Environment-friendly ceramic metallization paste as well as preparation method and application thereof

Abstract

The invention discloses an environment-friendly ceramic metallization paste as well as a preparation method and application thereof, and the preparation method comprises the following steps: adding ethyl cellulose into a butyl acetate solution, uniformly mixing and grinding, and filtering to prepare a binder; molybdenum powder and manganese powder are mixed into metallized powder, the metallized powder is mixed and ground evenly, and metallized powder is obtained; and adding the binder into the metallized powder, and uniformly mixing and grinding to obtain the environment-friendly ceramic metallized paste. According to the invention, firm combination between the metallization layer and the ceramic substrate is facilitated, the quality and reliability of the metallization layer are improved, and meanwhile, the use of nitrocotton in the ceramic metallization paste is successfully canceled, so that the problems of storage of the nitrocotton, high solution preparation difficulty and the like are solved, the preparation efficiency of the binder is effectively improved, and the production cost is reduced. The purpose that the ceramic metallization paste binder is safe and can be rapidly prepared is achieved.

Description

Technical Field

[0001] The invention belongs to the field of environmentally friendly ceramic metallization products and relates to an environmentally friendly ceramic metallization paste and a preparation method and application thereof. Background Art

[0002] In the manufacturing field of vacuum devices, vacuum ceramic shells are key components, and their performance and quality directly affect the overall performance and reliability of the devices. During the metallization production process, tube shells with shielding tube welding requirements generally require internal metallization. The quality of internal metallization is not only related to the connection strength and electrical performance between the vacuum ceramic shell and the metal parts, but also plays a decisive role in the long-term stable operation of the device. At present, the method of manually applying the paste with a brush is widely used. The manual application of the paste requires a low viscosity. If the viscosity of the paste is too high, it will not only increase the difficulty of application, but also easily lead to uneven application and uneven thickness, which will affect the quality and performance of the metallization layer. Secondly, the paste needs to have the characteristic of rapid volatilization. After the application is completed, the solvent in the paste can evaporate quickly, allowing the metallization layer to dry and solidify quickly, thereby improving production efficiency and reducing the production cycle.

[0003] To achieve rapid evaporation and strong adhesion of the paste, butyl acetate and nitrocellulose solution are generally added to the binder of the hand-applied paste. Butyl acetate has good volatility and can accelerate the evaporation rate of the solvent in the paste, allowing the metallized layer to reach a dry state in a relatively short time. The nitrocellulose solution can enhance the adhesion between the paste and the inner surface of the electric vacuum porcelain shell, ensuring that the metallized layer is not easily detached during subsequent processing and use. However, nitrocellulose is classified as an explosive and has high requirements for both the storage environment and the preparation process. Excessive temperature or humidity in the storage environment can cause the nitrocellulose to spontaneously combust or explode, resulting in serious safety accidents and property losses for the company. Therefore, it is crucial to develop environmentally friendly metallization formulas. Summary of the Invention

[0004] The purpose of the present invention is to provide an environmentally friendly ceramic metallization paste and a preparation method and application thereof, so as to solve the problems of the existing ceramic metallization paste preparation process and the difficulty in storing raw materials.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions: A method for preparing an environmentally friendly ceramic metallization paste, comprising: Add ethyl cellulose to the butyl acetate solution, mix and grind evenly, filter, and prepare a binder; Mixing molybdenum powder and manganese powder into metallized powder, and grinding them evenly to obtain metallized powder; The binder is added to the metallized powder, mixed and ground evenly to obtain an environmentally friendly ceramic metallized paste.

[0006] Furthermore, the mass of the ethyl cellulose is 2-3% of the mass of the butyl acetate solution.

[0007] Furthermore, the mixing and grinding speed of the binder is 30-35 r / min, and the mixing and grinding time is 12-18 h.

[0008] Furthermore, the filtration process uses a 300-mesh nylon mesh to filter through a glass funnel.

[0009] Furthermore, the mixing mass ratio of the molybdenum powder to the manganese powder is (6.5-7.5):1.

[0010] Furthermore, the mixing and grinding speed of the metallized powder is 500-550 r / min, and the mixing and grinding time is 4-6 h.

[0011] Furthermore, the mass ratio of the metallized powder to the binder is (3.5-4.5):1.

