Blue zirconia ceramic and preparation method thereof

Abstract

The invention discloses a blue zirconia ceramic and a preparation method thereof, and the preparation method comprises the following steps: powder mixing modification: mixing zirconia powder, alumina powder and cobalt oxide powder with an alcohol solvent, carrying out ball milling to uniformly mix the powder, adding a surface modifier to modify a ball milling suspension, and drying at 50-80 DEG C for 24-36 hours to obtain the blue zirconia ceramic. The dried powder is sieved, and lipophilic hydrophobic powder is formed; preparing a printing paste material: respectively adding a dispersing agent, a photoinitiator and light-cured resin into the lipophilic hydrophobic powder, and mixing to obtain the printing paste material; printing: printing the printing paste by adopting an SLA-3D printing technology to obtain a ceramic blank; soaking and washing; degreasing and sintering: degreasing and sintering the air-dried ligand in nitrogen; sintering in an oxygen environment to obtain a product; the invention has the advantages of uniform color distribution, stable material, long preservation time, high production efficiency and low cost.

Description

Technical Field

[0001] The invention relates to the technical field of ceramics, and in particular to a blue zirconia ceramic and a preparation method thereof. Background Art

[0002] The excellent properties of zirconia ceramics make it have a wide range of application prospects in the engineering field. In terms of structural ceramics, zirconia's excellent wear resistance, high temperature resistance and corrosion resistance make it often used to manufacture engineering parts such as valves, sleeves and nozzles. The working environment of such engineering parts is usually harsh. For example, valves used in the oil industry are often in highly corrosive media such as petroleum gas and natural gas. The use of traditional metal valves is prone to corrosion, has a short service life, increases replacement costs, and is not conducive to production safety. Accidents may occur due to valve failure. The corrosion resistance of zirconia ceramics can be well qualified for this field. In addition, zirconia ceramics also have high hardness and wear resistance physical properties, and can be made into abrasives for grinding. In terms of functional ceramics, zirconia ceramics with special optical and electrical properties also have great advantages. In addition to the above fields, zirconia ceramics also occupy an important position in the field of decorations. At present, the most widely used in the market is gem-like decorations. From the appearance point of view, zirconia ceramics have a high refractive index, and the surface can show a gem-like luster, which is more beautiful and suitable for making various decorations. And because of its high hardness and durability, the jewelry made from it feels smooth, is not easy to leave fingerprints and scratches, and is simple and convenient to maintain.

[0003] Stereolithography (SLA) technology has become a relatively successful commercial ceramic 3D printing technology with its high precision and high resolution advantages. This technology uses a paste component mixed with ceramic powder, photoinitiator, dispersant, etc. in the printing process. In addition, the printing process does not require a mold, which can achieve high production efficiency and structural design freedom, breaking away from the constraints of traditional manufacturing processes. When using SLA to print colored ceramics, the material utilization rate is high, and the unused ceramic paste can be pumped from the material tank to the workbench to recycle the remaining slurry.

[0004] Existing methods for manufacturing colored ceramics include molding technologies such as gel casting and injection molding. The coloring method usually uses a layer of colored glaze to coat the green body prepared by cold isostatic pressing or injection molding. This method has the advantages of simple operation and low manufacturing cost, but the sintering temperature of the ceramic is generally not higher than 1300 degrees, and the colored glaze cannot achieve uniform coloring inside the ceramic or manufacture complex green body shapes. Due to the high melting point of zirconia ceramics, a higher sintering temperature is required, generally around 1450°C, which causes the colored glaze used in the coating method to decompose and volatilize, resulting in coloring failure. Therefore, it is necessary to choose a better coloring method. For colored ceramics, there are two commonly used coloring methods: solid phase mixing method and liquid phase infiltration method. The liquid phase infiltration method is simple to operate, but the coloring solution may affect the performance of ceramic parts, resulting in defects or uneven color of the green body. Solid-phase mixing coloring is widely used due to its advantages such as simple process flow, easy operation and good mechanical properties of manufactured ceramics. However, when using traditional processes to produce parts, molds are required. However, the design and production of molds are relatively complicated, the production cycle is long, the manufacturing cost is high, and it is impossible to produce corresponding molds for parts with complex spatial three-dimensional structures such as hollowing out and internal channels. Summary of the invention

[0005] The object of the present invention is to provide a blue zirconia ceramic and a preparation method thereof, which has the advantages of uniform color distribution, stable material, long storage time, high production efficiency and low cost.

[0006] To achieve this object, the present invention adopts the following technical solutions: Provided is a blue zirconia ceramic, characterized in that, measured by mass, the components of the blue zirconia ceramic include: 70-80 parts of zirconium oxide powder, 3 parts of aluminum oxide powder, 1-3 parts of cobalt oxide powder, 1 part of surface modifier, 1 part of photoinitiator, 10-20 parts of photocurable resin and 3-5 parts of dispersant.

