CN115073213B - Coloring process of ceramic - Google Patents
Coloring process of ceramic Download PDFInfo
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- CN115073213B CN115073213B CN202210789036.7A CN202210789036A CN115073213B CN 115073213 B CN115073213 B CN 115073213B CN 202210789036 A CN202210789036 A CN 202210789036A CN 115073213 B CN115073213 B CN 115073213B
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Abstract
The invention relates to a coloring process of ceramics, which comprises the steps of dissolving a coloring material in a mixed solution of an organic solvent and water, adding a pH regulator to regulate the pH value to 3-5 to obtain a coloring solution, and dyeing a ceramic green body by using the coloring solution to obtain a dyed ceramic green body; the ratio of the organic solvent to water is 85-99wt%:1 to 15wt%. According to the invention, the ceramic green body is selected for dyeing, the solvent of the coloring solution can partially dissolve the plasticizer and/or the adhesive on the surface of the ceramic green body under the combined action of the mixed solution of the organic solvent and the water and the proper pH value, and the pigment is adhered by the plasticizer and/or the adhesive, so that the pigment enters the structure of the ceramic green body while the integral microstructure of the ceramic green body is not damaged, the process flow is saved, and the production cost is reduced.
Description
Technical Field
The invention relates to the technical field of ceramic coloring processes, in particular to a ceramic coloring process.
Background
The dental prosthesis is mostly prepared from white zirconia ceramics, and although the color of the primary tooth can be simulated easily, the actual use requirement of the dental prosthesis can not be completely met. By introducing a dyeing process to adjust the color and transmittance of the zirconia ceramic, the closeness of the aesthetic effect of the prepared dental prosthesis and the original teeth can be increased. The dyeing process of ceramics in the prior art generally has the problems of complicated dyeing process steps, complex colorant components, uneven distribution of the colorant in the dyed ceramics, low approach degree with the primary teeth when the dyed ceramics is used as the dental prosthesis, and the like.
Disclosure of Invention
The invention aims to solve the problems and provide a coloring process of ceramics.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a ceramic coloring process comprises the steps of dissolving a coloring material in a mixed solution of an organic solvent and water, adding a pH regulator to adjust the pH to 3-5 to obtain a coloring solution, and dyeing a ceramic green body by using the coloring solution to obtain a dyed ceramic green body; the ratio of the organic solvent to the water is 85-99wt%:1-15wt%.
According to the ceramic coloring process, the pigment is dissolved in the mixed solution of the organic solvent and the water, the pH value is adjusted, the pigment is dissolved in the mixed solution to generate coloring ions, organic matters such as a bonding agent and/or a plasticizer in the ceramic green body are partially dissolved by the mixed solution, and the bonding agent and/or the plasticizer liquid organic matters formed after the dissolution are wrapped and drive the coloring ions to move in the ceramic green body, so that the coloring ions are uniformly distributed in the ceramic green body. The pH value of 3-5 avoids the sedimentation of coloring ions on one hand, so that the coloring ions are suspended in the solution, and the uniform distribution of coloring ions is enhanced; on the other hand, the coloring ions are better attached to the ceramic green body by the erosion action on the ceramic green body.
Preferably, the ceramic green body comprises a binder and a plasticizer, and the mass ratio of the binder to the plasticizer is 1.5-5:1. the proportion of the adhesive and the plasticizer corresponds to the proportion of the organic solvent and the water in the mixed solution of the organic solvent and the water and the pH value of the mixed solution. It can be said that the ratio of the organic solvent to water and the pH value of the mixed solution are determined by the ratio of the binder and the plasticizer.
Preferably, the pH adjusting agent comprises one or more of acetic acid, citric acid, hydrochloric acid or nitric acid.
Preferably, the dyeing of the ceramic green body with the coloring solution includes: and immersing the ceramic green body in the coloring solution for 0.5-1min under the air pressure of 1-100Pa, and keeping for 0.5-1.5min after releasing the vacuum.
The vacuum degree is 1Pa to 100Pa, and even under relatively high vacuum degree, the ceramic green body can still maintain no deformation or no breakage, which shows that the process window of the ceramic coloring process is larger and is suitable for large-scale production.
