CN112341250A - Metallization process of zirconia ceramic - Google Patents
Metallization process of zirconia ceramic Download PDFInfo
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- C23C18/00—Chemical 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
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- C23C28/00—Coating 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
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Abstract
The invention provides a metallization process of zirconia ceramics, which relates to the technical field of ceramic metallization processing, and specifically comprises the following steps: degreasing, coarsening, adjusting, activating, dispergating, chemical copper and electroplating. The process has the advantages of simple operation, low equipment requirement and low cost, can etch uniform holes on the surface of the zirconia ceramic, is favorable for the smooth operation of the subsequent metal flow, and provides guarantee for the adhesion of a plating layer, thereby obtaining excellent adhesion.
Description
Technical Field
The invention relates to the technical field of ceramic metallization processing, in particular to a metallization process of zirconia ceramic.
Background
Zirconia ceramics have the characteristics of high melting point, high boiling point, high hardness, insulation at normal temperature and high temperature, stable chemical properties and the like, and in recent years, zirconia ceramics are used in the industry to meet the special requirements of precision instruments. But the chemical property is stable, the acid and alkali resistance is good, the general roughening process is difficult to achieve the roughening effect, and the adhesion of a subsequent plating layer is difficult to ensure. In response to such problems, researchers have conducted related studies to find a metallization method of zirconia ceramics.
Chinese patent CN109422547A discloses a method for metallizing the surface of zirconia ceramics, which comprises the following steps: A. cleaning the surface of the zirconia ceramic; B. coating a protective agent on a selected position of the zirconia ceramic, and curing; C. activating the surface of the zirconia ceramic; D. putting the zirconia ceramic into a vacuum chamber, and irradiating the surface of the zirconia ceramic by using an electron beam to realize the metallization of the surface of the zirconia ceramic. Can improve the defects of the prior art, and the produced zirconia ceramic has high metalized surface quality and strong controllability. However, since the metallization process in the invention does not undergo the steps of roughening and the like, holes cannot be formed on the surface of the product, and the adhesion of the subsequent plating layer is difficult to reach a better level.
Chinese patent CN103755390A discloses a method for improving the metallization strength of zirconia ceramics in an oxygen sensor, comprising the following steps: firstly, respectively preparing metalized transition layer slurry and metalized working layer slurry; then covering the surface of the zirconia chip substrate with the metalized transition layer slurry to form a metalized transition layer; covering the surface of the obtained metalized transition layer with the metalized working layer slurry, drying, and sintering at 1350-1600 ℃; the invention can improve the metallization strength of the zirconia ceramics, prolong the service life of the oxygen sensor and has practicability. However, the method of the invention requires a high-temperature sintering process, and has relatively high equipment requirements and high energy consumption requirements, thereby increasing the cost to a certain extent.
Aiming at the problems of high equipment requirement, high cost, poor adhesion and the like of the zirconia ceramic metallization process, the metallization process of the zirconia ceramic is needed to be found, so that the process is simple and convenient to operate, low in equipment requirement and low in cost, and meanwhile, the adhesion of a coating is guaranteed, and excellent adhesion is obtained.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a metallization process of zirconia ceramics. The process is simple and convenient to operate, has low equipment requirement, can etch uniform holes on the surface of the zirconia ceramic, is beneficial to smooth follow-up metal flow, and provides guarantee for the adhesion of a plating layer, thereby obtaining excellent adhesion.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a metallization process of zirconia ceramics, which comprises the following steps:
(1) oil removal: adding zirconia ceramic into an oil powder removing aqueous solution, soaking and performing ultrasonic treatment;
(2) coarsening: heating a mixed solution of hydrofluoric acid, microetching salt and a surfactant, adding the deoiled zirconia ceramic, and soaking;
(3) adjusting; heating the working solution of the regulator, adding the coarsened zirconia ceramic, and soaking;
(4) and (3) activation: heating the colloidal palladium working solution, adding the adjusted zirconia ceramic, and soaking;
(5) and (3) gel releasing: heating the working solution of the debonder, adding the activated zirconia ceramic, and soaking;
(6) chemical copper: heating the copper precipitation agent working solution, adding the peptized zirconia ceramics, and soaking;
(7) electroplating: and plating a metal coating on the surface of the oxidized ceramic zirconium subjected to chemical copper plating.