[0007] As a preferred solution of the blue zirconia ceramic, the surface modifier is one or both of stearic acid and a silane coupling agent.

[0008] As a preferred solution of the blue zirconium oxide ceramic, the photoinitiator is one or more of 2-benzyl-4'-morpholinobutyrophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbisphosphine oxide.

[0009] As a preferred solution of the blue zirconium oxide ceramic, the photocurable resin is one or more of 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, acryloyl morpholine and trimethylolpropane triacrylate.

[0010] As a preferred solution for blue zirconia ceramics, the dispersant is one or both of BYK-111 and BYK-9076.

[0011] The present invention also provides a method for preparing the blue zirconia ceramic described in any one of the above items, comprising the following steps: Powder mixing modification: zirconium oxide powder, aluminum oxide powder and cobalt oxide powder are mixed with an alcohol solvent, and the powders are evenly mixed by ball milling, a surface modifier is added to modify the ball milling suspension, and the mixture is dried at 50 to 80° C. for 24 to 36 hours, and the dried powder is sieved to form a lipophilic and hydrophobic powder; Preparing printing paste: adding dispersant, photoinitiator and photocurable resin to lipophilic and hydrophobic powder respectively, and mixing to obtain printing paste; Printing: Printing the printing paste using SLA-3D printing technology to obtain a ceramic embryo; Soaking and rinsing: Soak the printed ceramic body in a water bath at 70-80°C for 10 minutes, rinse with deionized water for 1 minute, repeat 3 times, and let the body air dry naturally; Debinding and sintering: The air-dried ligand is debinded and sintered under nitrogen at a heating rate of 0.3-10 °C / min, and finally kept at 1050 °C for 1-4 hours; and sintered in an oxygen environment at a heating rate of 5-10 °C / min, and finally kept at 1450 °C for 2-4 hours to obtain the product.

[0012] As a preferred solution of the method for preparing blue zirconia ceramics, in the step of powder mixing and modification, the mass ratio of powder, ball milling balls and alcohol is 1:1:2.

[0013] As a preferred solution of the method for preparing blue zirconia ceramics, in the step of mixing and modifying the powders, the ball mill is used for mixing at a rotation speed of 1500 rpm in an intermittent mode for 1 to 2 hours.

[0014] As a preferred solution of the preparation method of blue zirconia ceramics, in the step of powder mixing and modification, the modification is carried out in a water bath environment, the water bath temperature is 75° C., and the modification time is 1.5 h.

[0015] Beneficial effects of the present invention: the blue zirconia ceramic and preparation method proposed in the present invention can react with alumina at about 1100°C during sintering to form cobalt blue by adding cobalt oxide powder, and SLA printing can make the cobalt oxide and alumina powder in the paste evenly distributed inside the ceramic blank, so that the sintered ceramic sample presents a uniform blue appearance; wherein, since the use of SLA printing of ceramics brings the advantages of high precision, high printing structure freedom, and fast printing speed; since the use of various powders and photoinitiators, photocurable resin components and dispersants to configure low-viscosity colored zirconia paste brings the advantages of stable materials and long storage time; since the method of powder ball milling and material homogenization is used to make the material system uniform as a whole, the blue ceramic has the advantage of uniform color distribution; and the present invention starts from an easily processable blank, reduces the processing cost, and can also achieve better effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] 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.

[0017] Figure 1 1 is a comparison diagram of a printed embryo (top), a degreased sample (middle), and a sintered sample (bottom) in one embodiment of the present invention; Figure 2 This is a SEM electron microscope image of the printed embryo layer in one embodiment of the present invention; Figure 3 This is a SEM electron microscope image of the surface of the sample after sintering in one embodiment of the present invention. DETAILED DESCRIPTION

[0018] The embodiments of the present disclosure are described in detail below with reference to the accompanying drawings.

[0019] 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.

[0020] Example 1 This embodiment provides a method for preparing blue zirconia ceramics, comprising the following steps: S1: powder mixing modification: 75 parts of zirconium oxide, 3 parts of aluminum oxide, and 2 parts of cobalt oxide are mixed with an alcohol solvent, and the powder components are evenly distributed by ball milling. The ball milling suspension is modified, and the powder is dried at 65°C for 32 hours. The dried powder is sieved to form a lipophilic and hydrophobic powder.

[0021] S2: Prepare printing paste: add dispersant, photoinitiator and photocurable resin to lipophilic and hydrophobic powder respectively, and mix to obtain printing paste; use 4 parts of BYK-111 as dispersant to improve the viscosity of the paste, and select 1 part of phenyl bisphosphine oxide photoinitiator with strong ultraviolet light absorption ability to improve the curing depth of the printing paste, and select photocurable resin with similar thermal decomposition peak, 1,6-hexanediol diacrylate is 10 parts, acryloyl morpholine is 2 parts, and trimethylolpropane triacrylate is 3 parts.

