KR0175559B1 - Method for producing a sintered body having green color - Google Patents
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- KR0175559B1 KR0175559B1 KR1019960045015A KR19960045015A KR0175559B1 KR 0175559 B1 KR0175559 B1 KR 0175559B1 KR 1019960045015 A KR1019960045015 A KR 1019960045015A KR 19960045015 A KR19960045015 A KR 19960045015A KR 0175559 B1 KR0175559 B1 KR 0175559B1
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Abstract
본 발명은 밝은 녹색 내지 암녹색의 다양한 녹색을 내는 ZrO2소결체의 제조 방법에 관한 것이다.The present invention relates to a method for producing a ZrO 2 sintered body having a variety of bright green to dark green colors.
종래의 녹색 ZrO2소결체의 제조 방법은 ZrO2세라믹스에 단순히 발색 조제를 첨가하는 것으로, 명암 조절에 한계가 있고 플라스틱 소재의 느낌을 가지게 하며 시편간 편차 없이 재현성이 있도록 대량 생산하는 것이 불가능한 문제점이 있었다.Conventionally, a method of manufacturing a green ZrO 2 sintered body has a problem in that it is impossible to mass-produce ZrO 2 ceramics so that reproducibility can be achieved without deviation between the specimens, .
본 발명에 따르는 녹색 ZrO2소결체의 제조 방법은, 산화 분위기로 900 내지 1300℃에서 1 내지 4시간 동안 열처리한 후, ZrO2은 87 내지 94.7중량%, Y2O3은 5 내지 6중량%의 조성으로 발색 조제와 함께 혼합하여 성형한 후, 이를 산화물로에서 1300 내지 1600℃에서 1 내지 4시간동안 소결한 후, 이 소결체는 1200 내지 1550℃에서 500 내지 1000바아의 아르곤압으로 0.5 내지 2시간 동안 산화 열처리하여 제조되는 것을 특징으로 한다.The green ZrO 2 sintered body according to the present invention is manufactured by heat-treating the green ZrO 2 sintered body at 900 to 1300 ° C for 1 to 4 hours in an oxidizing atmosphere, then subjecting ZrO 2 to 87 to 94.7% by weight and Y 2 O 3 to 5 to 6% And then sintered in an oxide furnace at 1300 to 1600 ° C for 1 to 4 hours. The sintered body is then sintered at 1200 to 1550 ° C under an argon pressure of 500 to 1000 bar for 0.5 to 2 hours Lt; / RTI >
본 발명에 따라 제조된 녹색 ZrO2소결체는 투명도가 높으며, HIP 및 산화 열처리시의 온도에 따라 밝은 녹색 내지 암녹색의 다양한 녹색을 내는 ZrO2소결체를 시편간 편차없이 대량 생산할 수 있다. 또한, 고부가 가치 장식품에 적용할 수 있는 투명성이 좋은 미려한 암녹색 ZrO2소결체를 대량 생산할 수 있다.The green ZrO 2 sintered body manufactured according to the present invention has high transparency and can mass produce ZrO 2 sintered body having various green colors ranging from light green to dark green depending on the temperature during HIP and oxidation heat treatment without deviation between specimens. In addition, it is possible to mass-produce sophisticated dark green ZrO 2 sintered bodies with good transparency that can be applied to high value added ornaments.
Description
[발명의 명칭][Title of the Invention]
녹색 ZrO2소결체의 제조 방법Manufacturing method of green ZrO 2 sintered body
[발명의 상세한 설명]DETAILED DESCRIPTION OF THE INVENTION [
[발명의 목적][Object of the invention]
본 발명의 목적은 밝은 녹색 내지 암녹색의 다양한 녹색을 내는 ZrO2소결체의 제조 방법을 제공하는 것이다.An object of the present invention is to provide a method for producing a ZrO 2 sintered body having various green colors ranging from light green to dark green.
[발명이 속하는 기술 분야 및 그 분야의 종래 기술][TECHNICAL FIELD OF THE INVENTION AND RELATED ART OF THE SAME]
본 발명은 녹색 ZrO2소결체의 제조 방법에 관한 것으로, 더욱 상세하게는 사전 열처리한 ZrO2, Y2O3에 발색 조제를 첨가하여 소결한 후 HIP(고온 등압 압축 성형) 및 산화 열처리 과정을 실시함으로써 밝은 녹색 내지 암녹색의 다양한 녹색을 내는 ZrO2소결체를 제조하는 방법에 관한 것이다.More particularly, the present invention relates to a method of manufacturing a green ZrO 2 sintered body. More specifically, the present invention relates to a method of manufacturing a green ZrO 2 sintered body by adding a coloring aid to ZrO 2 and Y 2 O 3 , To a method of producing a ZrO 2 sintered body having a variety of bright green to dark green colors.