Further, the oil removing powder in the step (1) is a product of Madei science and technology (Suzhou) Limited with model number ENPREP NS 35; the microetching salt in the step (2) is a product of Midamei technology (Suzhou) ltd with the model number ENPLATE BS70, and the surfactant is a product of Midamei technology (Suzhou) ltd with the model number ENPREP FLEX G; the regulator in the step (3) is a product with the model number of M-Condition of McSt, Inc; the colloidal palladium in the step (4) is a product with the model number of M-ACTIVATE HA of McSt & technologies (Suzhou); the dispergator in the step (5) is a product with the model number of M-Accelalate of Madei science and technology (Suzhou) Limited; the copper precipitation agent in the step (6) is a product of Midamei technology (Suzhou) Limited with model number MID Cu XD.
Furthermore, the dosages of the mixed liquid of the oil removing powder, the hydrofluoric acid, the microetching salt and the surfactant, the regulator, the colloidal palladium, the dispergator and the copper deposition agent in the steps are based on the capability of immersing the zirconia ceramics.
Further, the operation temperature of the ultrasound in the step (1) is 50-60 ℃, the heating temperature in the step (2) is 50-60 ℃, the heating temperature in the step (3) is 52-55 ℃, the heating temperature in the step (4) is 35-40 ℃, the heating temperature in the step (5) is 45-55 ℃, and the heating temperature in the step (6) is 50-55 ℃.
Preferably, the heating temperature in step (1) and step (2) is 55 ℃, the heating temperature in step (3) is 53 ℃, the heating temperature in step (4) is 36 ℃, the heating temperature in step (5) is 50 ℃, and the heating temperature in step (6) is 52 ℃.
Further, the soaking time in the step (1) is 3-5min, the soaking time in the step (2) is 30-60min, the soaking time in the step (3) is 3-8min, the soaking time in the step (4) is 5-10min, and the soaking time in the step (5) is 3-5 min. And (4) determining the soaking time in the step (6) according to the requirement of the copper thickness.
Preferably, the soaking time in the step (1) is 4min, the soaking time in the step (2) is 45min, the soaking time in the step (3) is 5min, the soaking time in the step (4) is 6min, and the soaking time in the step (5) is 3 min.
Further, the operational concentrations of the hydrofluoric acid, the microetching salt and the surfactant in the step (2) are respectively as follows: 300-500ml/L, 100-300g/L and 5-10 ml/L.
Preferably, the operational concentrations of the hydrofluoric acid, the microetching salt and the surfactant in the step (2) are respectively as follows: 400ml/L, 200g/L and 8 ml/L.
Further, the concentration of the oil powder removing aqueous solution in the step (1) is 40-60g/L, the operating concentration of the colloidal palladium working solution in the step (4) is 30-70ppm, and the operating concentration of the dispergator working solution in the step (5) is 5-20 ml/L.
Preferably, the concentration of the oil powder removing aqueous solution in the step (1) is 50g/L, the operating concentration of the colloidal palladium working solution in the step (4) is 50ppm, and the operating concentration of the dispergator working solution in the step (5) is 10 ml/L.
Further, the modifier in the step (3) includes M-Condition PartA, M-Condition PartB and M-Condition PartC.
Preferably, the operating concentrations of M-Condition PartA, M-Condition PartB, and M-Condition PartC are 60-140ml/L, 30-80ml/L, and 10-40ml/L, respectively.
Further preferably, the operating concentrations of M-Condition PartA, M-Condition PartB, and M-Condition PartC are 100ml/L, 50ml/L, and 25ml/L, respectively.
The invention also provides the zirconia ceramic prepared by the metallization process.
The technical effects obtained by the invention are as follows:
1. the process flow of the invention can etch uniform holes on the surface of the zirconia ceramic, is beneficial to the smooth operation of the subsequent metal flow, and provides guarantee for the adhesion of the coating, thereby obtaining excellent adhesion. 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 catalyst colloid palladium and provides reliable adhesive force for a subsequent plating layer, and is the most critical step in the process and the guarantee of the binding force of a sample 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 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 MID Cu XD series products in the chemical copper step can ensure that a layer of metal copper is uniformly deposited on the surface of a catalyzed sample, and then copper ions can be continuously deposited (with the speed of 4-6um/H) under the catalysis of fresh copper so as to provide a conductive layer for subsequent electroplating; the plating step may be performed by adding gold or nickel or the like as necessary.
2. The process is convenient to operate, the whole process is a wet process, and only soaking is needed; in addition, the requirement on equipment is reduced, and the production cost of the product is reduced.