Preferably, the colorant includes a metal cation having a concentration of 1 to 100g/L in the coloring solution; the metal cations comprise one or more of praseodymium ions, erbium ions, cerium ions, iron ions, cobalt ions or neodymium ions. The colorant is a soluble metal salt, which further comprises an anion; the anion comprises one or more of chloride ion, acetate, nitrate, thiocyanate or sulfate.
Alternatively, the coloring material may be a metal oxide, the metal oxide is melted into paraffin to form a coloring solution, and after the green body is sufficiently impregnated with the paraffin-based coloring solution, the coloring material oxide is fixed in the ceramic green body through solidification of the paraffin. The coloring solution is adopted for impregnation, so that the drying procedure can be omitted, the process is simplified, and the impregnation effect same as that of the water-alcohol-based coloring solution can be prepared.
Further preferably, the dyeing of the ceramic green body with the coloring solution further comprises: applying a pulsed current to the coloring solution while the ceramic green body is immersed in the coloring solution; the current of the pulse current is 1-20mA, the action period is 1-3, and one single period comprises 8-20s of action time, 4-10s of power-off time and 8-20s of action time.
In order to avoid the phenomenon that metal ions cannot reach the inside of the green body due to the aggregation on the surface or near surface of the green body and cause uneven dyeing, for example, in praseodymium ions, cerium ions, neodymium ions and erbium ions, the larger the atomic number of the erbium ions is, the smaller the ion radius is, the smallest the erbium ion radius is, and the erbium ions are most likely to aggregate on the surface layer of the green body because the number of electrons of the 4 kinds of ions is the same. Pulse current is applied, so that positively charged metal cations can be fully transferred to the interior of a ceramic green body under the drive of negative charges in the current, and are orderly attached to the inner wall of the pore structure of the green body, and the deposition and attachment of the cations have self-saturation under the action of an electric field, so that the uniform distribution of the metal cations with dyeing effect in the green body is further ensured.
Preferably, the organic solvent comprises one or more of methanol, ethanol or glycerol.
Preferably, the obtained dyed ceramic green body is dried at 80-85 ℃, and the dried dyed ceramic green body is subjected to press forming, degumming treatment and sintering treatment in sequence. After the dyed ceramic green body is treated, coloring ions are firmly pinned on the ceramic green body, and the ceramic or ceramic composite material prepared by the dyed ceramic green body is ensured to have uniform color.
Preferably, the sintering treatment further comprises an annealing treatment.
The beneficial effects of the invention at least comprise:
according to the ceramic coloring process, the coloring solution is obtained by adjusting the proportion of the organic solvent and the water and the pH value, and the obtained coloring solution is used for coloring the ceramic green body, so that pigment ions are uniformly dispersed and firmly combined with the ceramic green body on the premise of ensuring that the integral structure of the ceramic green body is not damaged, and further, the ceramic or ceramic composite material prepared from the colored ceramic green body is uniform in color.
According to the invention, the ceramic green body is selected for dyeing, so that the process flow is saved, and the production cost is reduced; the coloring process is suitable for various ceramic green bodies; the dyed ceramic which is closer to the aesthetic effect of the primary teeth is obtained while the mechanical property of the dyed ceramic is ensured.
Drawings
FIG. 1 is a scanning electron microscope test chart of the dyed ceramic obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope test chart of the dyed ceramic obtained in example 2 of the present invention;
FIG. 3 is a scanning electron microscope test chart of the dyed ceramics obtained in example 5 of the present invention.
Detailed Description
In order to facilitate an understanding of the invention, preferred embodiments of the invention are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Example 1
Preparation of ceramic green bodies: in the embodiment, the dispersant is selected from Zhongjing grease SELOSOL920, and the plasticizer is selected from polyvinyl alcohol (PVA for short); dispersing zirconium oxide ceramic powder, 0.8wt% of dispersant, 3wt% of binder and 1wt% of plasticizer in a solvent, and then performing ball milling treatment to obtain slurry; the content of the zirconia ceramic powder in the obtained slurry is 15vol%. And (3) defoaming the obtained slurry, then performing bidirectional freeze casting, and then performing low-pressure freeze drying to obtain parallel layered ceramic green bodies.
