KR20210031115A - Nickel-free decorative zirconia ceramic composite materials and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a nickel (Ni)-free decorative zirconia ceramic composite material and a method for manufacturing the same. The present invention provides a decorative zirconia ceramic composite material comprising: ZrO_2; at least one titanium compound selected from TiC and TiN; and a sintering agent, wherein the sintering agent includes at least one selected from Co and TiCN, and a manufacturing method thereof. According to the present invention, the zirconia ceramic composite material is harmless to the human body, has excellent metallic luster and a unique color, thereby having excellent decorative properties and the like, along with improved mechanical strength and the like. The zirconia ceramic composite material also has a color of green or blue.

Description

Nickel-Free DECORATIVE ZIRCONIA CERAMIC COMPOSITE MATERIALS AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a nickel-free decorative zirconia ceramic composite material and a manufacturing method thereof, and more particularly, to a nickel (Ni)-free nickel-free (Ni-free) decorative zirconia ceramic composite material, zirconia (ZrO ₂ ) as the base component, but including certain sintering agents and coloring agents, harmless to the human body, excellent metallic luster and unique color, excellent decorative properties, and excellent mechanical strength, and zirconia ceramic composite materials and manufacturing thereof It's about the method.

Zirconia (ZrO ₂ , zirconium oxide) has high wear resistance, high strength, and high melting point along with high toughness, and has a low coefficient of thermal expansion. In addition, zirconia (ZrO ₂ ) has a large refractive index and excellent corrosion resistance. Due to having such physical/thermal properties, zirconia (ZrO ₂ ) can be usefully used not only as a material for mechanical parts, but also as a decorative material.

However, zirconia is a white crystal and is difficult to be used as a decorative material by itself. Accordingly, in the case of decorative zirconia, a pigment for color is added and then color is realized through a high-temperature sintering process. In addition, a sintering agent is added together with the pigment for stability and strength during high-temperature sintering. For example, Korean Patent No. 10-0147085, Korean Patent No. 10-1397426, and Japanese Patent Application No. 2011-093725 disclose decorative zirconia ceramic composite materials and decorative parts related to the above.

In manufacturing a zirconia ceramic composite material, the selection of the pigment and the sintering agent together with the sintering conditions (temperature, etc.) is important. Pigments and sintering agents act as important factors not only for the appearance (color, etc.) of the product, but also for mechanical properties. In general, metal oxide or nickel (Ni) is mainly used as a sintering agent. Among them, nickel (Ni) is more advantageous in terms of decorative properties and strength than metal oxides.

However, nickel (Ni) is harmful to the human body, and this has a problem of causing skin allergies, for example. Several countries, including Europe, regulate the use of nickel (Ni). Accordingly, in manufacturing a decorative zirconia ceramic composite material, there is a need for a technical means capable of providing excellent decoration and strength without using nickel (Ni). In addition, the conventional decorative zirconia ceramic composite material is yellow, gray and black, and has a problem in that the color is limited.

Korean Patent Registration No. 10-0147085 Korean Patent Registration No. 10-1397426 Japanese Patent Application Publication No. 2011-093725

Accordingly, the present invention is a nickel-free (Ni-free) decorative zirconia ceramic composite material that does not contain nickel (Ni), which is harmless to the human body and has excellent metallic luster and unique color, so it has excellent decorative properties, and mechanical strength. An object of the present invention is to provide an excellent nickel-free decorative zirconia ceramic composite material and a manufacturing method thereof.

Another object of the present invention is to provide a nickel-free decorative zirconia ceramic composite material having a green or blue color as a characteristic color and a method for manufacturing the same.

In order to achieve the above object, the present invention,

As a nickel-free (Ni-free) decorative zirconia ceramic composite material that does not contain nickel,

ZrO ₂ ;

At least one titanium compound selected from TiC and TiN; And

Containing a sintering agent,

The sintering agent provides a decorative zirconia ceramic composite material comprising at least one selected from Co and TiCN.