Detailed Description
It should be noted that the oil removing powder used in the present invention is a product of the company EnPREP NS 35, Madea technologies, Inc. (Suzhou); the microetching salt is a product of Midamei technology (Suzhou) Inc. model number ENPLATE BS70, and the surfactant is a product of Midamei technology (Suzhou) Inc. model number ENPREP FLEX G; the regulator is M-Condition product of Midamei technology (Suzhou) Limited; the colloidal palladium is a product of Mr-ACTIVATE HA, McSt.Technolgica (Suzhou); the dispergator is a product with the model number of M-Accelalate of McCleis technology (Suzhou) and Co; the copper precipitation agent is a product with the model number MID Cu XD of Midamei technology (Suzhou) and limited, and other raw materials are common commercial products, so the source of the copper precipitation agent is not particularly limited.
Example 1
A process for metallizing zirconia ceramics comprising the steps of:
(1) oil removal: adding zirconia ceramic into an oil powder removing aqueous solution, soaking for 3min and carrying out ultrasonic treatment at an operating temperature of 60 ℃;
(2) coarsening: heating the mixed solution of hydrofluoric acid, microetching salt and surfactant to 50 ℃, adding the deoiled zirconia ceramic, and soaking for 60 min;
(3) adjusting; heating the working solution of the regulator to 52 ℃, adding the coarsened zirconia ceramic, and soaking for 8 min;
(4) and (3) activation: heating the colloidal palladium working solution to 35 ℃, adding the adjusted zirconia ceramics, and soaking for 10 min;
(5) and (3) gel releasing: heating the working solution of the debonder to 45 ℃, adding the activated zirconia ceramic, and soaking for 5 min;
(6) chemical copper: heating the copper precipitation agent working solution to 50 ℃, adding the peptized zirconia ceramics, and soaking for 15 min;
(7) electroplating: and plating other metal plating layers on the surface of the zirconia ceramic subjected to chemical copper plating.
Wherein, the operational concentrations of the hydrofluoric acid, the microetching salt and the surfactant in the step (2) are respectively as follows: 300ml/L, 100g/L and 5 ml/L. The operation concentration of the oil powder removing aqueous solution in the step (1) is 40g/L, the operation concentration of the colloidal palladium working solution in the step (4) is 70ppm, and the operation concentration of the dispergator working solution in the step (5) is 5 ml/L. The working solution of the regulator in the step (3) comprises M-Condition PartA, M-Condition PartB and M-Condition PartC working solutions, and the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC working solutions are 60ml/L, 30ml/L and 10ml/L respectively.
Example 2
A process for metallizing zirconia ceramics comprising the steps of:
(1) oil removal: adding zirconia ceramic into an oil powder removing aqueous solution, soaking for 5min and carrying out ultrasonic treatment at an operating temperature of 50 ℃;
(2) coarsening: heating the mixed solution of hydrofluoric acid, microetching salt and surfactant to 60 ℃, adding the deoiled zirconia ceramic, and soaking for 30 min;
(3) adjusting; heating the working solution of the regulator to 55 ℃, adding the coarsened zirconia ceramic, and soaking for 3 min;
(4) and (3) activation: heating the colloidal palladium to 40 ℃, adding the adjusted zirconia ceramic, and soaking for 5 min;
(5) and (3) gel releasing: heating the working solution of the debonder to 55 ℃, adding the activated zirconia ceramic, and soaking for 3 min;
(6) chemical copper: heating the copper precipitation agent working solution to 55 ℃, adding the peptized zirconia ceramics, and soaking for 15 min;
(7) electroplating: and plating a metal coating on the surface of the oxidized ceramic zirconium subjected to chemical copper plating.
Wherein, the operational concentrations of the hydrofluoric acid, the microetching salt and the surfactant in the step (2) are respectively as follows: 500ml/L, 300g/L and 10 ml/L. The operation concentration of the oil powder removing aqueous solution in the step (1) is 60g/L, the operation concentration of the colloidal palladium working solution in the step (4) is 30ppm, and the operation concentration of the dispergator working solution in the step (5) is 20 ml/L. The working solution of the regulator in the step (3) comprises M-Condition PartA, M-Condition PartB and M-Condition PartC working solutions, and the operating concentrations of the M-Condition PartB, the M-Condition PartC and the M-Condition PartC working solutions are 140ml/L, 80ml/L and 40ml/L respectively.