[0022] S3: Printing: Use modular design software to set the printing layer thickness, call up an existing printing model library for design, and print the printing paste using SLA-3D printing technology to obtain a ceramic embryo.

[0023] S4: Soaking and rinsing: Soak the printed ceramic body in a 75°C water bath for 10 minutes, rinse with deionized water for 1 minute, repeat 3 times, and let the body air dry naturally.

[0024] S5: Debinding and sintering: The sample was debinded and sintered under nitrogen, with a heating rate of 2.5 degrees Celsius / minute, and finally kept at 1050°C for 2 hours. This allows the sample to evenly decompose the resin components to avoid cracks during the debinding process. It was then sintered in an oxygen environment, with a heating rate of 8 degrees Celsius / minute, and finally kept at 1450°C for 3 hours to avoid thermal stress during the sintering process.

[0025] Among them, in step S2: soak each powder component in an anhydrous alcohol solution, add agate ball milling balls, the mass ratio of powder, ball milling balls and alcohol is 1:1:2, and the ball mill is mixed for 1.5 hours in an intermittent mode at a speed of 1500rpm. After the ball milling is completed, the modification treatment is carried out in a water bath environment, the water bath temperature is 75°C, and the modification time is 1.5 hours. This helps the powder to be evenly mixed and transformed into lipophilic and hydrophobic.

[0026] In this embodiment, the addition of cobalt oxide powder can react with aluminum oxide to form cobalt blue during sintering at about 1100°C. SLA printing can evenly distribute the cobalt oxide and aluminum oxide powders in the paste inside the ceramic body, so that the ceramic sample presents a uniform blue appearance after sintering. Figure 3It can be proved that the generated cobalt blue is evenly distributed on the surface of the ceramic sample (the raised parts of the surface are cobalt blue), and the chemical reaction formula for producing cobalt blue is: Example 2 This embodiment provides a method for preparing blue zirconia ceramics, comprising the following steps: S1: Powder mixing modification: 70 parts of zirconium oxide, 3 parts of aluminum oxide, and 3 parts of cobalt oxide are mixed with an alcohol solvent, and the powder components are evenly distributed by ball milling. The ball milling suspension is modified, and the powder is dried at 50°C for 24 hours. The dried powder is sieved to form a lipophilic and hydrophobic powder.

[0027] S2: Prepare printing paste: add dispersant, photoinitiator and photocurable resin to lipophilic and hydrophobic powder respectively, and mix to obtain printing paste; use 3 parts of BYK-111 as dispersant to improve the viscosity of the paste, and select 1 part of phenyl bisphosphine oxide photoinitiator with strong ultraviolet light absorption ability to improve the curing depth of the printing paste, and select photocurable resin with similar thermal decomposition peak, 1,6-hexanediol diacrylate is 10 parts, acryloyl morpholine is 5 parts, and trimethylolpropane triacrylate is 5 parts.

[0028] S3: Printing: Use modular design software to set the printing layer thickness, call up an existing printing model library for design, and print the printing paste using SLA-3D printing technology to obtain a ceramic embryo.

[0029] S4: Soaking and rinsing: Soak the printed ceramic body in a water bath at 80°C for 10 minutes, rinse with deionized water for 1 minute, repeat 3 times, and allow the body to air dry naturally.

[0030] S5: Debinding and sintering: The sample was debinded and sintered under nitrogen, with a heating rate of 0.3 degrees Celsius / minute, and finally kept at 1050°C for 1 hour. This allows the sample to evenly decompose the resin components to avoid cracks during the debinding process. It was then sintered in an oxygen environment, with a heating rate of 5 degrees Celsius / minute, and finally kept at 1450°C for 2 hours to avoid thermal stress during the sintering process.

[0031] Among them, in step S2: soak each powder component in an anhydrous alcohol solution, add agate ball milling balls, the mass ratio of powder, ball milling balls and alcohol is 1:1:2, and the ball mill is mixed for 1 hour in an intermittent mode at a speed of 1500rpm. After the ball milling is completed, the modification treatment is carried out in a water bath environment, the water bath temperature is 70℃, and the modification time is 1 hour. This helps the powder to be evenly mixed and transformed into lipophilic and hydrophobic.

[0032] Example 3 This embodiment provides a method for preparing blue zirconia ceramics, comprising the following steps: S1: Powder mixing modification: 80 parts of zirconium oxide, 3 parts of aluminum oxide, and 1 part of cobalt oxide are mixed with an alcohol solvent, and the powder components are evenly distributed by ball milling. The ball milling suspension is modified, and the powder is dried at 80°C for 36 hours. The dried powder is sieved to form a lipophilic and hydrophobic powder.