[0012] Furthermore, the mixing and grinding speed of the environmentally friendly ceramic metallization paste is 20-30 r / min, and the mixing and grinding time is 12-18 h.

[0013] An environmentally friendly ceramic metallization paste is prepared by the preparation method.

[0014] The application of the environmentally friendly ceramic metallization paste is to apply the environmentally friendly ceramic metallization paste to the inner platform of the ceramic metallization product, and then undergo primary metallization sintering, electroplating and secondary metallization sintering.

[0015] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides a method for preparing an environmentally friendly ceramic metallization paste. The method comprises the following steps: adding ethyl cellulose to a butyl acetate solution and grinding the mixture to form a binder; mixing molybdenum powder and manganese powder to form a metallization powder, and grinding the mixture to form a metallization powder. Molybdenum has a high melting point, good electrical conductivity and corrosion resistance, and manganese can improve the weldability and oxidation resistance of the metallization layer. The synergistic effect of the two enables the prepared ceramic metallization paste to achieve an efficient metallization effect and meet the requirements for good electrical and mechanical connection between ceramic and metal. The binder is added to the metallization powder and ground to form an environmentally friendly ceramic metallization paste. The present invention provides a good bonding effect for the metallization powder by fully mixing the binder with the metallization powder and uniformly wrapping the metallization powder, thereby helping to form a strong bond between the metallization layer and the ceramic substrate, improving the quality and reliability of the metallization layer, and reducing the occurrence of defects such as shedding and cracking of the metallization layer. At the same time, the successful elimination of the use of nitrate wool in ceramic metallization pastes solves problems such as nitrate wool storage and the difficulty in preparing solutions, effectively improving the efficiency of adhesive preparation and achieving the goal of safe and rapid preparation of ceramic metallization paste adhesives. This provides a safer, more environmentally friendly, and more efficient solution for the ceramic metallization industry, helping to promote the transformation of the entire industry towards green and sustainable development and promote the innovation and upgrading of related technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0017] Figure 1 This is a comparison chart of the tensile strength of the environmentally friendly ceramic metallization paste-coated product prepared in Example 1 of the present invention after sintering and the tensile strength of the metallization paste-coated product prepared using butyl acetate and nitre-cotton solution after sintering. DETAILED DESCRIPTION

[0018] To facilitate understanding of the features and effects of the present invention by those skilled in the art, the following provides a general description and definition of the terms and expressions used in the specification and claims. Unless otherwise indicated, all technical and scientific terms used herein have the ordinary meanings as understood by those skilled in the art regarding the present invention. In the event of conflict, the definitions in this specification shall prevail.

[0019] The theories or mechanisms described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, that is, the present invention can be implemented without being limited by any specific theory or mechanism.

[0020] All features, such as values, amounts, contents, and concentrations, described herein as numerical ranges or percentage ranges are provided for simplicity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to include and specifically disclose all possible subranges and individual values ​​within the range (including integers and fractions).

[0021] In this document, unless otherwise specified, “include,” “including,” “contains,” “has” or similar terms cover the meanings of “consisting of” and “mainly consisting of,” for example, “A includes a” covers the meanings of “A includes a and other” and “A only includes a.”

[0022] In this document, for the sake of brevity, not all possible combinations of the various technical features in each embodiment or example are described. Therefore, as long as there are no contradictions in the combination of these technical features, the various technical features in each embodiment or example can be combined in any way, and all possible combinations should be considered to be within the scope of this specification.

[0023] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. The present invention will be further elaborated in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention. The embodiments described are part of the embodiments of the present invention, not all of the embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention claimed for protection, but merely represents selected embodiments of the present invention. In addition, it should be understood that after reading the contents taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the scope defined by the claims attached to this application. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention.

[0024] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the embodiments of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and the features of different embodiments or examples, unless they are contradictory.

[0025] In order to make those skilled in the art more clearly understand the technical solutions of the present invention, the following examples are given for illustration. It should be pointed out that the following examples do not limit the scope of protection claimed by the present invention. Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial channels, or can be obtained by existing known methods. Conventional instruments and equipment in the field are used in the following examples. The experimental methods for which specific conditions are not specified in the following examples are generally carried out under conventional conditions or under conditions recommended by the manufacturer. Various raw materials used in the following examples are conventional commercial products, unless otherwise specified, and their specifications are conventional specifications in the field. In the specification of the present invention and the following examples, unless otherwise specified, "%" represents weight percentage, "part" represents weight part, and ratio represents weight ratio.