According to one embodiment, the decorative zirconia ceramic composite material according to the present invention further includes a colorant, and the colorant includes _{at least one selected from SiC and Si 3} N ₄ , and may have a green or blue color.

In addition, the present invention,

A first step of obtaining a composite powder comprising ZrO ₂ , at least one titanium compound selected from TiC and TiN, and at least one sintering agent selected from Co and TiCN;

A second step of obtaining a mixed material obtained by mixing the composite powder with a liquid material containing a solvent and a caking agent;

A third step of obtaining a molded article obtained by molding the mixed material; And

It provides a method of manufacturing a decorative zirconia ceramic composite material comprising a fourth step of sintering the molded body.

According to one embodiment, in the first step, ZrO ₂ 35 to 70% by weight based on the total weight of the composite powder, 0.5 to 60% by weight of at least one titanium compound selected from TiC and TiN, and at least one selected from Co and TiCN It is possible to obtain a composite powder containing 0.1 to 15% by weight of the sintering agent. In addition, in the first step, a composite powder further comprising 2 to 30% by weight of one or more colorants selected from _{SiC and Si 3} N _{4 based on the total weight of the composite powder may be obtained.}

According to the present invention, as a nickel-free (Ni-free) decorative zirconia ceramic composite material that does not contain nickel (Ni), it is harmless to the human body and has excellent metallic luster and unique color, and thus has excellent decorative properties. Further, according to the present invention, mechanical strength such as breaking strength has an improved effect.

The term "and/or" used in the present invention is used to mean including at least one or more of the components listed before and after. The term "one or more" used in the present invention means one or two or more pluralities.

The present invention provides a nickel-free decorative zirconia ceramic composite material (hereinafter abbreviated as "ceramic composite material") containing _{zirconia (ZrO 2) as a main component and not containing nickel (Ni).} In addition, the present invention provides a method of manufacturing the ceramic composite material.

[Ceramic composite material]

The ceramic composite material according to the present invention includes (1) ZrO ₂ ; (2) at least one titanium compound selected from TiC and TiN; And (3) a sintering agent. At this time, the sintering agent includes at least one selected from Co and TiCN. In addition, the ceramic composite material according to the present invention may further include (4) a colorant and/or (5) an additive as an optional component. The colorant may include at least one selected from _{SiC and Si 3} N _4. The additive may be selected from metals and/or metal compounds. The additive may include, for example, at least one selected from _{Co 3} O ₄ and Cr ₂ O _3.

The ceramic composite material according to the present invention contains the above components as an active ingredient, and exhibits excellent metallic luster and unique color, and thus has excellent decorative properties. In addition, since the ceramic composite material according to the present invention does not contain nickel (Ni), it is harmless to the human body, and there is no skin side effects such as allergy. In addition, it has excellent mechanical strength such as breaking strength.

The ceramic composite material according to the present invention is usefully used as a decorative material, and can be used, for example, for watches (watches, etc.), jewelry, jewelry, and the like. The ceramic composite material according to the present invention may be used as a wristwatch component according to one embodiment, and specific examples include a case body, a bezel, a dial, and a front cover constituting a wristwatch. It can be usefully used as a (front cover) and/or a rear cover. In addition, the ceramic composite material according to the present invention may have various shapes such as a ring, an original plate, and/or a polygonal plate, depending on the type of product to be applied. Hereinafter, an exemplary embodiment for each component will be described.

(1) ZrO ₂

The ZrO ₂ (zirconia) is used as a main component, and a commercially available product that is commercially available can be used without limitation. The ZrO ₂ may be used, for example, having an average particle size of 0.3 μm to 0.8 μm. In this case, when a powder having an average particle size of less than 0.3 μm is used, shrinkage may occur during the sintering process, and when a powder exceeding 0.8 μm is used, sintering may be difficult and coloring may be difficult.

