阅读说明：本技术 一种钛酸钙镁陶瓷的化学粗化及金属化工艺 (Chemical roughening and metallization process of calcium magnesium titanate ceramic ) 是由 邢洪滨 冯虎荣 于 2020-11-09 设计创作，主要内容包括：本发明公开了一种钛酸钙镁陶瓷的化学粗化及金属化工艺,涉及陶瓷表面处理技术领域,旨在解决目前业界内还没有针对钛酸钙镁陶瓷的有效粗化工艺,继而导致后续镀层的附着力不佳的问题。其技术方案要点是,该工艺具体包括以下步骤：除油、粗化、调整、活化、解胶、化学铜和电镀,可有效粗化钛酸钙镁陶瓷表面,粗化前陶瓷样品的表面粗糙度为0.4-0.5um,粗化后样品表面粗糙度为0.8-1.0um,为后续的金属镀层提供良好的附着力,工艺操作方便,全流程为湿制程,操作温度较为温和,风险较小；另外对设备的要求降低,产品生产成本也会随之降低。(The invention discloses a chemical roughening and metallization process of calcium magnesium titanate ceramic, relates to the technical field of ceramic surface treatment, and aims to solve the problem that the adhesion of a subsequent plating layer is poor due to the fact that no effective roughening process aiming at the calcium magnesium titanate ceramic exists in the industry at present. The technical scheme is characterized in that the process specifically comprises the following steps: the method has the advantages that the surface of the calcium magnesium titanate ceramic can be effectively roughened by degreasing, roughening, adjusting, activating, dispergating, chemical copper and electroplating, the surface roughness of a ceramic sample before roughening is 0.4-0.5um, the surface roughness of the sample after roughening is 0.8-1.0um, good adhesive force is provided for subsequent metal coatings, the process operation is convenient, the whole process is a wet process, the operation temperature is mild, and the risk is small; in addition, the requirement on equipment is reduced, and the production cost of the product is reduced.)

1. A chemical coarsening and metallization process of calcium magnesium titanate ceramics is characterized in that: comprises the following steps of (a) carrying out,

step one, oil removal: adding calcium magnesium titanate ceramic into an oil powder removing aqueous solution, soaking and performing ultrasonic treatment;

step two, coarsening: heating a mixed solution of 98% sulfuric acid and a ceramic coarsening agent, adding the deoiled calcium magnesium titanate ceramic, and soaking;

step three, adjustment: heating the working solution of the regulator, adding the coarsened calcium magnesium titanate ceramic, and soaking;

step four, activation: heating the colloidal palladium working solution, adding the adjusted calcium magnesium titanate ceramic, and soaking;

step five, dispergation: heating the working solution of the debonder, adding the activated calcium magnesium titanate ceramic, and soaking;

step six, chemically depositing copper: heating the copper precipitation agent working solution, adding the peptized calcium magnesium titanate ceramic, and soaking;

step seven, electroplating: and adding a metal plating layer on the surface of the calcium magnesium titanate ceramic subjected to chemical copper deposition.

2. The chemical roughening and metallization process of a calcium magnesium titanate ceramic according to claim 1, wherein: the oil removing powder in the step one is a product of Midamei technology (Suzhou) Limited company with the model number Acid Cleaner 717; the ceramic coarsening agent in the step two is a product of Madei science and technology (Suzhou) Limited company model number BS-70; the regulator in the third step is a product of M-Condition of McSt, Inc; in the sixth step, the copper precipitation agent is a product of Midamei technology (Suzhou) Limited model MID Cu XD.

3. The chemical roughening and metallization process of the calcium magnesium titanate ceramic according to claim 2, wherein: the ultrasonic operation temperature in the first step is 45-55 deg.C, and the soaking time in the first step is 5-10 min.

4. The chemical roughening and metallization process of the calcium magnesium titanate ceramic according to claim 2, wherein: and in the second step, the heating temperature is 45-55 ℃, the soaking time in the second step is 5-15min, the operation concentration of the sulfuric acid in the second step is 80ml/L, and the operation concentration of the ceramic coarsening agent is 80 g/L.