일반적으로 ZrO2세라믹스는 다른 세라믹스에 비해 굴절율이 높아 광택성이 우수하며, 발색 조제를 첨가하여 흑색, 흰색 뿐만 아니라 다양한 색상을 낼 수 있어 시계류 등의 장식류 제품에 널리 활용되고 있다.In general, ZrO 2 ceramics has a higher refractive index than other ceramics, and is excellent in gloss. Further, since ZrO 2 ceramics can be provided with not only black and white but also various colors by adding a coloring aid, they are widely used in decorative products such as watches.
그러나, 종래의 녹색 ZrO2소결체의 제조방법은 ZrO2세라믹스에 단순히 발색 조제를 첨가하여 명암을 조절하는 것으로 명암 조절에 한계를 가졌다. 따라서, 코발트 녹색 등의 특정 색상의 명암을 조절하기 위해서는 성분의 함량을 달리한 발색 조제를 다시 준비하여 명암을 조절해야 하는 단점이 있었다.However, in the conventional method of manufacturing a green ZrO 2 sintered body, the contrast of the ZrO 2 ceramics is simply controlled by adding a coloring aid to limit the contrast. Therefore, in order to control the contrast of specific colors such as cobalt green, there is a drawback in that the contrast must be controlled by preparing a coloring composition having a different content of components.
또한, 종래의 방법으로 제조된 녹색 ZrO2소결체는 플라스틱 소재의 느낌을 가지므로, 보석류 등에서 느낄 수 있는 미려한 암녹색 ZrO2소결체를 제조하는 것이 불가능하여 고부가가치 장식품에 적용하기가 어려운 단점이 있었다.In addition, since the green ZrO 2 sintered body manufactured by the conventional method has a plastic material feel, it is impossible to produce a beautiful sintered body of dark green ZrO 2 that can be felt in jewelry or the like, so that it is difficult to apply it to high value added ornaments.
그리고, 녹색 ZrO2소결체에 해당하는 L, a, b값의 영역이 좁기 때문에 종래의 방법에 따른 일반적인 제조 공정으로는 시편간 편차 없이 재현성을 가지도록 녹색 ZrO2소결체를 제조하기가 어려웠다.Also, since the area of L, a, and b values corresponding to the green ZrO 2 sintered body is narrow, it is difficult to produce the green ZrO 2 sintered body so as to have reproducibility without variation between the specimens in a general manufacturing process according to the conventional method.
[발명이 이루고자 하는 기술적 과제][Technical Problem]
본 발명자들은 상기의 문제점을 개선시키기 위하여 연구한 결과, 발색 조제와 함께 ZrO2의 산소 결함을 미세 조절하여 제조된 녹색 ZrO2소결체가 천연 색상이 갖는 미려한 색상을 발현할 수 있으며, 소결 이후에 HIP 및 열처리 과정을 도입하면 동일 조합의 원료로도 5단계 이상의 명도를 갖는 녹색 ZrO2소결체를 제조할 수 있다는 것을 알게 되어 본 발명에 이르게 되었다.The inventors of the present invention have found that a green ZrO 2 sintered body prepared by finely controlling oxygen defects of ZrO 2 together with a coloring assistant can express a beautiful color of natural hue, And a heat treatment process were introduced, it was found that a green ZrO 2 sintered body having a lightness of 5 or more steps could be produced from the same combination of raw materials, leading to the present invention.
[발명의 구성 및 적용][Composition and Application of the Invention]
본 발명은 녹색 ZrO2소결체의 제조 방법에 있어서, ZrO2, Y2O3및 발색 조제의 분말을 산소 분위기하에서 900 내지 1300℃에서 1 내지 4시간 동안 열처리한 후, ZrO2은 87 내지 94.7중량%, Y2O3은 5 내지 6중량%의 조성으로 발색 조제와 함께 혼합하여 성형한 후, 이를 산화물로에서 1300 내지 1600℃에서 1 내지 4시간 동안 소결한 후, 이 소결체를 1200 내지 1550℃에서 500 내지 1000 바아의 아르곤압으로 0.5 내지 1시간 동안 HIP처리하고, HIP 처리한 소결체는 산화로에서 1200 내지 1600℃에서 0.5 내지 2시간동안 열처리하여서 되는 녹색 ZrO2소결체의 제조 방법인 것을 특징으로 한다.The present invention relates to a method of manufacturing a green ZrO 2 sintered body, ZrO 2, Y 2 O 3 and the powder of color development prepared at 900 to 1300 ℃ under an oxygen atmosphere after heat-treated for 1 to 4 hours, ZrO 2 is 87 to 94.7 wt. %, And Y 2 O 3 are mixed with a coloring aid in a composition of 5 to 6 wt%, molded and then sintered in an oxide furnace at 1300 to 1600 ° C for 1 to 4 hours, and then sintered at 1200 to 1550 ° C , And the HIP-treated sintered body is heat-treated in an oxidation furnace at 1200 to 1600 ° C for 0.5 to 2 hours to form a green ZrO 2 sintered body. do.