In addition, the ZrO ₂ may be included in an amount of 35 to 70% by weight based on the total weight of the ceramic composite material (based on solid content). When the _{content of ZrO 2} is less than 35% by weight, properties such as toughness, abrasion resistance, strength and corrosion resistance of the ceramic composite material may be insignificant. In addition, when _{the content of ZrO 2} exceeds 70% by weight, the content of the titanium compound or the sintering agent is relatively lowered, so that metallic luster or sinterability may be lowered. In consideration of this point, the ZrO ₂ may be included in 45 to 65% by weight, or 50 to 60% by weight based on the total weight of the ceramic composite material.

(2) titanium compound

The titanium compound is at least one selected from TiC (titanium carbide) and TiN (titanium nitride), and these are commercially available products available on the market without limitation. By the addition of such a titanium compound, the metallic luster and sense of quality of the ceramic composite material are improved. In addition, unique color development may be realized by the titanium compound. For example, when the TiC is used alone, a gray-based color may be implemented, and when the TiN is used alone, a yellow-based color may be implemented. In addition, when the TiC and TiN are mixed and used, various colors such as dark yellow to brown to dark gray may be implemented according to the addition ratio (content).

The titanium compound may be included in an amount of 0.5 to 60% by weight based on the total weight of the ceramic composite material. At this time, when the content of the titanium compound is less than 0.5% by weight, effects such as metallic luster and color development according to the addition thereof may be insignificant, and when it exceeds 60% by weight, _{the content of ZrO 2} may be relatively lowered, resulting in lower mechanical properties. . In consideration of this point, the titanium compound may be included in an amount of 2 to 50% by weight. According to a specific embodiment, when the TiC is used alone, it may be included in an amount of 30 to 55% by weight based on the total weight of the ceramic composite material. In addition, when the TiN is used alone, it may be included in an amount of 35 to 60% by weight based on the total weight of the ceramic composite material. In addition, when the TiC and TiN are mixed and used, 0.5 to 50% by weight of TiC and 2 to 55% by weight of TiN are used based on the total weight of the ceramic composite material, but the total amount thereof is preferably not more than 60% by weight.

(3) Sintering agent

The sintering agent is at least one selected from Co (cobalt) and TiCN (titanium carbon nitride), and these commercially available products can be used without limitation. According to the present invention, the Co and TiCN _{improves the sinterability of ZrO 2} and titanium compounds (TiC, TiN), which is advantageous in appearance and mechanical properties of ceramic composites, which are also harmless to the human body. More specifically, the Co and TiCN have the same or higher decorative properties and mechanical strength as compared to the case of using nickel (Ni) as a sintering agent, and there are no side effects on the human body such as skin allergies.

According to a preferred embodiment of the present invention, the sintering agent comprises at least TiCN. Specifically, as the sintering agent, TiCN may be used alone, or an appropriate amount of Co may be mixed with TiCN. As described above, when the sintering agent contains TiCN, at least mechanical strength and the like are effectively improved than when nickel (Ni) is used.

In addition, the sintering agent selected from Co and/or TiCN may be included in an amount of 0.1 to 15% by weight based on the total weight of the ceramic composite material. At this time, when the content of the sintering agent is less than 0.1% by weight, the effect of improving the sinterability according to the addition thereof may be insignificant, and when it exceeds 15% by weight _{, the content of ZrO 2} and titanium compounds (TiC, TiN) is relatively lowered, resulting in mechanical properties And metallicity, etc. may be lowered. In consideration of this point, the sintering agent may be included in an amount of 0.5 to 12% by weight, or 2 to 10% by weight. According to a preferred embodiment, the sintering agent includes at least TiCN, and the TiCN may be included in an amount of 1 to 10% by weight, or 2 to 8% by weight based on the total weight of the ceramic composite material. In addition, when a mixture of Co and TiCN is used as the sintering agent, 0.2 to 3% by weight of Co and 1 to 10% by weight of TiCN may be used based on the total weight of the ceramic composite material.