Preparation of coloring solution: in the embodiment, the coloring material is praseodymium nitrate, erbium nitrate and neodymium nitrate, the coloring material comprises 0.22g of praseodymium nitrate, 10.06g of erbium nitrate, 1.58g of neodymium nitrate, 96.5g of absolute ethyl alcohol and 3.5g of water, and the components are mixed and then adjusted to have a pH value of 4-5 by using acetic acid. Dyeing: slowly immersing the obtained ceramic green body in the coloring solution for 0.5min under the air pressure of 1Pa, and then immersing for 1min under the vacuum environment to obtain the dyed ceramic green body.
The resulting dyed ceramic green body was dried at 80 ℃ for 1h to evaporate the solvent.
Compression: and impregnating paraffin, and applying a compression force in a direction vertical to the laminated structure to compress the green body, wherein the magnitude of the compression force is 0.2MPa, and the volume shrinkage rate of the green body after paraffin impregnation after compression is 30%.
Degumming treatment and sintering treatment: degumming and sintering the compressed ceramic green body; wherein the degumming treatment temperature is 600 deg.C, the time is 2h, the sintering treatment temperature is 1350 deg.C, and the time is 2h.
Impregnating resin: filling liquid resin into the pore structure of the ceramic framework, and adding an initiator to carry out in-situ polymerization with the liquid resin to generate a high polymer material; and (4) annealing to obtain the dyed ceramic polymer composite material.
Example 2
The procedure of example 2 was the same as in example 1 except for the following steps.
Preparation of coloring solution: in the embodiment, the coloring material is praseodymium sulfate, the coloring agent comprises 1.3g of praseodymium sulfate, 95.5g of absolute ethyl alcohol and 4.5g of water, and the components are mixed and then adjusted to pH 4-5 by acetic acid.
Dyeing: the obtained ceramic green body is slowly immersed in the coloring solution for 1min under the air pressure of 1Pa, and then immersed for 1min under the vacuum environment.
Example 3
Preparation of ceramic green bodies: in the embodiment, the dispersant is Zhongjing grease SELOSOL920 and the plasticizer is PVA, and the ceramic powder comprises 95wt% of zirconia powder and 5wt% of alumina powder. Dispersing the ceramic powder, 0.8wt% of dispersant, 5wt% of binder and 1wt% of plasticizer in a solvent, and then performing ball milling treatment to obtain slurry; the content of the ceramic powder in the obtained slurry was 15vol%. And (3) defoaming the obtained slurry, then performing bidirectional freeze casting, and then performing low-pressure freeze drying to obtain ceramic green bodies with mutually parallel layered structures.
Preparation of coloring solution: in the embodiment, the coloring material is cobalt acetate and chromium sulfate, the coloring agent comprises 1.75g of cobalt acetate, 10g of chromium sulfate, 99g of absolute ethyl alcohol and 1g of water, and the components are mixed and then the pH value is adjusted to 4-5 by acetic acid.
Dyeing: the obtained ceramic green body is slowly immersed in the coloring solution for 0.8min under the air pressure of 1Pa, and then immersed for 1min under a vacuum environment. The resulting dyed ceramic green body was dried at 80 ℃ for 1h to evaporate the solvent.
Degumming treatment and sintering treatment: degumming and sintering the compressed ceramic green body; wherein the degumming treatment temperature is 600 deg.C, the time is 2h, the sintering treatment temperature is 1350 deg.C, and the time is 2h.
Impregnating resin: filling liquid resin into the pore structure, and adding an initiator to carry out in-situ polymerization with the liquid resin to generate a high polymer material; and (5) annealing to obtain the dyed ceramic polymer composite material.
Example 4
The method for preparing the ceramic green body, the method for preparing the coloring solution, and the method for dyeing in example 4 are the same as those described in example 1.
Drying the obtained dyed ceramic green body at 80 ℃ for 1h to volatilize the solvent;
degumming and sintering: degumming and sintering the obtained ceramic green body; wherein the degumming treatment temperature is 600 ℃ and the time is 2h, the sintering treatment temperature is 1350 ℃ and the time is 2h;
impregnating resin: filling liquid resin into the pore structure of the ceramic framework, and adding an initiator to carry out in-situ polymerization with the liquid resin to generate a high polymer material; and obtaining dyed ceramics after annealing treatment.
