CN110453220B - Method for mixed metallisation of ceramic filters, products and applications thereof - Google Patents

Method for mixed metallisation of ceramic filters, products and applications thereof Download PDF

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CN110453220B
CN110453220B CN201910845768.1A CN201910845768A CN110453220B CN 110453220 B CN110453220 B CN 110453220B CN 201910845768 A CN201910845768 A CN 201910845768A CN 110453220 B CN110453220 B CN 110453220B
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ceramic
ceramic substrate
plating
solution
palladium
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CN110453220A (en
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卜庆革
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QINGDAO HENGTONG X-SILVER SPECIALTY TEXTILE Co.,Ltd.
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卜庆革
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18Pretreatment of the material to be coated
    • C23C18/1851Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1875Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment only one step pretreatment
    • C23C18/1879Use of metal, e.g. activation, sensitisation with noble metals
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31Coating with metals
    • C23C18/42Coating with noble metals
    • C23C18/44Coating with noble metals using reducing agents
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/46Electroplating: Baths therefor from solutions of silver
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54Electroplating of non-metallic surfaces
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01PWAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P1/00Auxiliary devices
    • H01P1/20Frequency-selective devices, e.g. filters
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01PWAVEGUIDES; RESONATORS, LINES, OR OTHER DEVICES OF THE WAVEGUIDE TYPE
    • H01P11/00Apparatus or processes specially adapted for manufacturing waveguides or resonators, lines, or other devices of the waveguide type
    • H01P11/007Manufacturing frequency-selective devices

Abstract

The present invention provides methods for hybrid metallization of ceramic filters, products and applications thereof. The method of the present invention includes a pretreatment step, a first plating step, and a second plating step. According to the requirements of different filters, micron-sized ceramic filters with multiple metal layers and surface resistance less than or equal to 0.5 ohm can be prepared. The invention adopts mixed plating to form a metal layer on the surface of the ceramic substrate, thereby ensuring the integrity and the compactness of the ceramic substrate, and having the characteristics of easy control of the synthesis process and stable metal layer. The ceramic filter prepared by the mixed plating method can effectively improve the bonding performance between metal layers, obtains a material with good performance, has a yield up to 99 percent, and has wide application prospect in household appliances and electronic products.

Description

Method for mixed metallisation of ceramic filters, products and applications thereof
Technical Field
The invention belongs to the field of filters, and particularly relates to a ceramic filter, in particular to a mixed metal-plated ceramic filter and a preparation method thereof.
Background
Ceramic filters are classified into band-stop filters (also called traps) and band-pass filters (also called filters) according to their amplitude-frequency characteristics. The circuit is mainly used in circuits such as frequency selection networks, intermediate frequency tuning, frequency discrimination, filtering and the like, and achieves the purpose of separating currents with different frequencies. The phase-frequency-modulation-based high-power-factor amplifier has the characteristics of high Q value, good amplitude-frequency and phase-frequency characteristics, small volume, high signal-to-noise ratio and the like. Has been widely applied to household appliances such as color TV, radio and the like and other electronic products. The ceramic filter mainly utilizes the piezoelectric effect of the ceramic material to realize the conversion of the electric signal → the mechanical vibration → the electric signal, thereby replacing an LC filter circuit in part of electronic circuits and ensuring that the work of the ceramic filter is more stable.
The filter is used as a key component for frequency selection, and has the advantages of good frequency selectivity, small volume, light weight, stability, reliability, no need of debugging and the like in application, and is particularly more critical to the performance of the filter in the process research of carrying out metallization coating on a ceramic substrate.
At present, the ceramic filter is generally prepared by dipping silver powder slurry on a substrate and then sintering at high temperature. The silver layer obtained by the method has weak adhesion with the base material, and therefore, the sintering treatment needs to be repeatedly carried out for many times. Even so, the yield is still low, only 60%.
In addition, techniques of coating a ceramic surface with a slurry such as magnetron sputtering, electroplating, etc. are disclosed, for example, US6016091 and CN 105633518. However, these techniques have different disadvantages in practical applications, such as that the plating method realizes a good appearance of the metal plating layer by reducing ions in the electrolyte, but the formed metal layer is likely to generate bubbles and be detached at a large current or a high temperature, and is greatly affected by the purity of the electrolyte. Magnetron sputtering requires a higher-demand target material and is high in cost.
