A treatment method for enhancing the porosity of the surface of porous zirconia ceramics

Abstract

A processing method for enhancing the porosity of the surface of porous zirconia ceramics, comprising the following steps: preparing a corrosion solution, the corrosion solution is an acidic solution or an alkaline solution; heating the prepared corrosion solution in a water bath to 60°C-70°C; immersing the zirconia ceramic embryo body printed by direct writing into the corrosion solution heated in a water bath, stirring and corroding for 5min-200min, wherein the direct writing ink used for direct writing printing includes a pore-forming agent; removing the corroded sample from the corrosion solution and washing it with deionized water; drying the washed sample; placing the dried sample into a sintering furnace, sintering it in an air atmosphere, and taking out the sample after the temperature naturally drops to room temperature, completing sintering, and obtaining a porous ceramic product. The present invention can form a multi-scale and multi-structured pore structure on the outer surface of zirconia ceramics, with low cost, controllable material removal, overall uniformity, long storage time, and stable material system.

Description

Technical Field

[0001] The invention relates to the technical field of zirconia ceramics, and in particular to a processing method for enhancing the porosity of the surface of porous zirconia ceramics. Background Art

[0002] At present, the main method to increase the porosity of ceramic surfaces is to use laser etching, which uses high-power lasers to remove appropriate materials on the ceramic surface to prepare the corresponding pore structure. The disadvantage is that since ceramic materials generally have a high hardness, low-power lasers cannot destroy the ceramic structure. The use of high-power lasers means that more energy is consumed and the cost is high. At the same time, the laser etching light source can only directly irradiate the surface position that needs to be etched. For direct writing to form a multi-complex pore structure, the light source on the ceramic surface inside the overall structure cannot be directly irradiated, which means that the laser etching method is only suitable for simple structures whose surfaces can be directly irradiated by light. Another common surface treatment method is grinding, which also has the same defects as laser etching. It is costly and cannot achieve grinding treatment on the inner surface of complex structures. It is also difficult to grind the porosity of the grinding degree. It is easy to have uneven grinding degrees in various parts. Uneven treatment means that local defects are easy to occur. Summary of the invention

[0003] The purpose of the present invention is to provide a treatment method for enhancing the porosity of the surface of porous zirconia ceramics, which can form a multi-scale and multi-structure pore structure on the outer surface of zirconia ceramics, has low cost, controllable material removal amount, overall uniformity, long storage time, and stable material system.

[0004] To achieve this object, the present invention adopts the following technical solutions:

[0005] A method for enhancing the porosity of the surface of porous zirconia ceramics is provided, comprising the following steps:

[0006] preparing a corrosion solution, wherein the corrosion solution is an acidic solution or an alkaline solution;

[0007] Heat the prepared corrosion solution in a water bath to 60°C-70°C;

[0008] Immersing the direct-write printed zirconia ceramic body into a corrosion solution heated in a water bath, stirring and corroding for 5 minutes to 200 minutes, wherein the direct-write printing ink used in the direct-write printing includes a pore-forming agent;

[0009] The corroded sample was taken out from the corrosive solution and then cleaned with deionized water;

[0010] Dry the cleaned samples;

[0011] The dried sample is placed in a sintering furnace and sintered in an air atmosphere. The heating rate is controlled within the range of 0.2℃ / min-5℃ / min. The final sintering temperature is 1350℃-1550℃. The insulation time is 1 hour-4 hours. After the temperature naturally drops to room temperature, the sample is taken out and the sintering is completed to obtain a porous ceramic product.

[0012] As a preferred solution of the treatment method for enhancing the porosity of the surface of porous zirconia ceramics, the step of drying the cleaned sample comprises:

[0013] The cleaned samples are placed in a drying oven and dried at 40° C.-80° C. for 12 h-36 h.

[0014] As a preferred solution for the treatment method of enhancing the porosity of the surface of porous zirconia ceramics, the mass percentage concentration of the corrosion solution is 5%-40%.

[0015] As a preferred solution of the treatment method for enhancing the porosity of the surface of porous zirconia ceramics, the corrosion solution is sodium hydroxide, nitric acid or sulfuric acid.