Example 5
Preparation of ceramic green bodies: in the embodiment, the dispersant is selected from the Beijing grease SELOSOL920, the adhesive is selected from the Gillendon, and the plasticizer is selected from the PVA; dispersing zirconia ceramic powder, 0.8wt% of dispersant, 1.6wt% of binder and 1wt% of plasticizer in a solvent to obtain slurry; the content of the zirconia ceramic powder in the obtained slurry was 20vol%. And (3) defoaming the obtained slurry, then performing bidirectional freeze casting, and then performing low-pressure freeze drying to obtain a ceramic green body with a honeycomb structure.
Preparation of coloring solution: in the embodiment, the coloring material is praseodymium sulfate, erbium nitrate and neodymium chloride, the coloring agent comprises 0.22g of praseodymium sulfate, 10.06g of erbium nitrate, 1.58g of neodymium chloride, 85g of absolute ethyl alcohol and 15g of water, and the components are mixed and then the pH value is adjusted to 4-5 by acetic acid.
Dyeing: slowly immersing the obtained ceramic green body in the coloring solution for 0.5min under the air pressure of 1Pa, and then immersing for 1min under the vacuum environment to obtain the dyed ceramic green body.
Drying the obtained dyed ceramic green body at 80 ℃ for 1h to volatilize the solvent;
degumming treatment and sintering treatment: degumming and sintering the obtained ceramic green body; wherein the degumming treatment temperature is 600 ℃ and the time is 2h, the sintering treatment temperature is 1350 ℃ and the time is 2h;
impregnating resin: filling liquid resin into the pore structure of the ceramic framework, and adding an initiator to carry out in-situ polymerization with the liquid resin to generate a high polymer material; and obtaining dyed ceramics after annealing treatment.
Example 6
Example 6 differs from example 1 in that the dyeing: slowly immersing the obtained ceramic green body in a coloring solution under the air pressure of 1Pa for 0.5min, applying 15mA current for 1min, adopting intermittent current, electrifying for 8-20 seconds, powering off for 4-10 seconds, electrifying for 8-20 seconds, repeating for one cycle, and electrifying for 3 cycles to obtain the dyed ceramic green body.
Example 7
The difference compared to example 1 is the preparation of the coloring solution: the components of the colorant comprise 0.22g of praseodymium nitrate, 10.06g of erbium nitrate and 1.58g of neodymium nitrate, the praseodymium nitrate, the erbium nitrate and the neodymium nitrate are treated to form corresponding metal oxides, then the colorant metal oxides are melted into paraffin to form a coloring solution, and after the paraffin-based coloring solution is fully impregnated into the green body, the colorant oxides are fixed in the ceramic green body through the solidification of the paraffin.
The ceramic green body may be prepared by a method other than the methods described in examples 1 to 7 of the present invention, and the examples of the present invention are not limited thereto as long as a ceramic green body having a pore structure can be obtained.
Test example 1
Scanning electron microscope tests are respectively carried out on the dyed ceramics obtained in the embodiments 1 and 2 and the embodiment 5 of the present invention, fig. 1 is a scanning electron microscope test chart of the dyed ceramics obtained in the embodiment 1 of the present invention, fig. 2 is a scanning electron microscope test chart of the dyed ceramics obtained in the embodiment 2 of the present invention, and fig. 3 is a scanning electron microscope test chart of the dyed ceramics obtained in the embodiment 5 of the present invention, wherein white particles in the test chart are color-developing particles, as shown in fig. 1-3, the color-developing particles are uniformly distributed in the structures of the ceramic green compacts obtained by different preparation methods, and the ceramic green compacts maintain the original microstructure after being subjected to dyeing treatment. Therefore, during dyeing treatment in the scheme of the invention, the solvent partially dissolves part of the plasticizer and/or the adhesive in the ceramic green body structure, so that the dissolved plasticizer and/or the dissolved adhesive adhere to the pigment, the pigment is uniformly distributed in the ceramic green body structure, and the color-developing particles generated by the pigment are remained in the ceramic green body structure in the post-treatment process, so that the remaining rate of the color-developing particles is improved, the distribution uniformity of the color-developing particles is ensured, and the dyeing effect is further improved; meanwhile, the dissolved plasticizer and/or adhesive is cured again in the post-treatment process, the microstructure of the ceramic green body is not damaged, the mechanical property of the ceramic green body is not changed, and the obtained dyed ceramic has better physical properties.