Therefore, in practical application, according to different requirements on the filter, the filter which is low in cost, simple in preparation method, easy to control the preparation of the metal film layer, compact and provided with the surface multi-layer metallization has the advantages that the stability of the metal coating is ensured, and the performance meets the requirements, and the filter has positive significance to the field.
Disclosure of Invention
In order to solve the technical problems, the invention combines the chemical plating method with the electroplating method to carry out mixed plating, and obtains the metalized ceramic filter with excellent performance by optimizing the preparation process. The present invention has been accomplished, at least in part, based on this. Specifically, the present invention includes the following.
In a first aspect of the invention, there is provided a method of hybrid metallisation for a ceramic filter comprising the steps of:
(1) a pretreatment step: sequentially treating a ceramic substrate by using hydrochloric acid and an organic solvent, taking out and drying to obtain a pretreated ceramic substrate;
(2) a first plating step: the method comprises the steps of enabling the pretreated ceramic substrate to form a silver metal layer coated on the surface in a solution to obtain a ceramic substrate with a first coating, wherein the thickness of the first coating is 500 nm-3 mu m, and the resistance is 0.5-20 ohm;
(3) a second plating step: the method comprises the step of electroplating a first plating layer ceramic substrate to obtain a ceramic substrate with a second plating layer, namely a ceramic filter, wherein the thickness of the second plating layer is more than 3 mu m, and the resistance is less than 0.5 ohm.
In certain exemplary embodiments, the ceramic substrate is made of a lead zirconate titanate ceramic material and/or an aluminum-modified lead zirconate titanate ceramic material.
In certain exemplary embodiments, the step (2) comprises:
(2-1) soaking the pretreated ceramic substrate in a first solution containing palladium salt and glucose for 1-5min, taking out, and reacting in a high-temperature gas atmosphere at 200-800 ℃ for 2-4h to obtain a metallized ceramic substrate;
(2-2) soaking the metallized substrate in a second solution containing silver salt, and then adding formaldehyde to react for 30-80min to obtain the ceramic substrate with the first plating layer.
In certain exemplary embodiments, the first solution is an aqueous solution and the palladium salt is selected from at least one of palladium chloride, palladium nitrate, palladium sulfate, and palladium acetate; the concentration of the palladium salt is 1-10 g/L; the concentration of the glucose is 1-10 g/L.
In certain exemplary embodiments, the second solution comprises 10 to 90g/L silver nitrate and 0.5 to 20mol/L ammonia.
In certain exemplary embodiments, the concentration of hydrochloric acid in step (1) is 15 to 30%, and the time of hydrochloric acid treatment is 30 seconds to 5 minutes; the organic solvent is at least one selected from the group consisting of alcohol, toluene and acetone.
In certain exemplary embodiments, the electroplating in step (3) employs a cyanide-free silver plating process.
In certain exemplary embodiments, the plating solution in the cyanide-free silver plating process comprises a fluorine-substituted silver borate salt, an alkynol solvent, ammonium acetate, p-methoxybenzaldehyde, and benzoic acid.
In a second aspect of the present invention, there is provided a ceramic filter obtained by the production method according to the present invention.
In a third aspect of the invention, there is provided the use of the ceramic filter in household appliances and electronic products.
The invention adopts mixed plating on the surface of the ceramic substrate to form the metal layer, thereby ensuring the integrity and the compactness of the ceramic substrate, and then obtaining the micron-sized metallized ceramic filter with a plurality of metal layers according to the actual requirements of the filter, and the invention has the characteristics of easy control of the synthesis process and stable metal layer. The ceramic filter prepared by the mixed plating method can effectively improve the bonding performance between metal layers, obtains a material with good performance, has a yield up to 99 percent which is far higher than that of the traditional method, and has wide application prospect in household appliances and electronic products.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that the upper and lower limits of the range, and each intervening value therebetween, is specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents.