5. The chemical roughening and metallization process of the calcium magnesium titanate ceramic according to claim 2, wherein: the heating temperature in the third step is 50-55 deg.C, and the soaking time in the third step is 3-7 min.

6. The chemical roughening and metallization process of a calcium magnesium titanate ceramic according to claim 5, wherein: the modifier in the third step comprises M-Condition PartA, M-Condition PartB and M-Condition PartC, wherein the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC are 100ml/L, 50ml/L and 25ml/L respectively.

7. The chemical roughening and metallization process of the calcium magnesium titanate ceramic according to claim 2, wherein: the heating temperature in the fourth step is 30-40 ℃, the soaking time in the fourth step is 5-7min, and the operating concentration of the colloidal palladium working solution is 50 ppm.

8. The chemical roughening and metallization process of the calcium magnesium titanate ceramic according to claim 2, wherein: in the fifth step, the heating temperature is 48-52 ℃, and the soaking time in the fifth step is 2-4 min.

9. The chemical roughening and metallization process of the calcium magnesium titanate ceramic according to claim 2, wherein: and sixthly, the working temperature of copper deposition is 50-55 ℃, the copper deposition agent comprises a complexing agent, copper ions, sodium hydroxide and formaldehyde, and the operating concentrations of the complexing agent, the copper ions, the sodium hydroxide and the formaldehyde are 0.10mol/L, 3.0g/L, 5.0g/L and 4.0g/L respectively.

10. A calcium magnesium titanate ceramic produced by a chemical roughening and metallizing process of a calcium magnesium titanate ceramic according to any one of claims 1 to 9.

Technical Field

The invention relates to the technical field of ceramic surface treatment, in particular to a chemical roughening and metallization process of calcium magnesium titanate ceramic.

Background

The calcium magnesium titanate ceramic is a novel material, is a material with a dielectric constant temperature coefficient near zero, is widely used for manufacturing thermally stable ceramic capacitors, microwave dielectric resonators and the like, and is widely applied to 5G networks. Researches find that the use requirement can be met only by adding a silver coating on the surface of the calcium magnesium titanate ceramic.

At present, a layer of metal silver is attached to the surface of the ceramic by adopting a silver paste sintering method, but the cost is too high. In order to reduce the cost, the calcium magnesium titanate ceramic is expected to be produced by a common electroplating method, but the chemical properties of the calcium magnesium titanate ceramic are stable and are not easy to coarsen and metalize. Currently, no effective roughening process for the calcium magnesium titanate ceramic exists in the industry, which leads to poor adhesion of a subsequent plating layer, and therefore needs to be further improved.

Disclosure of Invention

The invention aims to provide a chemical roughening and metallization process of calcium magnesium titanate ceramic, which has the effects of roughening the surface of the calcium magnesium titanate ceramic, providing good adhesive force for a subsequent metal coating, being convenient to operate, adopting a wet process in the whole process, and having mild operation temperature and less risk.

The technical purpose of the invention is realized by the following technical scheme:

a chemical coarsening and metallization process of calcium magnesium titanate ceramics comprises the following steps,

step one, oil removal: adding calcium magnesium titanate ceramic into an oil powder removing aqueous solution, soaking and performing ultrasonic treatment;

step two, coarsening: heating a mixed solution of 98% sulfuric acid and a ceramic coarsening agent, adding the degreased calcium magnesium titanate ceramic, and soaking;

step three, adjustment: heating the working solution of the regulator, adding the coarsened calcium magnesium titanate ceramic, and soaking;

step four, activation: heating the colloidal palladium working solution, adding the adjusted calcium magnesium titanate ceramic, and soaking;

step five, dispergation: heating the working solution of the debonder, adding activated calcium magnesium titanate ceramic, and soaking;

step six, chemically depositing copper: heating the copper precipitation agent working solution, adding the peptized calcium magnesium titanate ceramic, and soaking;

step seven, electroplating: and adding a metal plating layer on the surface of the calcium magnesium titanate ceramic subjected to chemical copper deposition.