[0016] As a preferred solution for the treatment method of enhancing the porosity of the surface of porous zirconia ceramics, the direct-writing ink used for the direct-writing zirconia ceramics comprises the following components in weight percentage: 50% to 70% zirconia powder, 10% to 20% photosensitive resin, 2% to 5% dispersant, 0.2% to 2% photoinitiator, and 10% to 40% pore-forming agent.

[0017] As a preferred solution for the treatment method of enhancing the porosity of the surface of porous zirconia ceramics, the pore-forming agent includes: one or more of oxidized starch, polymethyl methacrylate, wool, wood chips, and carbon fibers.

[0018] As a preferred solution for the treatment method of enhancing the porosity of the surface of porous zirconia ceramics, the photosensitive resin includes one or more of 1,6-hexanediol diacrylate, dipentaerythritol pentaacrylate, o-phenylphenoxyethyl acrylate, and trimethylolpropane triacrylate.

[0019] As a preferred solution for the treatment method of enhancing the porosity of the surface of porous zirconia ceramics, the dispersant includes one or more of fish oil, corn oil, ammonium citrate, and BYK-111.

[0020] As a preferred solution for the treatment method of enhancing the porosity of the surface of porous zirconia ceramics, the photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexyl-phenyl ketone.

[0021] Beneficial effects of the present invention: The processing method for enhancing the porosity of the surface of porous zirconia ceramics proposed in the present invention can form a multi-scale and multi-structure pore structure on the outer surface of zirconia ceramics, with low cost, controllable material removal amount, overall uniformity, long storage time, and stable material system. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments of the present invention. Obviously, the drawings described below are only some embodiments of the present invention, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0023] Figure 1 1. It is an appearance diagram of a zirconia ceramic embryo after direct writing printing (above) and a zirconia ceramic after surface treatment (below) according to an embodiment of the present invention;

[0024] Figure 2 This is a microscopic electron microscope image of the surface of the zirconium oxide ceramic after the pore-forming agent is removed according to an embodiment of the present invention;

[0025] Figure 3 This is a microscopic electron microscope image of the surface of the zirconia ceramic after treatment in one embodiment of the present invention;

[0026] Figure 4 (1) is a microscopic electron microscope image of the uncorroded zirconia ceramic embryo after direct writing printing;

[0027] Figure 4 (2) and (3) are microscopic electron microscope images of the zirconia ceramic blank after direct writing printing with different degrees of corrosion;

[0028] Figure 5 yes Figure 4 The corresponding electron microscope image after sintering. DETAILED DESCRIPTION

[0029] The embodiments of the present disclosure are described in detail below with reference to the accompanying drawings.

[0030] The following describes the embodiments of the present disclosure through specific examples, and those skilled in the art can easily understand other advantages and effects of the present disclosure from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present disclosure, rather than all of the embodiments. The present disclosure can also be implemented or applied through other different specific embodiments, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present disclosure. It should be noted that the following embodiments and features in the embodiments can be combined with each other without conflict. Based on the embodiments in the present disclosure, all other embodiments obtained by ordinary technicians in the field without making creative work are within the scope of protection of the present disclosure.

[0031] Example 1

[0032] Preparation of direct-write printed zirconia ceramic embryos

[0033] The direct-write printing ink used for direct-write printed zirconium oxide ceramics comprises the following components in percentage by weight: 15% photosensitive resin, 3.5% dispersant, 1% photoinitiator, 25% pore former and the balance zirconium oxide powder.

[0034] Wherein: the pore-forming agent is oxidized starch, the photosensitive resin is o-phenylphenoxyethyl acrylate, the dispersant is fish oil, and the photoinitiator is phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and a zirconium oxide ceramic embryo body after direct writing printing is prepared, such as Figure 1 (top) and Figure 4 As shown in (1).

[0035] Comparative Example 1

[0036] Preparation of direct-write printed zirconia ceramic embryos

[0037] The difference between this embodiment and embodiment 1 is that the pore-forming agent is removed, and other proportions remain unchanged; a zirconium oxide ceramic embryo body after direct writing printing is prepared.