Considering the limitation of the prior art on the method for metalizing the surface of the ceramic filter, particularly, the surface of the silver layer is not smooth; b. the operation is complex, and the conductivity of the metal layer is low due to the introduction of impurities in the preparation process; c. the metal layer falls off in practical application and environment, the adhesive force between the metal layer and the base material is poor, and the yield is low; d. the thickness of the metal layer is not uniform and is not easy to control in the preparation process. In one aspect the invention provides a method of hybrid metallisation for a ceramic filter comprising the steps of:
(1) a pretreatment step: sequentially treating a ceramic substrate by using hydrochloric acid and an organic solvent, taking out and drying to obtain a pretreated ceramic substrate;
(2) a first plating step: the method comprises the steps of enabling the pretreated ceramic substrate to form a silver metal layer coated on the surface in a solution to obtain a ceramic substrate with a first plating layer, wherein the thickness of the first plating layer is 500nm to 3 mu m, preferably 800nm to 3 mu m, the resistance is 0.5 to 20 ohm, preferably 5 to 20 ohm, and further preferably 10-20 ohm;
(3) a second plating step: the method comprises the step of electroplating a first plating layer ceramic substrate to obtain a ceramic substrate with a second plating layer, namely a ceramic filter, wherein the thickness of the second plating layer is more than 3 mu m, and the resistance is less than 0.5 ohm.
The respective steps are explained in detail below.
Step (1)
The step (1) of the invention is a step of pretreating the ceramic substrate, which comprises the steps of sequentially treating the ceramic substrate by using hydrochloric acid and an organic solvent, taking out and drying to obtain the pretreated ceramic substrate.
The filter ceramic substrate used in the present invention is preferably made of a lead zirconate titanate ceramic material and/or an aluminum-modified lead zirconate titanate ceramic material, and the shape of the ceramic material is not particularly limited, and may be a ceramic filter of various suitable shapes, for example, the body of the ceramic filter includes, but is not limited to, a rectangular parallelepiped, a cube, a cylinder, or a prism, and other shapes may be designed according to actual needs.
The ceramic material of the invention is required to have a perovskite structure, the composition of which may generally consist of Mea-XbTicOdAnd (4) showing. Wherein Me and X comprise at least one of Mg, Zn, Ba, Ca, Bi, Zr, Li, Al and Pb; wherein 0 < a + b + c + d < 9, b ≧ 0, and optionally Me may be one or more metal compositions. In certain embodiments, the ceramic substrate of the present invention is PbZrO3And PbTiO3A solid solution of (2). In another embodiment, the starting material of the ceramic substrate of the present invention comprises PbZrO3、PbTiO3And partial alumina, thereby obtaining the aluminum modified lead zirconate titanate ceramic material. The present invention has found that the adhesion between the metal coating and the ceramic material can be greatly improved by adding a raw material containing Al, such as alumina, to the conventional lead zirconate titanate ceramic raw material. The reason for this may be that Al-Ag has a small thermal expansion coefficient, high thermal stability, large adhesion and is not easy to fall off, and a stable metal layer structure is formed controllably. Thus, aluminum modified ceramic materials are preferred in the present invention. The content of Al is not particularly limited, and is generally 0.08 wt% or less based on the total weight of the ceramic material.
The concentration of the hydrochloric acid of the present invention is generally 15 to 30%, preferably 15 to 25%, more preferably 18 to 20%. The hydrochloric acid treatment time is not excessively long, and is generally from 30 seconds to 5 minutes, preferably from 50 seconds to 3 minutes, and more preferably from 1 minute to 2 minutes. The hydrochloric acid treatment of the present invention facilitates the adhesion of metal to ceramic. The reason for this may be that the hydrochloric acid treatment forms a minute uneven structure on the surface of the ceramic, thereby facilitating the adhesion of the metal.
The organic solvents of the present invention are typically alcohols, toluene and acetone. One or more of the above three organic solvents may be used in the present invention. Preferably, the present invention uses alcohol. The organic solvent is beneficial to removing organic matters on the surface of the ceramic and is beneficial to plating of subsequent metal.
After the organic solvent treatment, the ceramics of the present invention are subjected to a baking treatment, which is generally carried out at a relatively high temperature, for example, 80 to 200 ℃, preferably 90 to 150 ℃.