The invention is further configured to: in the step one, the oil removing powder is a product of Midamei technology (Suzhou) limited company model Acid Cleaner 717; the ceramic coarsening agent in the step two is a product of Ma De Mei science and technology (Suzhou) Limited company model number BS-70; the regulator in the third step is a product of M-Condition of McSt, Inc; in the sixth step, the copper precipitation agent is a product of Midamei technology (Suzhou) Limited model MID Cu XD.

The invention is further configured to: the ultrasonic operation temperature in the first step is 45-55 deg.C, and the soaking time in the first step is 5-10 min.

The invention is further configured to: and in the second step, the heating temperature is 45-55 ℃, the soaking time in the second step is 5-15min, the operation concentration of the sulfuric acid in the second step is 80ml/L, and the operation concentration of the ceramic coarsening agent is 80 g/L.

The invention is further configured to: the heating temperature in the third step is 50-55 deg.C, and the soaking time in the third step is 3-7 min.

The invention is further configured to: the modifier in the third step comprises M-Condition PartA, M-Condition PartB and M-Condition PartC, wherein the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC are 100ml/L, 50ml/L and 25ml/L respectively.

The invention is further configured to: the heating temperature in the fourth step is 30-40 ℃, the soaking time in the fourth step is 5-7min, and the operating concentration of the colloidal palladium working solution is 50 ppm.

The invention is further configured to: in the fifth step, the heating temperature is 48-52 ℃, and the soaking time in the fifth step is 2-4 min.

The invention is further configured to: and sixthly, depositing copper at the working temperature of 50-55 ℃, wherein the copper depositing agent comprises a complexing agent, copper ions, sodium hydroxide and formaldehyde, and the operating concentrations of the complexing agent, the copper ions, the sodium hydroxide and the formaldehyde are 0.10mol/L, 3.0g/L, 5.0g/L and 4.0g/L respectively.

The invention also provides the calcium magnesium titanate ceramic prepared by the chemical roughening and metallization process.

In conclusion, the beneficial technical effects of the invention are as follows:

1. the process flow can effectively coarsen the surface of the calcium magnesium titanate ceramic, the surface roughness of the ceramic sample before coarsening is 0.4-0.5um, and the surface roughness of the sample after coarsening is 0.8-1.0um, so that good adhesive force is provided for the subsequent metal plating layer;

2. the oil removing step can effectively remove particle pollutants on the surface of the product, reduce the surface tension of the sample and facilitate the infiltration of subsequent liquid medicine; the coarsening step can enable a layer of uniform holes to appear on the surface of the product, is favorable for the adsorption of the catalyst colloid palladium and provides reliable adhesive force for the subsequent plating layer; the adjustment step can change the electrical property of the surface of the product and promote the adhesion of the subsequent colloidal palladium; the colloidal palladium is adsorbed on the surface of the sample in the activation step, so as to provide catalysis for the subsequent chemical copper process; in the step of glue dissolving, part of colloid wrapping palladium atoms is decomposed, so that the atomic palladium is exposed, and the deposition of copper is catalyzed in subsequent chemical copper bath solution; the chemical copper deposition step can uniformly deposit a layer of metal copper on the surface of the sample after catalysis, and then copper ions can be continuously deposited (with the speed of 4-6um/H) under the catalysis of fresh copper, and the layer of copper provides a conductive layer for subsequent electroplating; in the electroplating step, metals such as copper or silver can be added according to the requirement;

3. the process is convenient to operate, the whole process is a wet process, the operating temperature is mild, and the risk is low; in addition, the requirement on equipment is reduced, and the production cost of the product is reduced.

Detailed Description

The following detailed description of the preferred embodiments of the present invention is provided to enable those skilled in the art to more readily understand the advantages and features of the present invention and to clearly and unequivocally define the scope of the present invention.

It should be noted that the oil removing powder used in the present invention is a product of Maidamei technologies (Suzhou) Inc. type number Acid Cleaner 717; the ceramic coarsening agent is a product of Ma De Mei science and technology (Suzhou) Limited company model number BS-70; the regulator is a product of M-Condition of McSt, McSt; the copper precipitating agent is a product of Midamei technology (Suzhou) Limited model MID Cu XD. The other raw materials are common commercial products, so the sources are not particularly limited.

Example one

And selecting a sample I of the calcium magnesium titanate ceramic, and measuring the original surface roughness of the calcium magnesium titanate ceramic.