Comparative example 1
Comparative example 1 differs from example 1 in that the Ph of the coloring solution is 8 and the other treatment methods are the same.
Comparative example 2
The difference between the comparative example 2 and the example 1 is that the mass ratio of the organic solvent to the water is 80:20, and the rest treatment modes are the same.
Comparative example 3
Comparative example 3 differs from example 1 in that the mass ratio of binder to plasticizer in the green body is 1:2, the rest treatment modes are the same.
Test example 2
The ceramics obtained in examples 1 to 7 and comparative examples 1 to 3 were respectively tested for fracture toughness, flexural strength, visible light transparency and color parameters, 5 samples of each group were tested, and the average value of 5 measurements and the deviation value of visible light transparency and color parameters were recorded.
Table 1 shows the average values of the tests for fracture toughness, flexural strength, visible light transparency and color parameters of the dyed ceramics obtained in examples 1 to 7 and comparative examples 1 to 3.
The Ph value in comparative example 1 is out of the preferable range of the present invention, the mass ratio of the organic solvent and water in comparative example 2 is out of the preferable range of the present invention, and the mass ratio of the binder to the plasticizer in the ceramic green body in comparative example 3 is out of the preferable range of the present invention. As can be seen from Table 1, the bending strength and fracture toughness of the dyed ceramics obtained in comparative examples 1-3 are inferior to those of the dyed ceramics obtained in the embodiment of example 1, which shows that in the preparation of the dyed ceramics by the ceramic dyeing process of the present invention, the mixed solution of the organic solvent and water partially dissolves part of the plasticizer and/or binder in the ceramic green body and does not destroy the microstructure of the ceramic green body within the preferable range in the technical solution of the present invention, and the physical properties of the obtained dyed ceramics are the best.
The color parameters of the dyed ceramics obtained in examples 1 to 7 and comparative examples 1 to 3 are known: the color of the dyed ceramics obtained in examples 1 and 7 is similar to the color number PANTONE 11-4301TCX in the PANTONE color chart, corresponding to the neutral color zone of the dental color palette; the color of the dyed ceramic obtained in example 2 is similar to the color number PANTONE 7553C in the PANTONE color chart, corresponding to the yellowish color region of the dental color palette; the color of the dyed ceramic obtained in example 3 is similar to the color number PANTONE P102-14C in the PANTONE color chart, and corresponds to the reddish color region of the dental color palette; the color of the dyed ceramic obtained in example 4 is similar to the color number PANTONE 482XGC in the PANTONE color chart, corresponding to the yellowish or neutral color region of the dental shade guide; the color of the dyed ceramic obtained in example 5 is similar to the color number PANTONE 13-1009TPX in the PANTONE color chart, corresponding to the yellowish or neutral color region of the dental color palette; the color of the dyed ceramic obtained in example 6 is similar to the color number PANTONE 9081C in the PANTONE color chart, and corresponds to the neutral color region of the dental color palette. The color of the dyed ceramic obtained in comparative example 1 is similar to the color number PANTONE 13-1009TPX in the PANTONE color chart, corresponding to the yellowish color region of the dental color palette; the color of the dyed ceramic obtained in comparative example 2 is similar to the color number PANTONE 12-6207TCX in the PANTONE color chart, and corresponds to the neutral color area of the dental color comparison board; comparative example 3 the dyed ceramic obtained had a color similar to the color number PANTONE 13-0607TCX in the PANTONE color chart, corresponding to a yellowish color zone of a dental color palette. However, the dyed ceramics obtained in comparative examples 1 to 3 have a large light transmittance compared to example 1, and when used as a dental prosthesis, the light transmittance and color coordination effect are poor, and the aesthetic effect of the original teeth cannot be approximated.