이하, 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명에 따르면, 종래의 녹색 ZrO2소결체가 원료의 조합, 성형 및 소결 과정을 거쳐서 제조되는 것과는 달리 본 발명의 녹색 ZrO2소결체는 원료의 사전 열처리, 조합, 성형 및 소결 과정을 거친 후 추가로 HIP 과정과 산화 열처리 과정을 거쳐서 제조되는 것을 특징으로 한다.According to the present invention, unlike the conventional green ZrO 2 sintered body manufactured through the combination of raw materials, molding and sintering process, the green ZrO 2 sintered body of the present invention is subjected to a preheating treatment, a combination, HIP process and oxidation heat treatment process.
본 발명에 따르면, 발색 조제와 함께 ZrO2의 산소 결함을 미세 조절하기 위해서 각 조성물을 화학 양론적인 면에서 조절한다. 이를 위해, 발색 조제를 생분말로 조합하는 대신에 산화 열처리하여 조합한다. 즉, ZrO2, Y2O3외에 발색 조제인 Cr2O3, Al2O3, CoO, MnO2, Fe2O3을 분말 상태에서 900 내지 1300℃의 산화 분위기(산소 유출 상태)에서 1 내지 4시간 동안 열처리한다. 그 결과, 제조된 녹색 ZrO2소결체가 투명성이 좋고 미려한 색상을 발현할 수 있다.According to the present invention, each composition is adjusted stoichiometrically in order to finely control the oxygen defects of ZrO 2 with the color development aid. For this purpose, the coloring aid is combined with an oxidative heat treatment instead of combining with the raw powder. In other words, Cr 2 O 3 , Al 2 O 3 , CoO, MnO 2 and Fe 2 O 3 , which are chromogenic additives in addition to ZrO 2 and Y 2 O 3 , For 4 hours. As a result, the produced green ZrO 2 sintered body can exhibit an excellent color with good transparency.
사전 열처리한 ZrO2, Y2O3및 발색 조제의 분말을 ZrO2: Y2O3: Cr2O3=92 내지 94.7 : 5 내지 6 : 0.3 내지 2 중량%, ZrO2: Y2O3: Cr2O3: Al2O3=91 내지 94.4 : 5 내지 6 : 0.3 내지 1.5 : 0.3 내지 1.5중량%, ZrO2: Y2O3: Cr2O3: Al2O3: CoO=90 내지 94.1 : 5 내지 6 : 0.3 내지 1.5 : 0.3 내지 1.5 : 0.3 내지 1.3중량% 또는 ZrO2: Y2O3: Cr2O3: Al2O3: CoO : MnO2: Fe2O3=87 내지 94.7 : 5 내지 6 : 0.3 내지 1.0 : 0.3 내지 1.0 : 0.3 내지 1.5 : 0.1 내지 0.8 : 0.1 내지 0.8중량%의 조성으로 혼합하여 성형한다.The pre-heat-treated ZrO 2 , Y 2 O 3 and color developer powder are mixed with ZrO 2 : Y 2 O 3 : Cr 2 O 3 = 92 to 94.7: 5 to 6: 0.3 to 2% by weight, ZrO 2 : Y 2 O 3 : Cr 2 O 3 : Al 2 O 3 = 91 to 94.4: 5 to 6: 0.3 to 1.5: 0.3 to 1.5 wt%, ZrO 2 : Y 2 O 3 : Cr 2 O 3 : Al 2 O 3 : CoO = 90 to 94.1: 5 to 6: 0.3 to 1.5: 0.3 to 1.5: 0.3 to 1.3%, or ZrO 2 by weight: Y 2 O 3: Cr 2 O 3: Al 2 O 3: CoO: MnO 2: Fe 2 O 3 = 87 To 94: 5 to 6: 0.3 to 1.0: 0.3 to 1.0: 0.3 to 1.5: 0.1 to 0.8: 0.1 to 0.8% by weight.