A chemical coarsening and metallization process of calcium magnesium titanate ceramics comprises the following steps,

step one, oil removal: adding the sample I of calcium magnesium titanate ceramic into an oil removing powder aqueous solution, soaking for 5min and carrying out ultrasonic treatment at an operation temperature of 55 ℃;

step two, coarsening: heating the mixed solution of 98% sulfuric acid and a ceramic roughening agent to 45 ℃, adding the deoiled calcium magnesium titanate ceramic, and soaking for 15min, wherein the concentration of the 98% sulfuric acid is 80ml/L, and the operation concentration of the ceramic roughening agent is 80 g/L;

step three, adjustment: heating the working solution of the regulator to 50 ℃, adding the coarsened calcium magnesium titanate ceramic, and soaking for 7 min; the regulator comprises M-Condition PartA, M-Condition PartB and M-Condition PartC, and the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC are respectively 100ml/L, 50ml/L and 25 ml/L;

step four, activation: heating the colloidal palladium working solution to 30 ℃, adding the adjusted calcium magnesium titanate ceramic, and soaking for 7min, wherein the operating concentration of the colloidal palladium working solution is 50 ppm;

step five, dispergation: heating the working solution of the debonder to 48 ℃, adding the activated calcium magnesium titanate ceramic, and soaking for 4 min;

step six, chemically depositing copper: heating the copper precipitation agent working solution to 50 ℃, adding the peptized calcium magnesium titanate ceramic, and soaking; the copper deposition agent comprises a complexing agent, copper ions, sodium hydroxide and formaldehyde, wherein the operating concentrations of the complexing agent, the copper ions, the sodium hydroxide and the formaldehyde are respectively 0.10mol/L, 3.0g/L, 5.0g/L and 4.0 g/L;

step seven, electroplating: and adding a metal plating layer on the surface of the calcium magnesium titanate ceramic subjected to chemical copper deposition.

Example two

And selecting a second sample of the calcium magnesium titanate ceramic, and measuring the original surface roughness of the calcium magnesium titanate ceramic.

A chemical coarsening and metallization process of calcium magnesium titanate ceramics comprises the following steps,

step one, oil removal: adding the second sample calcium magnesium titanate ceramic into the oil removing powder aqueous solution, soaking for 10min and carrying out ultrasonic treatment at the operating temperature of 45 ℃;

step two, coarsening: heating the mixed solution of 98% sulfuric acid and a ceramic roughening agent to 55 ℃, adding the deoiled calcium magnesium titanate ceramic, and soaking for 5min, wherein the concentration of the 98% sulfuric acid is 80ml/L, and the operation concentration of the ceramic roughening agent is 80 g/L;

step three, adjustment: heating the working solution of the regulator to 55 ℃, adding the coarsened calcium magnesium titanate ceramic, and soaking for 3 min; the regulator comprises M-Condition PartA, M-Condition PartB and M-Condition PartC, and the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC are respectively 100ml/L, 50ml/L and 25 ml/L;

step four, activation: heating the colloidal palladium working solution to 40 ℃, adding the adjusted calcium magnesium titanate ceramic, and soaking for 5min, wherein the operating concentration of the colloidal palladium working solution is 50 ppm;

step five, dispergation: heating the working solution of the debonder to 52 ℃, adding the activated calcium magnesium titanate ceramic, and soaking for 2 min;

step six, chemically depositing copper: heating the copper precipitation agent working solution to 55 ℃, adding the peptized calcium magnesium titanate ceramic, and soaking; the copper deposition agent comprises a complexing agent, copper ions, sodium hydroxide and formaldehyde, wherein the operating concentrations of the complexing agent, the copper ions, the sodium hydroxide and the formaldehyde are respectively 0.10mol/L, 3.0g/L, 5.0g/L and 4.0 g/L;

step seven, electroplating: and adding a metal plating layer on the surface of the calcium magnesium titanate ceramic subjected to chemical copper deposition.

EXAMPLE III

And selecting a third sample of the calcium magnesium titanate ceramic, and measuring the original surface roughness of the calcium magnesium titanate ceramic.