[0026] The present invention is described in further detail below with reference to the accompanying drawings: The present invention provides a method for preparing an environmentally friendly ceramic metallization paste, which specifically comprises the following steps: Step 1: Preparation of environmentally friendly ceramic metallization binder Use a glass bottle to add the butyl acetate solution, followed by 2-3% by weight of ethyl cellulose. Stir continuously with a glass rod during the addition process. Once the ethyl cellulose is completely soaked, tightly cap the bottle and place the bottle in a jar mill for uniform mixing. The mixing parameters are: a speed of 30-35 rpm and a cumulative mixing time of 12-18 hours. After mixing, filter the mixture through a 300-mesh nylon mesh and a glass funnel to prepare the binder. Place the mixture in a clean glass bottle and set aside.

[0027] Step 2: Preparation of environmentally friendly ceramic metallization paste Mix molybdenum powder and manganese powder in a metallization formula with a mass ratio of 6.5-7.5:1 to form a metallized powder. Place it in a 1200ml nylon ball mill and grind it on a planetary grinder for 4-6 hours at a speed of 500-550 r / min. After the metallized powder is evenly ground, sieve out the agate balls with a 50-mesh stainless steel screen. Then, place the metallized powder in a 1000ml ground-mouth bottle and set aside.

[0028] According to the formula, the metallizing powder and agate balls are mixed in a ratio of 300g: 100-200g. The agate balls are φ4-φ8 in size. The mixed metallizing powder and agate balls are added to a plastic bottle. The binder is then measured in a beaker and added to the plastic bottle. The mass ratio of the metallizing powder to the binder is 3.5-4.5:1. The bottle is capped and placed on a pot mill for uniform mixing. The mixing speed is 20-30 r / min and the mixing time is 12-18 hours to prepare an environmentally friendly ceramic metallizing paste.

[0029] The present invention is described in further detail below through specific embodiments: Example 1: A method for preparing an environmentally friendly ceramic metallization paste comprises the following steps: Step 1: Preparation of environmentally friendly ceramic metallization binder Use a glass bottle to add 1500g of butyl acetate solution, followed by 30g of ethyl cellulose. Stir continuously with a glass rod during the addition process. Once the ethyl cellulose is completely soaked, tightly cap the bottle and place the bottle in a jar mill for uniform mixing. The mixing parameters are: a speed of 30 rpm and a cumulative mixing time of 18 hours. After mixing, filter the mixture through a 300-mesh nylon mesh and a glass funnel to prepare the binder. Place the mixture in a clean glass bottle and set aside.

[0030] Step 2: Preparation of environmentally friendly ceramic metallization paste According to the metallization formula, 1000g of molybdenum powder and 153.85g of manganese powder were mixed into a metallized powder. The mixture was placed in a 1200ml nylon ball mill and ground on a planetary grinder for 4 hours at 550 rpm. After the metallized powder was evenly ground, the agate balls were screened out using a 50-mesh stainless steel sieve. The metallized powder was then placed in a 1000ml ground-mouth bottle and set aside.

[0031] The metallizing powder and agate balls were mixed in a ratio of 300g:100g, with the agate balls being φ4. 85.71g of binder was then measured in a beaker and added to the bottle. The bottle was capped and ground evenly in a pot mill. The grinding speed was set at 20 rpm and the grinding time was 16 hours to produce an environmentally friendly ceramic metallizing paste.

[0032] Example 2: A method for preparing an environmentally friendly ceramic metallization paste comprises the following steps: Step 1: Preparation of environmentally friendly ceramic metallization binder Use a glass bottle to add 1500g of butyl acetate solution, followed by 34.5g of ethyl cellulose. Stir continuously with a glass rod during the addition process. Once the ethyl cellulose is completely soaked, tightly cap the bottle and place the bottle in a jar mill for uniform mixing. The mixing parameters are: a speed of 32 rpm and a cumulative mixing time of 15 hours. After mixing, filter the mixture through a 300-mesh nylon mesh and a glass funnel to prepare the binder. Place the mixture in a clean glass bottle and set aside.