Step (2)
Step (2) of the present invention is an electroless plating step in the hybrid plating. Unlike conventional electroless plating, the electroless plating of the present invention requires two successive layers of metal on the ceramic surface. Specifically, in the present invention, a palladium layer is first formed on the surface of the ceramic substrate by electroless plating, and the palladium salt is at least one selected from the group consisting of palladium chloride, palladium nitrate, palladium sulfate, and palladium acetate. The invention finds that the bonding force between palladium metal and ceramic is stronger during chemical plating, and the palladium metal can also improve the bonding force between silver and the surface of the ceramic. In addition, the palladium metal characteristic can catalyze the oxidation-reduction reaction controllably, silver metal ions can be further deposited on the surface of the ceramic substrate, and the deposited layer still has catalytic capability in the plating process, so that a thicker silver metal layer can be formed.
In an exemplary embodiment, step (2) of the present invention comprises the following two substeps:
(2-1) soaking the pretreated ceramic substrate in a first solution containing palladium salt and glucose for 1-5min, preferably, for 2-4 min. The concentration of palladium salt is 1-10g/L, preferably 2-8g/L, and the concentration of glucose is 1-10g/L, preferably 2-8 g/L. Then taking out and placing in a high-temperature gas atmosphere at 200-800 ℃ for reaction for 2-4h, preferably, the temperature is 400-800 ℃, more preferably, 700-800 ℃, and obtaining a metallized ceramic substrate;
(2-2) immersing the metallized substrate in a solution containing 1-10g/L silver nitrate and 0.5-20mol/L ammonia water, preferably, the concentration of silver nitrate is 2-8g/L, more preferably 3-5 g/L. And adding formaldehyde for reaction for 30-80min, preferably 40-70min, more preferably 45-65min, such as 50min, to obtain the ceramic substrate with the first coating.
In the present invention, the first plating layer formed by electroless plating in step (2) has an average thickness of generally 500nm to 3 μm and a high resistance of generally 0.5 or more, due to the limitations of electroless plating. Such a plating layer is not satisfactory for a ceramic filter.
Step (3)
Step (3) of the present invention is a second plating step of further performing a plating treatment on the ceramic base material having the first plating layer of step (2). Namely, the micron-sized metallized ceramic substrate prepared in the step (2) is used as a cathode, electroplating solution containing metal ions is used as an anode, and the metal ions are reduced at the cathode through external current, so that different micron-sized metal coatings are formed on the ceramic substrate. The plating method employed herein in the present invention can use known methods. The cyanide-free silver plating method, i.e., the method of performing electroplating using a system of cyanide-free silver plating solution, is preferably used. Preferably, the cyanide-free electroplating solution of the present invention includes a fluorine-containing substituted silver borate salt, an alkynol solvent, ammonium acetate, p-methoxybenzaldehyde, and benzoic acid. Examples of fluorine-containing substituted silver borate salts of the present inventionIncluding but not limited to silver tetrafluoroborate and the like. Examples of the alkynol solvent of the present invention include methylpentylynol and/or 1, 4-butynediol, and the like. Preferably, the fluorine substituted silver borate salt is 25 to 35g/L, the alkynol solvent is 0.2 to 1.2g/L, the p-methoxybenzaldehyde is 8 to 20g/L and the benzoic acid is 15 to 24 g/L. Adopting a direct current or pulse power supply, taking the anode as a silver plating solution and the cathode as the metallized ceramic substrate obtained in the step (2), wherein the temperature is 25-35 ℃, and the current density is 0.1-0.5A/dm2Electroplating for 20-80 min. The invention finds that the product obtained by the electroplating solution has better stability, the resistance between metal layer structures is reduced by the conversion of current, and finally the metalized ceramic filter with different micron-sized metal coatings and the resistance less than or equal to 0.5 omega is obtained.
The invention adopts mixed plating on the surface of the ceramic substrate to form the metal layer, thereby ensuring the integrity and the compactness of the ceramic substrate, and then obtaining the micron-sized metallized ceramic filter with a plurality of metal layers according to the actual requirements of the filter, and the invention has the characteristics of easy control of the synthesis process and stable metal layer. The ceramic filter prepared by the mixed plating method can effectively improve the bonding performance between metal layers, obtains a material with good performance, has a yield up to 99 percent which is far higher than that of the traditional method, and has wide application prospect in household appliances and electronic products.