A chemical coarsening and metallization process of calcium magnesium titanate ceramics comprises the following steps,

step one, oil removal: adding the third sample calcium magnesium titanate ceramic into the oil removing powder aqueous solution, soaking for 7min and carrying out ultrasonic treatment at the operation temperature of 50 ℃;

step two, coarsening: heating the mixed solution of 98% sulfuric acid and a ceramic roughening agent to 50 ℃, adding the deoiled calcium magnesium titanate ceramic, and soaking for 10min, wherein the concentration of the 98% sulfuric acid is 80ml/L, and the operation concentration of the ceramic roughening agent is 80 g/L;

step three, adjustment: heating the working solution of the regulator to 52 ℃, adding the coarsened calcium magnesium titanate ceramic, and soaking for 5 min; the regulator comprises M-Condition PartA, M-Condition PartB and M-Condition PartC, and the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC are respectively 100ml/L, 50ml/L and 25 ml/L;

step four, activation: heating the colloidal palladium working solution to 35 ℃, adding the adjusted calcium magnesium titanate ceramic, and soaking for 6min, wherein the operating concentration of the colloidal palladium working solution is 50 ppm;

step five, dispergation: heating the working solution of the debonder to 50 ℃, adding the activated calcium magnesium titanate ceramic, and soaking for 3 min;

step six, chemically depositing copper: heating the copper precipitation agent working solution to 53 ℃, adding the peptized calcium magnesium titanate ceramic, and soaking; the copper deposition agent comprises a complexing agent, copper ions, sodium hydroxide and formaldehyde, wherein the operating concentrations of the complexing agent, the copper ions, the sodium hydroxide and the formaldehyde are respectively 0.10mol/L, 3.0g/L, 5.0g/L and 4.0 g/L;

step seven, electroplating: and adding a metal plating layer on the surface of the calcium magnesium titanate ceramic subjected to chemical copper deposition.

According to GB/T13841-1992GB/T13841-1992 surface roughness of electronic ceramic parts, the original surface roughness and the roughness after coarsening of the first sample, the second sample and the third sample of the calcium magnesium titanate ceramic are respectively measured.

TABLE I surface roughness of non-roughened calcium magnesium titanate ceramics and roughened calcium magnesium titanate ceramics

	Sample No. one	Sample No. two	Sample No. three
				Not coarsened	Ra＝0.4μm	Ra＝0.5μm	Ra＝0.4μm
After coarsening	Ra＝0.8μm	Ra＝1.0μm	Ra＝0.9μm

As can be seen from the above table, after roughening, the surface roughness of the calcium magnesium titanate ceramic is increased, and good adhesion is provided for the subsequent metal plating layer.

The process flow can effectively coarsen the surface of the calcium magnesium titanate ceramic, the surface roughness of the ceramic sample before coarsening is 0.4-0.5um, and the surface roughness of the sample after coarsening is 0.8-1.0um, so that good adhesive force is provided for the subsequent metal plating layer;

the oil removing step can effectively remove particle pollutants on the surface of the product, reduce the surface tension of the sample and facilitate the infiltration of subsequent liquid medicine; the coarsening step can enable a layer of uniform holes to appear on the surface of the product, is beneficial to the adsorption of the catalyst colloid palladium and provides reliable adhesive force for the subsequent plating layer; the adjustment step can change the electrical property of the surface of the product and promote the adhesion of the subsequent colloid palladium; the colloid palladium is adsorbed on the surface of the sample in the activation step, and the catalysis is provided for the subsequent chemical copper process; in the step of glue dissolving, part of colloid wrapping palladium atoms is decomposed, so that the atomic palladium is exposed, and the deposition of copper is catalyzed in subsequent chemical copper bath solution; the chemical copper deposition step can uniformly deposit a layer of metal copper on the surface of the sample after catalysis, and then under the catalysis of fresh copper, copper ions can be continuously deposited (the speed is 4-6um/H), and the layer of copper provides a conductive layer for subsequent electroplating; the electroplating step may be carried out by plating copper or silver as required.

The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications made by the equivalent structures or equivalent processes in the present specification, or directly or indirectly applied to other related technical fields are included in the scope of the present invention.