[0033] Step 2: Preparation of environmentally friendly ceramic metallization paste According to the metallization formula, mix 1000 g of molybdenum powder and 147.06 g of manganese powder to form a metallized powder. Place the mixture in a 1200 ml nylon ball mill and grind it on a planetary grinder for 5 hours at 520 rpm. After the metallized powder is evenly ground, sieve out the agate balls using a 50-mesh stainless steel sieve. The metallized powder is then placed in a 1000 ml ground-mouth bottle and set aside.

[0034] The metallizing powder and agate balls were mixed in a ratio of 300g:125g, with the agate balls being φ6. The mixed metallizing powder and agate balls were then added to a plastic bottle. 78.95g of binder was then measured out using a beaker and added to the bottle. The bottle was capped and ground evenly in a jar mill at a speed of 25 rpm for 13 hours to produce an environmentally friendly ceramic metallizing paste.

[0035] Example 3: A method for preparing an environmentally friendly ceramic metallization paste comprises the following steps: Step 1: Preparation of environmentally friendly ceramic metallization binder Use a glass bottle to add 1500g of butyl acetate solution, followed by 37.5g of ethyl cellulose. Stir continuously with a glass rod during the addition process. Once the ethyl cellulose is completely soaked, tightly cap the bottle and place the bottle in a jar mill for uniform mixing. The mixing parameters are: a speed of 35 rpm and a cumulative mixing time of 12 hours. After mixing, filter the mixture through a 300-mesh nylon mesh and a glass funnel to prepare the binder. Place the mixture in a clean glass bottle and set aside.

[0036] Step 2: Preparation of environmentally friendly ceramic metallization paste According to the metallization formula, 1000g of molybdenum powder and 142.86g of manganese powder were mixed into a metallized powder. The mixture was placed in a 1200ml nylon ball mill and ground on a planetary grinder for 6 hours at 500 rpm. After the metallized powder was evenly ground, the agate balls were screened out using a 50-mesh stainless steel sieve. The metallized powder was then placed in a 1000ml ground-mouth bottle and set aside.

[0037] The metallizing powder and agate balls were mixed in a ratio of 300g:150g, with the agate balls being φ8 in size. 75g of binder was then measured in a beaker and added to the bottle. The bottle was capped and ground evenly in a pot mill. The grinding speed was set at 30 rpm for 12 hours to produce an environmentally friendly ceramic metallizing paste.

[0038] Example 4: A method for preparing an environmentally friendly ceramic metallization paste comprises the following steps: Step 1: Preparation of environmentally friendly ceramic metallization binder Use a glass bottle to add 1500g of butyl acetate solution, followed by 42g of ethyl cellulose. Stir continuously with a glass rod during the addition process. Once the ethyl cellulose is completely soaked, tightly cap the bottle and place the bottle in a jar mill for uniform mixing. The mixing parameters are: a speed of 33 rpm and a cumulative mixing time of 14 hours. After mixing, filter the mixture through a 300-mesh nylon mesh and a glass funnel to prepare the binder. Place the mixture in a clean glass bottle and set aside.

[0039] Step 2: Preparation of environmentally friendly ceramic metallization paste According to the metallization formula, 1000g of molybdenum powder and 136.99g of manganese powder were mixed into a metallized powder. The mixture was placed in a 1200ml nylon ball mill and ground on a planetary grinder for 5 hours at 540 rpm. After the metallized powder was evenly ground, the agate balls were screened out using a 50-mesh stainless steel sieve. The metallized powder was then placed in a 1000ml ground-mouth bottle and set aside.

[0040] The metallizing powder and agate balls were mixed in a ratio of 300g:175g, with the agate balls being φ4. The mixed metallizing powder and agate balls were then added to a plastic bottle. 69.77g of binder was then measured in a beaker and added to the bottle. The bottle was capped and ground evenly in a pot mill at a speed of 28 rpm for 15 hours to produce an environmentally friendly ceramic metallizing paste.

[0041] Example 5: A method for preparing an environmentally friendly ceramic metallization paste comprises the following steps: Step 1: Preparation of environmentally friendly ceramic metallization binder Use a glass bottle to add 1500g of butyl acetate solution, followed by 45g of ethyl cellulose. Stir continuously with a glass rod during the addition process. Once the ethyl cellulose is completely soaked, tightly cap the bottle and place the bottle in a jar mill for uniform mixing. The mixing parameters are: a speed of 31 rpm and a cumulative mixing time of 14 hours. After mixing, filter the mixture through a 300-mesh nylon mesh and a glass funnel to prepare the binder. Place the mixture in a clean glass bottle and set aside.