[0033] S2: Prepare printing paste: add dispersant, photoinitiator and photocurable resin to lipophilic and hydrophobic powder respectively, and mix to obtain printing paste; use 5 parts of BYK-111 as dispersant to improve the viscosity of the paste, and select 1 part of phenyl bisphosphine oxide photoinitiator with strong ultraviolet light absorption ability to improve the curing depth of the printing paste, and select photocurable resin with similar thermal decomposition peak, 1,6-hexanediol diacrylate is 6 parts, acryloyl morpholine is 2 parts, and trimethylolpropane triacrylate is 2 parts.

[0034] S3: Printing: Use modular design software to set the printing layer thickness, call up an existing printing model library for design, and print the printing paste using SLA-3D printing technology to obtain a ceramic embryo.

[0035] S4: Soaking and rinsing: Soak the printed ceramic body in a 70°C water bath for 10 minutes, rinse with deionized water for 1 minute, repeat 3 times, and allow the body to air dry naturally.

[0036] S5: Debinding and sintering: The sample is debinded and sintered under nitrogen, with a heating rate of 10 degrees Celsius / minute, and finally kept at 1050°C for 4 hours. This allows the sample to evenly decompose the resin components to avoid cracks during the debinding process. It is then sintered in an oxygen environment, with a heating rate of 10 degrees Celsius / minute, and finally kept at 1450°C for 4 hours to avoid thermal stress during the sintering process.

[0037] Among them, in step S2: soak each powder component in an anhydrous alcohol solution, add agate ball milling balls, the mass ratio of powder, ball milling balls and alcohol is 1:1:2, and the ball mill is mixed for 2 hours at a speed of 1500rpm in an intermittent mode. After the ball milling is completed, the modification treatment is carried out in a water bath environment, the water bath temperature is 80℃, and the modification time is 1 hour. This helps the powder to be evenly mixed and transformed into lipophilic and hydrophobic.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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 blue zirconia ceramic, characterized in that: The components of the blue zirconia ceramic include, by mass, 70-80 parts of zirconia powder, 3 parts of aluminum oxide powder, 1-3 parts of cobalt oxide powder, 1 part of surface modifier, 1 part of photoinitiator, 10-20 parts of photocurable resin and 3-5 parts of dispersant.

2. The blue zirconia ceramic according to claim 1, characterized in that: The surface modifier is one or both of stearic acid and a silane coupling agent.

3. The blue zirconia ceramic according to claim 1, characterized in that: The photoinitiator is one or more of 2-benzyl-4'-morpholinobutyrophenone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and phenylbisphosphine oxide.

4. The blue zirconia ceramic according to claim 1, characterized in that: The photocurable resin is one or more of 1,6-hexanediol diacrylate, dipentaerythritol hexaacrylate, acryloyl morpholine and trimethylolpropane triacrylate.

5. The blue zirconia ceramic according to claim 1, characterized in that: The dispersant is one or both of BYK-111 and BYK-9076.

6. A method for preparing the blue zirconia ceramic according to any one of claims 1 to 5, comprising the following steps: Powder mixing modification: zirconium oxide powder, aluminum oxide powder and cobalt oxide powder are mixed with an alcohol solvent, and the powders are evenly mixed by ball milling, a surface modifier is added to modify the ball milling suspension, and the mixture is dried at 50 to 80° C. for 24 to 36 hours, and the dried powder is sieved to form a lipophilic and hydrophobic powder; Preparing printing paste: adding dispersant, photoinitiator and photocurable resin to lipophilic and hydrophobic powder respectively, and mixing to obtain printing paste; Printing: Printing the printing paste using SLA-3D printing technology to obtain a ceramic embryo; Soaking and rinsing: Soak the printed ceramic body in a water bath at 70-80°C for 10 minutes, rinse with deionized water for 1 minute, repeat 3 times, and let the body air dry naturally; Debinding and sintering: The air-dried ligand is debinded and sintered under nitrogen at a heating rate of 0.3-10 °C / min, and finally kept at 1050 °C for 1-4 hours; and sintered in an oxygen environment at a heating rate of 5-10 °C / min, and finally kept at 1450 °C for 2-4 hours to obtain the product.

7. The method for preparing blue zirconia ceramics according to claim 6, characterized in that: In the powder mixing and modification step, the mass ratio of powder, ball milling balls and alcohol is 1:1:

2.

8. The method for preparing blue zirconia ceramics according to claim 6, characterized in that: In the powder mixing and modification step, the ball mill is mixed in an intermittent mode at a rotation speed of 1500 rpm for 1 to 2 hours.

9. The method for preparing blue zirconia ceramics according to claim 6, characterized in that: In the powder mixing and modification step, the modification is carried out in a water bath environment, the water bath temperature is 75° C., and the modification time is 1.5 h.

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