Example 1
This example is an exemplary hybrid metallized ceramic filter fabrication procedure, as follows:
1. and cleaning the lead zirconate titanate ceramic by using 30% hydrochloric acid, then cleaning the lead zirconate titanate ceramic again by using alcohol, and drying the lead zirconate titanate ceramic to obtain the pretreated ceramic substrate.
2. Soaking the pretreated ceramic substrate in an aqueous solution containing 5g/L of palladium acetate and 5g/L of glucose for 3min, then placing the pretreated ceramic substrate in a high-temperature oven to react for 4h at the temperature of 800 ℃ to obtain a metallized ceramic substrate, then placing the metallized ceramic substrate in a silver nitrate solution containing 8mol/L of ammonia water and 4g/L of formaldehyde to react for 50min, and obtaining the micron-sized metallized ceramic substrate.
3. The adopted electroplating solution comprises 25g/L of silver tetrafluoroborate, 0.2g/L of methyl pentynol, 0.9g/L of 1, 4-butynediol and 8g/L of p-methoxylBenzaldehyde and 18g/L benzoic acid, pH5.3, temperature 30 deg.C, current density 2.4A/dm2Electroplating for 80 min.
4. Sample mass determination
The thickness is measured by adopting a light section microscope and an XRF thickness gauge; the adhesive force of the metal coating is tested by a scratching method, a sample is cut into 2mm multiplied by 2mm grids by a small knife, the surface is observed to have the phenomena of peeling, falling off and the like, the sample is heated to 200 ℃, then is insulated for 1h, is quenched in water to room temperature, and is observed to have the phenomena of peeling and bubbling; and (4) carrying out resistance test on the production sample by using a multimeter.
5. Measurement results
The adhesion results show that the individual samples subjected to the production test have the peeling, peeling and bubbling phenomena of different degrees, the yield is 96 percent, the average thickness of the metal coating is 8 mu m, and the surface resistance is 0.45 ohm.
Example 2
This example is an exemplary hybrid metallized ceramic filter fabrication procedure, as follows:
1. and cleaning the lead zirconate titanate ceramic by using 30% hydrochloric acid, then cleaning the lead zirconate titanate ceramic again by using alcohol, and drying the lead zirconate titanate ceramic to obtain the pretreated ceramic substrate.
2. Soaking the pretreated ceramic substrate in an aqueous solution containing 3g/L of palladium acetate and 3g/L of glucose for 3min, then placing the pretreated ceramic substrate in a high-temperature oven to react for 4h at the temperature of 800 ℃ to obtain a metallized ceramic substrate, then placing the metallized ceramic substrate in a silver nitrate solution containing 6mol/L of ammonia water and 2g/L of ammonia water, and adding formaldehyde to react for 50min to obtain the micron-sized metallized ceramic substrate.
3. The adopted electroplating solution comprises 25g/L silver tetrafluoroborate, 0.5g/L methyl pentynol, 0.7g/L1, 4-butynediol, 9g/L p-methoxybenzaldehyde and 15g/L benzoic acid, the pH value is 6, the temperature is 30 ℃, and the current density is 2.4A/dm2Electroplating for 80 min.
4. Sample mass determination
The thickness is measured by adopting a light section microscope and an XRF thickness gauge; the adhesive force of the metal coating is tested by a scratching method, a sample is cut into 2mm multiplied by 2mm grids by a small knife, the surface is observed to have the phenomena of peeling, falling off and the like, then the sample is heated to 200 ℃ and is insulated for 1h, then the sample is quenched in water to room temperature, and the phenomena of peeling and bubbling are observed to be present or not; and (4) carrying out resistance test on the production sample by using a multimeter.
5. Measurement results
The adhesion results show that the individual samples subjected to the production test have the peeling, peeling and bubbling phenomena of different degrees, the yield is 93 percent, the average thickness of the metal coating is 6 mu m, and the surface resistance is 0.49 ohm.