[0042] Step 2: Preparation of environmentally friendly ceramic metallization paste According to the metallization formula, 1000g of molybdenum powder and 133.33g of manganese powder were mixed into a metallized powder. The mixture was placed in a 1200ml nylon ball mill and ground on a planetary grinder for 6 hours at 530 rpm. After the metallized powder was evenly ground, the agate balls were screened out using a 50-mesh stainless steel sieve. The metallized powder was then placed in a 1000ml ground-mouth bottle and set aside.

[0043] The metallizing powder and agate balls were mixed in a ratio of 300g:200g, with the agate balls being φ4. The mixed metallizing powder and agate balls were then added to a plastic bottle. 66.67g of binder was then measured out using a beaker and added to the bottle. The bottle was capped and ground evenly in a jar mill. The grinding speed was set at 22 rpm for 14 hours to produce an environmentally friendly ceramic metallizing paste.

[0044] The environmentally friendly ceramic metallization paste prepared in Example 1 of the present invention was poured into an agate bowl and manually applied to the inner surface of the ceramic metallization product using a brush. The coating thickness was measured by an X-ray fluorescence thickness gauge to be ≥5μm. After primary metallization sintering, electroplating, and secondary metallization sintering, the application of the environmentally friendly ceramic metallization paste was achieved. The tensile strength value was tested using a three-point method. Figure 1 As shown, it can be seen that the tensile values ​​of the environmentally friendly ceramic metallization paste-coated product prepared in Example 1 of the present invention after sintering are: 456.72 MPa, 430.01 MPa, 443.25 MPa and 427.81 MPa, while the average tensile values ​​of the metallization paste-coated product prepared using butyl acetate and nitre-cotton solution after sintering are 383.1 MPa, 323.81 MPa, 354.42 MPa and 398.15 MPa. The results show that after sintering, the environmentally friendly ceramic metallization paste-coated product prepared by the present invention has a higher tensile strength than the metallization paste-coated product prepared using butyl acetate and nitre-cotton solution after sintering.

[0045] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A method for preparing an environmentally friendly ceramic metallization paste, characterized in that: include: Add ethyl cellulose to the butyl acetate solution, mix and grind evenly, filter, and prepare a binder; Mixing molybdenum powder and manganese powder into metallized powder, and grinding them evenly to obtain metallized powder; The binder is added to the metallized powder, mixed and ground evenly to obtain an environmentally friendly ceramic metallized paste.

2. The method for preparing an environmentally friendly ceramic metallization paste according to claim 1, characterized in that: The mass of the ethyl cellulose is 2-3% of the mass of the butyl acetate solution.

3. The method for preparing an environmentally friendly ceramic metallization paste according to claim 1, characterized in that: The mixing and grinding speed of the binder is 30-35 r / min, and the mixing and grinding time is 12-18 h.

4. The method for preparing an environmentally friendly ceramic metallization paste according to claim 1, characterized in that: The filtration process was carried out using a 300-mesh nylon mesh and a glass funnel for filtration.

5. The method for preparing an environmentally friendly ceramic metallization paste according to claim 1, characterized in that: The mixing mass ratio of the molybdenum powder to the manganese powder is (6.5-7.5):

1.

6. The method for preparing an environmentally friendly ceramic metallization paste according to claim 1, characterized in that: The mixing and grinding speed of the metallized powder is 500-550 r / min, and the mixing and grinding time is 4-6 hours.

7. The method for preparing an environmentally friendly ceramic metallization paste according to claim 1, characterized in that: The mass ratio of the metallized powder to the binder is (3.5-4.5):

1.

8. The method for preparing an environmentally friendly ceramic metallization paste according to claim 1, characterized in that: The mixing and grinding speed of the environmentally friendly ceramic metallization paste is 20-30 r / min, and the mixing and grinding time is 12-18 hours.

9. An environmentally friendly ceramic metallization paste prepared by the preparation method according to any one of claims 1 to 8.

10. The use of the environmentally friendly ceramic metallization paste according to claim 9, characterized in that: The environmentally friendly ceramic metallization paste is applied to the inner platform of the ceramic metallization product, and undergoes primary metallization sintering, electroplating and secondary metallization sintering.

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