(4) colorant

The colorant is at least one selected from SiC (silicon carbide) and Si ₃ N _{4 (silicon nitride).} The SiC and/or Si ₃ N ₄ may be commercially available products available on the market without limitation. At this time, the SiC may be selected from black or green. According to the present invention, when SiC and/or Si ₃ N ₄ are added as the colorant, the ceramic composite material has a characteristic color, such as green, cyan, or blue. This color is realized by the addition of at least the colorant (SiC and/or Si ₃ N ₄ ), and a combination of the colorant (SiC and/or Si ₃ N ₄ ) and the titanium compound (TiC and/or TiN) with this Can be implemented by

In the present invention, the green color is included here as long as it can be recognized as green when observed with the naked eye, and this includes light green to dark green. In addition, even in the case of blue, if it is recognized as blue when observed with the naked eye, it is included here, and this includes light blue to dark blue. The same is as above in the case of the greenish blue color. In the case of having such colors as green, cyan, and blue, the ceramic composite material may have a sense of quality such as emerald.

The colorant selected from SiC and/or Si ₃ N ₄ may be included in an amount of 2 to 30% by weight based on the total weight of the ceramic composite material. At this time, when the content of the colorant is less than 2% by weight, the coloring effect due to the addition thereof may be insignificant, and when it exceeds 30% by weight _{, the content of ZrO 2} and titanium compounds (TiC, TiN) is relatively low, and thus mechanical properties and Metallicity, etc. may be lowered. In consideration of this point, the colorant may be included in an amount of 5 to 20% by weight. According to one embodiment, the colorant may be SiC alone or Si ₃ N ₄ alone, but may be used in an amount of 5 to 20% by weight based on the total weight of the ceramic composite material.

(5) additives

The additive is not particularly limited, and it may include a metal and/or a metal compound. The additives are, for example, W (tungsten), Co (cobalt), Cr (chromium), Cu (copper), Al (aluminum), Ta (tantalum), Fe (iron), Zn (zinc), Mn (manganese). ), at least one metal selected from Ba (barium), Ge (germanium), Sn (tin), Sb (antimony), V (vanadium), and Bi (bismuth); A metal carbide containing one or more of the metal elements listed above; And/or metal oxides including one or more of the metal elements listed above. In this case, examples of the metal carbide include WC (tungsten carbide) and/or TaC (tantalum carbide).

According to one embodiment, the additive is selected from metal oxides, and the metal oxide preferably includes at least one selected _{from Co 3} O ₄ and Cr ₂ O _3. The Co ₃ O ₄ and Cr ₂ O ₃ may act as a sintering aid and/or a brightening agent to improve sintering strength and/or appearance.

In addition, the additive may be included in an amount of 0.1 to 20% by weight based on the total weight of the ceramic composite material. At this time, when the content of the additive is less than 0.1% by weight, the effect of improving sintering strength and/or appearance according to the addition thereof may be insignificant, and when it exceeds 20% by weight, ZrO ₂ and titanium compounds (TiC, TiN ), etc. may be lowered, resulting in lower mechanical properties and metallic properties. According to one embodiment, the additive uses Co ₃ O ₄ and/or Cr ₂ O _{3 as a metal oxide, but Co 3} O ₄ 0.5 to 5% by weight and/or Cr ₂ O based on the total weight of the ceramic composite material. ₃ 1 to 8% by weight may be used.

The ceramic composite material according to the present invention may be manufactured by various methods, and may be manufactured through the method of manufacturing the ceramic composite material according to the present invention described below according to one embodiment. However, the ceramic composite material according to the present invention is not limited to being manufactured through the manufacturing method described below.

[Method of manufacturing ceramic composite material]

The method of manufacturing a ceramic composite material according to the present invention comprises: a first step of obtaining a composite powder; A second step of obtaining a mixed material obtained by mixing the composite powder with a liquid material; A third step of obtaining a molded article obtained by molding the mixed material; And a fourth step of sintering the molded body. Each step is explained as follows.