Example 3
This example is an exemplary hybrid metallized ceramic filter fabrication procedure, as follows:
1. and (3) cleaning the aluminum modified lead zirconate titanate ceramic by using 30% hydrochloric acid, then cleaning the aluminum modified lead zirconate titanate ceramic again by using alcohol, and drying the aluminum modified lead zirconate titanate ceramic to obtain the pretreated ceramic substrate.
2. Soaking the pretreated ceramic substrate in an aqueous solution containing 4g/L of palladium acetate and 4g/L of glucose for 3min, then placing the pretreated ceramic substrate in a high-temperature oven to react for 4h at the temperature of 800 ℃ to obtain a metallized ceramic substrate, then placing the metallized ceramic substrate in a silver nitrate solution containing 8mol/L of ammonia water and 4g/L of formaldehyde to react for 50min, and obtaining the micron-sized metallized ceramic substrate.
3. The adopted electroplating solution comprises 25g/L silver tetrafluoroborate, 0.5g/L methyl pentynol, 0.7g/L1, 4-butynediol, 9g/L p-methoxybenzaldehyde and 15g/L benzoic acid, the pH value is 6, the temperature is 30 ℃, and the current density is 2.4A/dm2Electroplating for 80 min.
4. Sample mass determination
The thickness is measured by adopting a light section microscope and an XRF thickness gauge; the adhesive force of the metal coating is tested by a scratching method, a sample is cut into 2mm multiplied by 2mm grids by a small knife, the surface is observed to have the phenomena of peeling, falling off and the like, then the sample is heated to 200 ℃ and is insulated for 1h, then the sample is quenched in water to room temperature, and the phenomena of peeling and bubbling are observed to be present or not; and (4) carrying out resistance test on the production sample by using a multimeter.
5. Measurement results
The adhesion results show that the individual samples subjected to the production test have the peeling, peeling and bubbling phenomena of different degrees, the yield is 99%, the average thickness of the metal coating is 11 mu m, and the surface resistance is 0.40 ohm.
Comparative example 1
The comparative example is a comparative ceramic filter preparation process, which specifically includes:
1. and cleaning the lead zirconate titanate ceramic by using 30% hydrochloric acid, then cleaning the lead zirconate titanate ceramic again by using alcohol, and drying the lead zirconate titanate ceramic to obtain the pretreated ceramic substrate.
2. The adopted electroplating solution comprises 25g/L silver tetrafluoroborate, 0.2g/L methyl pentynol, 0.9g/L1, 4-butynediol, 8g/L p-methoxybenzaldehyde and 18g/L benzoic acid, the pH value is 5.3, the temperature is 30 ℃, and the current density is 2.4A/dm2Electroplating for 80 min.
3. Sample mass determination
The thickness is measured by adopting a light section microscope and an XRF thickness gauge; the adhesive force of the metal coating is tested by a scratching method, a sample is cut into 2mm multiplied by 2mm grids by a small knife, the surface is observed to have the phenomena of peeling, falling off and the like, then the sample is heated to 200 ℃ and is insulated for 1h, then the sample is quenched in water to room temperature, and the phenomena of peeling and bubbling are observed to be present or not; and (4) carrying out resistance test on the production sample by using a multimeter.
4. Measurement results
The adhesion results show that half of samples subjected to production tests have the phenomena of peeling, peeling and bubbling in different degrees, the yield is 53 percent, the average thickness of a metal coating is 7 mu m, and the surface resistance is 2.2 ohms.
Comparative example 2
The comparative example is a comparative ceramic filter preparation process, which specifically includes:
1. and cleaning the lead zirconate titanate ceramic by using 30% hydrochloric acid, then cleaning the lead zirconate titanate ceramic again by using alcohol, and drying the lead zirconate titanate ceramic to obtain the pretreated ceramic substrate.
2. And (3) putting the pretreated ceramic substrate into a silver nitrate solution containing 8mol/L ammonia water and 4g/L, and adding formaldehyde to react for 50min to obtain the micron-sized metallized ceramic substrate.
3. The adopted electroplating solution comprises 25g/L of silver tetrafluoroborate, 0.2g/L of methylpentylenol and 0.9g/L1, 4-butynediol, 8g/L p-methoxybenzaldehyde and 18g/L benzoic acid, pH5.3, temperature 30 ℃, current density 2.4A/dm2Electroplating for 80 min.