Therefore, on the premise of having better physical properties, within the preferable scope of the invention, the adjustment of the transmittance and the color of the dyed ceramic is realized, so that the obtained dyed ceramic presents different color tones, which can correspond to yellow, neutral and red areas in the dental color palette. When the dyed ceramic is used for manufacturing the dental restoration, the dental restoration with light transmittance and surface color texture closer to the original teeth can be provided according to the specific situation of the original teeth, so that more personalized service is provided for customers; the dyed ceramic with the similar aesthetic effect to the original teeth is obtained, and is coordinated with the original teeth, so that the tooth tissues of customers can be kept as much as possible, the principle requirements of oral restoration are met, meanwhile, the material preparation amount in the oral restoration process can be reduced, the cost of oral restoration is reduced, and the treatment cost of customers is further reduced.
Table 2 is a table of the difference between the maximum and minimum values in the visible light transparency test and the color parameter test for dyed ceramics made in examples 1-6 (example 7 performs substantially the same as example 1, and the performance data for example 7 is not separately listed)) and comparative examples 1-3.
As can be seen from Table 2, the deviation values of the visible light transmittance and the color parameters of the dyed ceramics obtained in examples 1 to 6 are smaller than those of the dyed ceramics obtained in comparative examples 1 to 3, which indicates that the dyed ceramics prepared by the technical scheme of the present invention have more uniform distribution of dyed ions and better color uniformity of the dyed ceramics; further, in example 6, compared with example 1, the dyed ceramics obtained in example 6 and example 1 belong to the same color tone, and the difference between the maximum value and the minimum value of the performance test results of the dyed ceramics obtained in example 6 is smaller than the difference between the maximum value and the minimum value of the performance test results of the dyed ceramics described in example 1, which shows that as a further preferable scheme, the dyed ions in the dyed ceramics obtained in example 6 are distributed more uniformly in the ceramic matrix.
All possible combinations of the technical features in the above embodiments may not be described for the sake of brevity, but should be considered as being within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above examples only express the preferred embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as the limitation of the invention patent scope. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (5)
1. A ceramic coloring process is characterized by comprising the steps of dissolving a coloring material in a mixed solution of an organic solvent and water, adding a pH regulator to adjust the pH to 3-5 to obtain a coloring solution, and dyeing a ceramic green body by using the coloring solution to obtain a dyed ceramic green body; the ratio of the organic solvent to the water is 85-99wt%:1-15wt%;
the coloring solution for dyeing the ceramic green body further comprises: applying a pulsed current to the coloring solution while the ceramic green body is immersed in the coloring solution; the current of the pulse current is 1-20mA, the action period is 1-3, and one single period comprises the action time of 8-20s, the power-off time of 4-10s and the action time of 8-20s;
the colorant comprises metal cations, and the concentration of the metal cations in the coloring solution is 1-100g/L;
the ceramic green body comprises a bonding agent and a plasticizer, wherein the plasticizer is PVA, and the mass ratio of the bonding agent to the plasticizer is (1.5-5): 1;
the pH regulator comprises one or more of acetic acid, citric acid, hydrochloric acid or nitric acid;
further comprising the steps of: and drying the obtained dyed ceramic green body at the temperature of 80-85 ℃, and sequentially carrying out compression molding, degumming treatment and sintering treatment on the dried dyed ceramic green body.
2. The coloring process of claim 1, wherein the coloring solution to color the ceramic green body comprises: and immersing the ceramic green body in the coloring solution for 0.5-1min under the pressure of 1-100Pa, and keeping for 0.5-1.5min after releasing the vacuum.
3. The coloring process according to claim 1, wherein the metal cations comprise one or more of praseodymium, erbium, cerium, iron, chromium, cobalt or neodymium ions.
4. The coloring process of claim 1, wherein the organic solvent comprises one or more of methanol, ethanol, or glycerol.
5. The coloring process according to claim 1, further comprising an annealing treatment after the sintering treatment.
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| JP2000144493A (en) * | 1998-11-17 | 2000-05-26 | Nippon Light Metal Co Ltd | Method for preventing fading in aluminum electrolytically pigmented material |
| CN102674888A (en) * | 2012-05-15 | 2012-09-19 | 深圳市爱尔创科技有限公司 | Coloring solution for dental zirconia ceramic product and using method of coloring solution |
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