[1] The first step (composite powder)

First, a composite powder constituting the ceramic composite material is obtained. Specifically, _{to obtain a composite powder comprising ZrO 2} , at least one titanium compound selected from TiC and TiN, and at least one sintering agent selected from Co and TiCN. In addition, according to another embodiment, in the first step, a sintering agent and/or an additive may be further mixed with the composite powder. Each component constituting this composite powder is as described above.

According to one embodiment, in the first step, ZrO ₂ 35 to 70% by weight based on the total weight of the composite powder, 0.5 to 60% by weight of at least one titanium compound selected from TiC and TiN, and at least one selected from Co and TiCN A composite powder is prepared by mixing 0.1 to 15% by weight of a sintering agent. _{In addition, 2 to 30% by weight of one or more colorants selected from SiC and Si 3} N ₄ based on the total weight of the composite powder may be further mixed, and/or 0.1 to 20% by weight of an additive may be further included. At this time, the additive is a metal oxide as described above _{, but using Co 3} O ₄ and/or Cr ₂ O _{3 , Co 3} O ₄ 0.5 to 5% by weight and/or Cr ₂ O ₃ 1 based on the total weight of the composite powder ~ 8% by weight can be used.

[2] The second step (mixing)

A mixed material obtained by mixing the composite powder with a liquid material is obtained. At this time, the liquid material has a predetermined viscosity, which includes a solvent and a binder. These liquid materials are removed (volatilized) in a high temperature sintering process. The solvent may be selected from water and/or organic solvents, which may be specifically selected from water, alcohols (ethanol, etc.) and/or ketones. The binder is for moldability, and it is possible to use one capable of having a predetermined viscosity while bonding the composite powder before sintering. Such a binder may be selected from polymers such as polyvinyl butyral (PVB) and/or polyvinyl alcohol (PVA), but is not limited thereto.

In addition, the liquid material may further include one or more additives selected from a dispersant, a lubricant (release agent), a plasticizer, and an antifoaming agent, in addition to a solvent and a caking agent. The additive may be selected from those commonly used in the art.

According to one embodiment, the liquid material may include 0.5 to 20 parts by weight of a binder based on 100 parts by weight of the solvent. In addition, the liquid material may further include 0.2 to 5 parts by weight of a dispersant, 0.5 to 10 parts by weight of a lubricant (release agent), 0.1 to 5 parts by weight of a plasticizer, and/or 0.1 to 5 parts by weight of an antifoaming agent based on 100 parts by weight of the solvent. The composite powder is mixed with such a liquid material to obtain a mixed material having a predetermined viscosity. The mixed material may have a viscosity advantageous for molding. The mixed material may include a composite powder and a liquid material in a weight ratio of 100:10 to 80. Such a mixed material can be prepared by putting the composite powder and the liquid material into a mixing stirrer and then mixing and stirring.

According to another embodiment, in preparing the mixed material, the composite powder and the liquid material may be mixed and then spray-dried. Specifically, first, the composite powder and the liquid material are put into a mixing stirrer to obtain a mixed and stirred mixture. And after spraying the mixture in the form of droplets using a sprayer, it is possible to prepare a mixed material in the form of granules having a uniform size through drying. In this case, homogeneous mixing of each component can be achieved.

[3] The third stage (molding)

A molded article obtained by molding the mixed material is obtained. The molded body may have any shape, which may have various shapes such as a ring, a disk, a cylinder, a cylinder, a polygonal plate, a polygonal cylinder, and a polyhedron. For another example, the molded body may have a shape such as a finished product or a semi-finished product of an actual product (such as a watch part).

The molding method in this third step is not particularly limited. The molding method can be selected from, for example, press molding, injection molding, and extrusion molding. For example, a molded article having an arbitrary shape may be manufactured by applying a predetermined temperature and pressure through press molding.