4. Sample mass determination
The thickness is measured by adopting a light section microscope and an XRF thickness gauge; the adhesive force of the metal coating is tested by a scratching method, a sample is cut into 2mm multiplied by 2mm grids by a small knife, the surface is observed to have the phenomena of peeling, falling off and the like, then the sample is heated to 200 ℃ and is insulated for 1h, then the sample is quenched in water to room temperature, and the phenomena of peeling and bubbling are observed to be present or not; and (4) carrying out resistance test on the production sample by using a multimeter.
5. Measurement results
The adhesion results show that the samples subjected to the production test have the peeling, peeling and bubbling phenomena of different degrees, the yield is 68%, the average thickness of the metal coating is 6 mu m, and the surface resistance is 2.6 ohms.
While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Many modifications and variations may be made to the exemplary embodiments of the present description without departing from the scope or spirit of the present invention. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all modifications and equivalent structures and functions.

Claims (5)

1. A method of cyanide-free mixed metallization for ceramic filters, comprising the steps of:
(1) a pretreatment step: the method comprises the steps of sequentially treating a ceramic substrate by using hydrochloric acid and an organic solvent, taking out the ceramic substrate, and drying the ceramic substrate at 80-200 ℃ to obtain a pretreated ceramic substrate, wherein the ceramic substrate is made of an aluminum-modified lead zirconate titanate ceramic material, and the ceramic substrate comprises PbZrO as a raw material3、PbTiO3And partial alumina to obtain an aluminum-modified lead zirconate titanate ceramic material;
(2) a first plating step: soaking the pretreated ceramic substrate in a first solution containing glucose and 1-10g/L palladium salt for 1-5min, taking out the pretreated ceramic substrate, placing the pretreated ceramic substrate in a high-temperature gas atmosphere at 700-800 ℃ for reaction for 2-4h to obtain a metallized ceramic substrate, soaking the metallized substrate in a second solution containing silver salt, adding formaldehyde for reaction for 30-80min to form a silver metal layer coated on the surface, and obtaining the ceramic substrate with a first plating layer, wherein the average thickness of the first plating layer is 500 nm-3 mu m, and the resistance is 0.5-20 ohm;
(3) a second plating step: the method comprises the steps of enabling a first plating layer ceramic substrate to be subjected to cyanide-free electroplating to obtain a ceramic substrate with a second plating layer, namely a ceramic filter, wherein the thickness of the second plating layer is more than 3 mu m, the resistance is less than 0.5 ohm, electroplating solution in the cyanide-free electroplating process comprises fluorine-substituted silver borate, alkynol solvent, ammonium acetate, p-methoxybenzaldehyde and benzoic acid,
wherein the first solution is an aqueous solution, and the palladium salt is at least one selected from palladium chloride, palladium nitrate, palladium sulfate and palladium acetate; the concentration of the glucose is 1-10 g/L.
2. The method of cyanide-free mixed metallization for ceramic filters according to claim 1, characterized in that the second solution comprises 1-10g/L silver nitrate and 0.5-20mol/L ammonia water.
3. The method of cyanide-free mixed metallization for a ceramic filter according to claim 1, wherein the concentration of hydrochloric acid in the step (1) is 15 to 30%, and the time of the hydrochloric acid treatment is 30 seconds to 5 minutes; the organic solvent is at least one selected from the group consisting of alcohol, toluene and acetone.
4. A ceramic filter produced by the method according to any one of claims 1 to 3.
5. Use of the ceramic filter according to claim 4 in household appliances and electronic products.
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US4965094A (en) * 1988-12-27 1990-10-23 At&T Bell Laboratories Electroless silver coating for dielectric filter
CN105648485A (en) * 2016-03-07 2016-06-08 昆明理工大学 Cyanide-free silver electroplating liquid

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US4965094A (en) * 1988-12-27 1990-10-23 At&T Bell Laboratories Electroless silver coating for dielectric filter
CN105648485A (en) * 2016-03-07 2016-06-08 昆明理工大学 Cyanide-free silver electroplating liquid

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