obtained glass liquid is water quenched to obtain modified glass slag, the water quenching temperature is 25°C, the volume of water during water quenching is 80 times the volume of the smelted powder, the glass slag is dry-milled to a particle size D50 less than 2μm, passed through a 325-mesh stainless steel sieve, and dried in a 120°C blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel sieve, and finally the glass powder is sealed and placed under low temperature conditions of -50°C for refrigeration for 5 hours, and then naturally warmed to obtain a second intermediate;

[0177] (3) Preparation of finished glass powder by melt infiltration method

[0178] According to the formula, manganese dioxide and the second intermediate prepared in step (2) are weighed, and the weight percentage composition is: MnO2 0.54%, and the second intermediate 99.46%. The materials are mixed by ball milling and stirring, so that the manganese dioxide can be adsorbed on the surface of the second intermediate to obtain a third mixed material. The third mixed material is slightly melted at a relatively low melting temperature, so that the surface of the second intermediate is in a slightly melted state, and the manganese dioxide melt can penetrate into the surface layer of the second intermediate. The melting temperature is: 1000° C., and the holding time is 40 min to obtain a finished glass slag. The glass slag is dry-milled to a particle size D50 of less than 2 μm, and then passed through a 325-mesh stainless steel screen and dried in a 120° C. blast oven for 36 hours. The dried glass powder is then passed through an 80-mesh stainless steel screen to obtain a finished glass powder.

[0179] The glass powder prepared in the above-mentioned Examples 1 to 3 and Comparative Examples 1 to 3, the organic carrier and the conductive phase were respectively used to prepare resistor pastes, and the obtained pastes contained 44wt% of glass powder, 49wt% of organic carrier and 7wt% of conductive phase. Among them, the organic carrier contained 80wt% of pine alcohol and 20wt% of ethyl cellulose, and the conductive phase contained 85.71wt% of lead ruthenate and 14.29wt% of silver powder. The resistor pastes were prepared through the preparation process, screen printing, sintering, and samples that can test the withstand voltage characteristics and temperature coefficient, and then tested. The test results are shown in Table 1.

[0180] Table 1 Performance test results of Examples 1 to 3 and Comparative Examples 1 to 3

[0181]

[0182] As can be seen from Table 1, the resistor pastes prepared in Examples 1 to 3 of the present invention have good temperature coefficients and strong withstand voltage characteristics in the corresponding resistance range. Compared with Example 3, the resistance value of Example 1 is significantly increased, and the temperature coefficient is significantly deteriorated, expanding from ±50 Ppm / ℃ to ±150 Ppm / ℃; the resistance value of Example 2 is significantly increased, and the temperature coefficient is expanded from ±50 Ppm / ℃ to ±80 Ppm / ℃, and the 5S overload capacity is significantly deteriorated; the resistance value of Example 3 is reduced, and the temperature coefficient is expanded from ±50 Ppm / ℃ to ±100 Ppm / ℃.

[0183] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0184] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the invention patent. It should be pointed out that for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be based on the attached claims, and the description and drawings may be used to interpret the content of the claims.

Claims

1. A method for preparing glass powder, characterized in that: The method for preparing the glass powder comprises the following steps: The first mixed material is first smelted, quenched, and first ground to prepare a particle size D 50 A first intermediate no larger than 2 μm; Grinding and mixing the modifier and the first intermediate to prepare a second mixture; The second mixed material is subjected to a second smelting, a first stirring, a water quenching, and a second grinding to prepare a particle size D 50 Powders no larger than 2μm; Freezing the powder and returning it to the temperature to prepare a second intermediate; ball-milling manganese dioxide and the second intermediate to prepare a third mixed material; The third mixed material is subjected to a third smelting to allow the manganese dioxide melt to infiltrate the surface layer of the second intermediate, and the third grinding is performed to prepare the glass powder; Calculated by feed amount, the first mixed material contains 10wt% to 40wt% of SiO2, 20wt% to 80wt% of PbO, and 2wt% to 25wt% of metal oxide.

2. The preparation method according to claim 1, characterized in that: Meet one or more of the following characteristics: (1) The modifier contains Al2O3, CaO and SnO, and the mass ratio of Al2O3, CaO and SnO is (1-15): (1-15): (0.01-15); (2) Based on the amount of materials added, the second mixed material contains 1wt% to 15wt% of Al2O3, 1wt% to 15wt% of CaO, 0.01wt% to 15wt% of SnO and 75wt% to 95wt% of the first intermediate; (3) Based on the amount of materials added, the third mixed material contains 0.1wt% to 10wt% of manganese dioxide and 90wt% to 99.9wt% of the second intermediate.

3. The preparation method according to claim 1 or 2, characterized in that: Meet one or more of the following characteristics: (1) Based on the amount of materials added, the first mixed material contains 15wt% to 35wt% of SiO2, 50wt% to 80wt% of PbO, and 2wt% to 25wt% of metal oxides; (2) The mass ratio of Al2O3, CaO and SnO in the modifier is (1-15): (1-15): (0.01-8.5); (3) Based on the amount of materials added, the second mixed material contains 1wt% to 15wt% of Al2O3, 1wt% to 15wt% of CaO, 0.01wt% to 8.5wt% of SnO and 75wt% to 95wt% of the first intermediate; (4) Based on the amount of materials added, the third mixed material contains 0.1 wt % to 2 wt % of manganese dioxide and 98 wt % to 99.9 wt % of the second intermediate.

4. The preparation method according to claim 1 or 2, characterized in that: Meet one or more of the following characteristics: (1) The metal oxide in the first mixed material includes at least one of Bi2O3 and BaO; (2) The temperature for performing the first smelting is 1300° C. to 1600° C.; (3) The holding time for the first smelting is 30 min to 60 min; (4) using a roller cooling device to perform the quenching; (5) The temperature for performing the second smelting is 1200° C. to 1400° C.; (6) The holding time for the second smelting is 30 min to 60 min.

5. The preparation method according to any one of claims 1 to 3, characterized in that The temperature for the third smelting is 550° C. to 650° C., and the insulation time for the third smelting is 60 min to 120 min.

6. The preparation method according to any one of claims 1 to 4, characterized in that Meet one or more of the following characteristics: (1) The quenching temperature is 15°C to 30°C; (2) The first stirring speed is 40 r / min to 60 r / min; (3) The water quenching temperature is 15°C to 30°C; (4) The volume of water during the water quenching process is 50 to 100 times the volume of the smelted powder; (5) freezing the powder in a sealed environment; (6) The freezing temperature is -100°C to -20°C; (7) The freezing time is 3h to 5h; (8) The temperature recovery rate is 1.5°C / h to 5°C / h.

7. A glass powder, characterized in that: The glass powder is prepared according to the method for preparing the glass powder according to any one of claims 1 to 6.

8. The glass powder according to claim 7, characterized in that The glass powder meets at least one of the following characteristics: (1) The particle size of the glass powder is 500nm to 5μm; (2) The softening point of the glass powder is 600°C to 800°C; (3) The system of the glass powder is Si-Pb-Bi-Al system glass powder, Si-Pb-Bi-Ca system glass powder, or Si-Pb-Ba-Al system glass powder.

9. Use of the glass powder according to claim 7 or 8 in preparing resistor paste or electronic products.

10. A resistor paste, characterized in that: The invention comprises the glass powder as claimed in claim 7 or 8.

11. An electronic product, characterized in that: Containing the glass powder according to claim 7 or 8 or the resistor paste according to claim 10, optionally, the electronic product is at least one of a thick film resistor, a resistor network, a hybrid integrated circuit and a converter valve.

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