[4] The fourth stage (sintering)

Next, the molded body is sintered (fired). The sintering can be carried out in a vacuum sintering furnace or a gas pressure sintering furnace, and the like, which can also be carried out according to conventional ceramic sintering conditions.

According to one embodiment, the sintering may be carried out for about 30 minutes or more at a high temperature of about 1,400° C. or higher in a reducing atmosphere or a vacuum atmosphere. Specifically, the sintering may be performed at a temperature of 1,400°C to 2,500°C, or 1,600°C to 2,200°C for 30 minutes to 6 hours. Upon completion of this sintering, a sintered body of ceramic composite material having excellent metallic luster and mechanical properties is produced, which also has a unique color.

Meanwhile, the method of manufacturing a ceramic composite material according to the present invention may further include a fifth step of processing the sintered body obtained through the sintering. The fifth step (processing) may include surface polishing and/or cutting. For example, when the sintered body has an arbitrary shape, cutting may be performed so that it has the shape of an actual product (watch parts, etc.). In this case, the cutting process may be performed through, for example, laser processing, and the shape of parts such as a case body, a bezel and/or a dial constituting the wrist watch may be formed through such cutting processing.

According to the present invention described above, as described above, as a nickel-free zirconia ceramic composite material that does not contain nickel (Ni), it is harmless to the human body and has excellent metallic luster and mechanical properties. It also has a distinctive color with metallic luster. In addition, as described above, it has a green or blue color, so it has excellent sense of quality and decoration.

Hereinafter, examples and comparative examples of the present invention are illustrated. The following examples are provided merely to help the understanding of the present invention, and the technical scope of the present invention is not limited thereby. In addition, the following comparative examples do not imply a prior art, which is provided only for comparison with the examples.

[Examples 1 to 6]

First, as a composite powder, ZrO ₂ , titanium compounds (TiC, TiN), sintering agents (Co, TiCN), colorants (SiC, Si ₃ N ₄ ) and additives (Co ₃ O ₄ , Cr ₂ O ₃ , CuO) are prepared. I did. Then, a liquid material was prepared in which 12 parts by weight of a binder (PVB), 2 parts by weight of a dispersant, and 5 parts by weight of a lubricant were mixed with respect to 100 parts by weight of a solvent (ethanol). Thereafter, the composite powder and the liquid material were mixed in a weight ratio of 100:55, and a mixed material mixed while performing ball milling was prepared. At this time, the composition and content of the composite powder were different according to each example.

Next, the mixed material was spray-dried to prepare a granule form, and then it was introduced into a press mold to form a plate-shaped molded body. Thereafter, the formed body was sintered for about 2 hours at a temperature of about 1,800° C. in a vacuum atmosphere in a vacuum sintering furnace to prepare a ceramic composite material specimen (sintered body) according to each example. The composition (components and contents) of the ceramic composite material specimen according to each example are shown in Table 1 below. In the following [Table 1], the content (% by weight) of each component is based on the total weight of the solid content (composite powder) constituting the ceramic composite material.

[Comparative Examples 1 to 2]

Compared with Example 1, a ceramic composite material specimen (sintered body) according to each comparative example was prepared in the same manner as in Example 1, except that the components and contents of the composite powder were different. As shown in the following [Table 1], Comparative Example 1 is a specimen using Ni as a sintering agent.

<Components and contents of ceramic composite specimens> Remark ZrO ₂ Ti compound Sintering agent coloring agent Additive (metal oxide) TiC TiN Co TiCN Ni SiC Si ₃ N ₄ Co ₃ O ₄ Cr ₂ O ₃ CuO Example 1 50 35 - One 4 - 10 ^(B) - - - - Example 2 50 35 - - 5 - 10 ^(G) - - - - Example 3 50 35 - 5 - - 10 ^(G) - - - - Example 4 50 35 - One 4 - - 10 - - - Example 5 50 31 - One 4 - 10 ^(G) - 4 - - Example 6 50 3 28 One 4 - - 10 - 4 - Comparative Example 1 50 42 - - - 5 - - - - 3 Comparative Example 2 50 - 42 - - - - - 2 - 6 (B): Black SiC
(G): Green SiC

The mechanical properties (toughness, hardness, breaking strength), gloss, and color of the ceramic composite material specimens according to each of the Examples and Comparative Examples were evaluated. The mechanical properties (toughness, hardness, breaking strength) were evaluated by the following method. And the gloss and color were evaluated visually. The above evaluation results are shown in the following [Table 2].