Example 3
A process for metallizing zirconia ceramics comprising the steps of:
(1) oil removal: adding zirconia ceramic into an oil powder removing aqueous solution, soaking for 4min and carrying out ultrasonic treatment at an operation temperature of 55 ℃;
(2) coarsening: heating the mixed solution of hydrofluoric acid, microetching salt and surfactant to 55 ℃, adding the deoiled zirconia ceramic, and soaking for 45 min;
(3) adjusting; heating the working solution of the regulator to 53 ℃, adding the coarsened zirconia ceramic, and soaking for 5 min;
(4) and (3) activation: heating the colloidal palladium working solution to 36 ℃, adding the adjusted zirconia ceramics, and soaking for 6 min;
(5) and (3) gel releasing: heating the working solution of the debonder to 50 ℃, adding the activated zirconia ceramic, and soaking for 3 min;
(6) chemical copper: heating the copper precipitation agent working solution to 52 ℃, adding the peptized zirconia ceramics, and soaking for 15 min;
(7) electroplating: and plating a metal coating on the surface of the oxidized ceramic zirconium subjected to chemical copper plating.
Wherein, the operational concentrations of the hydrofluoric acid, the microetching salt and the surfactant in the step (2) are respectively as follows: 400ml/L, 200g/L and 8 ml/L. The operation concentration of the oil powder removing aqueous solution in the step (1) is 50g/L, the operation concentration of the colloidal palladium working solution in the step (4) is 50ppm, and the operation concentration of the dispergator working solution in the step (5) is 10 ml/L. The working solution of the regulator in the step (3) comprises M-Condition PartA, M-Condition PartB and M-Condition PartC working solutions, and the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC working solutions are respectively 100ml/L, 50ml/L and 25 ml/L.
Comparative example 1
The only difference from example 3 is that the microetching salt in step (2) was replaced with ammonium chloride.
Comparative example 2
The only difference from example 3 is that the colloidal palladium in step (4) was replaced with colloidal palladium in a hydrochloric acid system (a colloidal palladium product of model MACTIVATE 360 from mideme technologies, su, ltd.).
Comparative example 3
The only difference from example 3 is that the surfactant in step (2) was replaced with a product of METEX T103, a company, madmet technologies (suzhou).
Comparative example 4
The only difference from example 3 is that the operative concentrations of hydrofluoric acid, microetching salt and surfactant in step (2) were 280ml/L, 320g/L and 4ml/L, respectively.
Comparative example 5
The difference from the example 3 is only that the operation concentration of the degreasing powder aqueous solution in the step (1) is 35g/L, the operation concentration of the colloidal palladium working solution in the step (4) is 75ppm, and the operation concentration of the dispergator working solution in the step (5) is 3 ml/L.
Comparative example 6
The only difference from example 3 is that no surfactant was added in step (2).
Adhesion test
Test 1: marking a cross grid shape on the surface of a product by using a hundred grid cutter, counting 100 grids (1cm multiplied by 1cm), slightly sweeping the cut to a base material by using a soft brush along each diagonal line of the cross grid for several times, then sweeping forwards and backwards for several times, pulling 3 times by using 3M600# adhesive tape, observing the conditions of respective areas, counting the percentage of the area without falling to the total area, and obtaining the following table 1:
TABLE 1
| Examples of the invention | Non-shedding area ratio (%) |
| Example 1 | 100 |
| Example 2 | 100 |
| Example 3 | 100 |
| Comparative example 1 | 92 |
| Comparative example 2 | 94 |
| Comparative example 3 | 88 |
| Comparative example 4 | 95 |
| Comparative example 5 | 90 |
| Comparative example 6 | 83 |
As can be seen from table 1, after the tape was scratched with a hundred-grid knife, the tape was pulled 3 times using 3M600# tape, and no peeling occurred on the surfaces of the products in examples 1 to 3, indicating that the surfaces of the products in the present invention have excellent adhesion. Comparing each proportion with example 3, it is found that when the microetching salt or the surfactant in the roughening step is replaced or the operating concentration of each substance is changed, the adsorption condition of the catalyst colloid palladium is correspondingly changed due to the influence on the size and uniformity of the surface holes of the product, and the adhesion of the subsequent plating layer is further influenced, and especially when the surfactant is not added, the adhesion of the surface of the product is obviously reduced. When the operating concentration of various working solutions is changed in other steps, the adhesion of the coating is also affected to a certain extent due to the change of properties such as the surface electrical property of the product, and the corresponding reduction is further caused.