[0038] Comparative Example 2

[0039] The zirconia ceramics are processed, including the following steps:

[0040] S1: preparing a corrosion solution, wherein the corrosion solution uses sodium hydroxide with a mass percentage concentration of 40%;

[0041] S2: The prepared corrosion solution is heated to 70° C. in a water bath to improve the corrosion efficiency.

[0042] S3: immersing the direct-write printed zirconia ceramic body prepared in Comparative Example 1 into a corrosion solution heated in a water bath, stirring and corroding for 200 minutes;

[0043] S4: After the corroded sample is taken out from the corrosive solution, it is cleaned with deionized water; it is rinsed with deionized water at least five times to prevent acid and alkali residues on the surface and to prevent the effect on the subsequent use of the porous ceramic sample.

[0044] S5: Drying the cleaned sample;

[0045] S6: Place the dried sample into a sintering furnace and sinter in an air atmosphere. Control the heating rate within the range of 5°C / min. The final sintering temperature is 1550°C. The heat preservation time is 4 hours. After the temperature naturally drops to room temperature, take out the sample and complete the sintering to obtain a ceramic product, such as Figure 2 shown.

[0046] Example 2

[0047] The zirconia ceramic body obtained in Example 1 was placed in a sintering furnace and sintered in an air atmosphere. The heating rate was controlled within the range of 0.2°C / min. The final sintering temperature was 1350°C. The heat preservation time was 1 hour. After the temperature naturally dropped to room temperature, the sample was taken out and the sintering was completed to obtain a ceramic product. Figure 5 As shown in (1) in .

[0048] Example 3

[0049] The zirconia ceramics are processed, including the following steps:

[0050] S1: preparing a corrosion solution, wherein the corrosion solution uses sodium hydroxide with a mass percentage concentration of 5%;

[0051] S2: The prepared corrosion solution is heated to 60° C. in a water bath to improve the corrosion efficiency.

[0052] S3: immersing the direct-write printed zirconia ceramic body prepared in Example 1 into a corrosion solution heated in a water bath, and stirring and corroding for 5 minutes;

[0053] S4: After the corroded sample is taken out from the corrosive solution, it is cleaned with deionized water; it is rinsed with deionized water at least five times to prevent acid and alkali residues on the surface and to prevent the effect on the subsequent use of the porous ceramic sample.

[0054] S5: Dry the cleaned sample. Figure 4 As shown in (2);

[0055] S6: Place the dried sample into a sintering furnace and sinter in an air atmosphere. Control the heating rate within the range of 0.2°C / min. The final sintering temperature is 1350°C. The heat preservation time is 1 hour. After the temperature naturally drops to room temperature, take out the sample and complete the sintering to obtain a porous ceramic product, such as Figure 5As shown in (2).

[0056] Example 4

[0057] The zirconia ceramics are processed, including the following steps:

[0058] S1: preparing a corrosion solution, wherein the corrosion solution uses sodium hydroxide with a mass percentage concentration of 40%;

[0059] S2: The prepared corrosion solution is heated to 70° C. in a water bath to improve the corrosion efficiency.

[0060] S3: immersing the direct-write printed zirconia ceramic body prepared in Example 1 into a corrosion solution heated in a water bath, stirring and corroding for 200 minutes;

[0061] S4: After the corroded sample is taken out from the corrosive solution, it is cleaned with deionized water; it is rinsed with deionized water at least five times to prevent acid and alkali residues on the surface and to prevent the effect on the subsequent use of the porous ceramic sample.

[0062] S5: Dry the cleaned sample. Figure 4 As shown in (3);

[0063] S6: Place the dried sample into a sintering furnace and sinter in an air atmosphere. Control the heating rate within the range of 5°C / min. The final sintering temperature is 1550°C. The heat preservation time is 4 hours. After the temperature naturally drops to room temperature, take out the sample and complete the sintering to obtain a porous ceramic product, such as Figure 1 (Down), Figure 3 and Figure 5 As shown in (3).

[0064] By comparing the above embodiments, it can be concluded that the present invention has the following advantages:

[0065] The amount of material removal is controllable and the overall uniformity is achieved: the entire material is placed in an acid-base solution, the solution can cover all outer surfaces of the sample, and appropriate stirring treatment keeps the concentration of each part of the solution consistent. The treatment effect of each part of the surface of the sample is consistent, thereby ensuring the mechanical properties and avoiding defects such as local notches and cracks caused by uneven treatment.