<Evaluation method>

* Toughness: Fracture toughness was measured with a load of 9.8N using a Vickers hardness tester (Mitutoyo, Japan, AVK-C2) by the Vickers indentation method.

* Hardness: Measured with a micro Vickers hardness tester with a load of 9.8N.

* Breaking strength: Measured through a three-point bending strength test (span distance 30mm, crosshead speed 0,5mm/min) using UTM (Model No. 4206 of Instron).

<Results of evaluation of characteristics of ceramic composite material specimens> Remark tenacity
[MPaㆍm ^1/2 ] Hardness
[Kgf/㎟] Breaking strength
[MPa] Polish color Example 1 9.7 1,223 762 good blue Example 2 10.4 1,094 781 good green Example 3 8.7 1,235 714 good green Example 4 9.5 1,154 759 good blue Example 5 11.3 1,032 814 excellent green Example 6 10.1 1,103 807 excellent Cyan blue Comparative Example 1 9.1 1,251 746 good grey Comparative Example 2 7.8 1,332 621 good yellow

As shown in [Table 1] and [Table 2], in the case of the specimens according to the examples using Co and/or TiCN as a sintering agent, it was found that the specimens have excellent mechanical properties equal to or higher than those of the comparative examples. Could know. In particular, it was found that when TiCN was used as the sintering agent, the breaking strength was remarkably increased. In addition, it was found that the specimens according to the examples had excellent gloss and had a green or blue color according to the addition of _{SiC and Si 3} N _{4 as colorants.}

Claims (7)

ZrO ₂ ;
At least one titanium compound selected from TiC and TiN; And
Containing a sintering agent,
The sintering agent decorative zirconia ceramic composite material, characterized in that it contains at least one selected from Co and TiCN.
The method of claim 1,
The decorative zirconia ceramic composite material further comprises a colorant,
The colorant comprises at least one selected from _{SiC and Si 3} N _4,
The decorative zirconia ceramic composite material is a decorative zirconia ceramic composite material, characterized in that the color of green, cyan blue or blue.
The method of claim 1,
The decorative zirconia ceramic composite material, characterized in that the sintering agent contains TiCN.
The method according to any one of claims 1 to 3,
The decorative zirconia ceramic composite material further comprises at least one additive selected _{from Co 3} O ₄ and Cr ₂ O _3.
A first step of obtaining a composite powder comprising ZrO ₂ , at least one titanium compound selected from TiC and TiN, and at least one sintering agent selected from Co and TiCN;
A second step of obtaining a mixed material obtained by mixing the composite powder with a liquid material containing a solvent and a caking agent;
A third step of obtaining a molded article obtained by molding the mixed material; And
A method for producing a decorative zirconia ceramic composite material comprising a fourth step of sintering the molded body.
The method of claim 5,
_{In the first step, 35 to 70% by weight of ZrO 2} based on the total weight of the composite powder, 0.5 to 60% by weight of at least one titanium compound selected from TiC and TiN, and 0.1 to 15% by weight of at least one sintering agent selected from Co and TiCN A method for producing a decorative zirconia ceramic composite material, characterized in that to obtain a composite powder comprising a.
The method of claim 6,
In the first step, a method for producing a decorative zirconia ceramic composite material further comprising 2 to 30% by weight of one or more colorants selected from _{SiC and Si 3} N ₄ based on the total weight of the composite powder.