Test 2: the adhesion of each example product was tested by the pull-off method (see in detail ASTM D4541-2017 standard test method for peel strength of coatings with a portable adhesion tester), 3 test points were set for each sample, the average was calculated and the test results were statistically reported to table 2:
TABLE 2
| Examples of the invention | Metallization Strength (MPa) |
| Example 1 | 62 |
| Example 2 | 68 |
| Example 3 | 70 |
| Comparative example 1 | 58 |
| Comparative example 2 | 62 |
| Comparative example 3 | 55 |
| Comparative example 4 | 62 |
| Comparative example 5 | 60 |
| Comparative example 6 | 50 |
As can be seen from table 2, the result of the drawing method test is closer to the result trend of the one hundred grid test, wherein the product in examples 1 to 3 has higher metallization strength, which can reach 62 to 70MPa, and when the material handling concentration in the processes of coarsening, activation, dispergation, etc. is changed, the product surface property is changed, and finally the metallization strength of the product is correspondingly reduced.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. A metallization process of zirconia ceramics is characterized in that: the method comprises the following steps:
(1) oil removal: adding zirconia ceramic into an oil powder removing aqueous solution, soaking and performing ultrasonic treatment;
(2) coarsening: heating a mixed solution of hydrofluoric acid, microetching salt and a surfactant, adding the deoiled zirconia ceramic, and soaking;
(3) adjusting; heating the working solution of the regulator, adding the coarsened zirconia ceramic, and soaking;
(4) and (3) activation: heating the colloidal palladium working solution, adding the adjusted zirconia ceramic, and soaking;
(5) and (3) gel releasing: heating the working solution of the debonder, adding the activated zirconia ceramic, and soaking;
(6) chemical copper: heating the copper precipitation agent working solution, adding the peptized zirconia ceramics, and soaking;
(7) electroplating: and plating a metal coating on the surface of the oxidized ceramic zirconium subjected to chemical copper plating.
2. The metallization process of claim 1, wherein: the oil removing powder in the step (1) is a product of Madei science and technology (Suzhou) Limited company with the model number of ENPREP NS 35; the microetching salt in the step (2) is a product of Midamei technology (Suzhou) ltd with the model number ENPLATE BS70, and the surfactant is a product of Midamei technology (Suzhou) ltd with the model number ENPREP FLEX G; the regulator in the step (3) is a product with the model number of M-Condition of McSt, Inc; the colloidal palladium in the step (4) is a product with the model number of M-ACTIVATE HA of McSt & technologies (Suzhou); the dispergator in the step (5) is a product with the model number of M-Accelalate of Madei science and technology (Suzhou) Limited; the copper precipitation agent in the step (6) is a product of Midamei technology (Suzhou) Limited with model number MID Cu XD.
3. The metallization process of claim 1, wherein: the operation temperature of the ultrasound in the step (1) is 50-60 ℃, the heating temperature in the step (2) is 50-60 ℃, the heating temperature in the step (3) is 52-55 ℃, the heating temperature in the step (4) is 35-40 ℃, the heating temperature in the step (5) is 45-55 ℃, and the heating temperature in the step (6) is 50-55 ℃.
4. The metallization process of claim 1, wherein: the soaking time in the step (1) is 3-5min, the soaking time in the step (2) is 30-60min, the soaking time in the step (3) is 3-8min, the soaking time in the step (4) is 5-10min, and the soaking time in the step (5) is 3-5 min.
5. The metallization process of claim 1, wherein: in the step (2), the operational concentrations of the hydrofluoric acid, the microetching salt and the surfactant are respectively as follows: 300-500ml/L, 100-300g/L and 5-10 ml/L.
6. The metallization process of claim 1, wherein: the concentration of the oil powder removing aqueous solution in the step (1) is 40-60 g/L.
7. The metallization process of claim 1, wherein: the operating concentration of the colloidal palladium working solution in the step (4) is 30-70ppm, and the operating concentration of the dispergator working solution in the step (5) is 5-20 ml/L.
8. The metallization process of claim 1, wherein: the modifier in the step (3) includes M-Condition PartA, M-Condition PartB and M-Condition PartC.
9. The metallization process of claim 8, wherein: the operating concentrations of the M-Condition PartA, the M-Condition PartB and the M-Condition PartC are 60-140ml/L, 30-80ml/L and 10-40ml/L respectively.
10. The zirconia ceramic produced by the metallization process of any one of claims 1 to 9.
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