[0066] Long storage time and stable material system: Compared with water-based binder system, resin-based binder has low volatility and good stability of pore-forming agent material. Therefore, the structure will not be damaged in the resin system for a long time, and it can be stored for a long time without defects such as solid-liquid separation and agglomeration, which is convenient for use and transportation at any time.

[0067] Able to form multi-scale and multi-structure pore structures: The formed porous ceramic structure realizes a four-level pore structure from nanometer to micrometer in scale, including not only long channel structure pores, but also micro-spherical pore structures. While having a rich pore structure, it can still maintain good mechanical strength. At the same time, after appropriate surface treatment, the mechanical properties of porous ceramics will not be greatly damaged.

[0068] In the description of the present invention, it is necessary to understand that the terms "middle", "length", "up", "down", "front", "back", "vertical", "horizontal", "inside", "outside", "radial", "circumferential" and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present invention.

[0069] In the present invention, unless otherwise clearly specified and limited, the first feature "on" the second feature may be that the first and second features are in direct contact, or the first and second features are in indirect contact through an intermediate medium. "Multiple" means at least two, such as two, three, etc., unless otherwise clearly and specifically limited.

[0070] In the present invention, unless otherwise clearly specified and limited, the terms "installed", "connected", "connected", "fixed" and the like should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral one; it can be a mechanical connection, an electrical connection, or communication with each other; it can be a direct connection, or an indirect connection through an intermediate medium, it can be the internal connection of two elements or the interaction relationship between two elements, unless otherwise clearly defined. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0071] The above is only for explaining the implementation mode of the present invention and is not intended to limit the present invention. For those skilled in the art, any modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention without creative work should be included in the protection scope of the present invention.

Claims

1. A method for enhancing the porosity of the surface of porous zirconia ceramics, characterized in that: The following steps are involved: Prepare a corrosion solution, wherein the corrosion solution is sodium hydroxide, wherein the mass percentage concentration of the corrosion solution is 5%-40%; Heat the prepared corrosion solution in a water bath to 60°C-70°C; The direct-write printed zirconia ceramic embryo is immersed in a corrosion solution heated in a water bath, and the corrosion is stirred for 5 minutes to 200 minutes, wherein the direct-write printing ink used in the direct-write printing includes a pore-forming agent, and the direct-write printing ink used in the direct-write printed zirconia ceramic contains the following components in weight percentage: 50% to 70% of zirconia powder, 10% to 20% of photosensitive resin, 2% to 5% of dispersant, 0.2% to 2% of photoinitiator, and 10% to 40% of pore-forming agent, and the photosensitive resin is o-phenylphenoxyethyl acrylate; The corroded sample was taken out from the corrosive solution and then cleaned with deionized water; Dry the cleaned samples; The dried sample is placed in a sintering furnace and sintered in an air atmosphere. The heating rate is controlled within the range of 0.2℃ / min-5℃ / min. The final sintering temperature is 1350℃-1550℃. The insulation time is 1 hour-4 hours. After the temperature naturally drops to room temperature, the sample is taken out and the sintering is completed to obtain a porous ceramic product.

2. The method for enhancing the porosity of the surface of porous zirconia ceramics according to claim 1, characterized in that: The step of drying the cleaned sample includes: The cleaned samples are placed in a drying oven and dried at 40° C.-80° C. for 12 h-36 h.

3. The method for enhancing the porosity of the surface of porous zirconia ceramics according to claim 1, characterized in that: The pore-forming agent includes: one or more of oxidized starch, polymethyl methacrylate, wool, wood chips, and carbon fiber.

4. The method for enhancing the porosity of the surface of porous zirconia ceramics according to claim 1, characterized in that: The dispersant includes: one or more of fish oil, corn oil, ammonium citrate, and BYK-111.

5. The method for enhancing the porosity of the surface of porous zirconia ceramics according to claim 1, characterized in that: The photoinitiator includes one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, and 1-hydroxycyclohexyl-phenyl ketone.

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