상기 발색 조제를 주성분인 ZrO2, Y2O3와 조합한 후, 소결 과정에서 1차로 산화로를 이용하여 1300 내지 1600℃에서 1 내지 4시간 동안 소결한다. 소결 과정을 통해 98% 이상의 치밀화된 녹색 ZrO2소결체를 얻을 수 있다.The coloring aid is combined with ZrO 2 and Y 2 O 3 as main components, and then sintered at 1,300 to 1,600 ° C. for 1 to 4 hours using an oxidation furnace in a sintering process. Through the sintering process, a green ZrO 2 sintered body having a densification of 98% or more can be obtained.
본 발명에 있어서 소결이라 함은 발색 조제를 열처리 한 후, 원료의 조합 및 성형 단계 후에 실시하는 과정으로, 종래의 녹색 ZrO2소결체의 제조 방법에 있어서 소결 과정으로 발색 단계를 끝내는 것과는 달리, 본 발명에 따른 소결 과정은 발색 단계에 포함되는 여러 과정 중 하나이다.In the present invention, sintering refers to a process in which a coloring aid is heat-treated, followed by a combination of raw materials and a molding step. Unlike the conventional method of finishing a coloring step in a sintering process in a method of manufacturing a green ZrO 2 sintered body, Sintering process is one of several processes involved in the color development stage.
상기에서 제조된 녹색 ZrO2소결체를 더욱 어둡게 하기 위해서 HIP 과정을 실시한다.To further darken the green ZrO 2 sintered body prepared above, the HIP process is performed.
본 발명의 HIP 과정에서는 상기의 치밀화된 녹색 ZrO2소결체를 2차로 1200 내지 1550℃의 온도에서 500 내지 1000 바아의 아르곤압으로 0.5 내지 1시간 동안 처리한다. 이 과정에 의해서 98% 치밀화된 녹색 ZrO2소결체는 더욱 치밀해지고, 진하고 균일한 암녹색의 ZrO2소결체가 된다.In the HIP process of the present invention, the densified green ZrO 2 sintered body is treated with an argon pressure of 500 to 1000 bar for 0.5 to 1 hour at a temperature of 1200 to 1550 ° C secondarily. By this process, the green ZrO 2 sintered body, which is 98% densified, becomes more dense and becomes a dark green uniformly dark green ZrO 2 sintered body.
HIP 과정은 Zr+4→Zr+3, Zr+2로 전자가가 변하면서 환원성 분위기가 되면서 발현되는 색상을 이용하는 것으로 녹색ZrO2소결체의 색상을 어둡게 한다.The HIP process darkens the color of the green ZrO 2 sintered body by using the color expressed in a reducing atmosphere as electrons change from Zr +4 to Zr +3 and Zr +2 .
일반적으로 흑연 발연체 로(爐)내의 환원도는 탄소 분위기하의 탄소 활동도에 비례하는데, 탄소 활동도는 온도가 높아질수록 증가한다. 따라서, 흑연 발열체로내의 온도를 높이면 탄소의 활동도가 증가하게 되고, 결과적으로 로내의 환원도가 증가하게 된다. 본 발명에 따르면 단순히 흑연 발열체 로내의 온도를 높이는 것으로 녹색 ZrO2소결체의 색상을 어둡게 할 수 있다.In general, the degree of reduction in a graphite furnace furnace is proportional to the carbon activity under a carbon atmosphere, and the carbon activity increases with increasing temperature. Therefore, increasing the temperature inside the graphite heating element increases the activity of carbon, and as a result, the degree of reduction in the furnace increases. According to the present invention, it is possible to darken the color of the green ZrO 2 sintered body simply by raising the temperature inside the graphite heating body.
HIP 처리시에는 일반 흑연 발열체 로와는 달리 고압을 가할 수 있는데, 고온에서 탄소 활동도는 온도뿐만 아니라 압력에 의해서도 변화한다. 따라서, 고온에 있는 흑연 발열체 로내의 압력을 변화시킴으로써 녹색ZrO2소결체의 색상을 어둡게 할 수 있다.Unlike normal graphite heating elements, high pressure can be applied during HIP treatment. At high temperature, carbon activity changes not only by temperature but also by pressure. Therefore, the color of the green ZrO 2 sintered body can be made dark by changing the pressure in the graphite heating element at a high temperature.
상기의 온도와 압력 이외에도 탄소 활동도의 공정 변수에는 흑연 발열체 로내의 시편 적재 도가니의 재질, 형상, 크기 또는 흑연 발열체 로내의 시편 적재방법 등이 있다.In addition to the above temperatures and pressures, the process parameters of carbon activity include the material, shape, size of the specimen loading crucible in the graphite heating furnace, and the method of loading the specimen in the graphite heating furnace.
본 발명에 따르면, 어두워진 녹색 ZrO2소결체의 명도를 다시 조절하기 위한 최종 단계로 산화 열처리 과정을 실시한다.According to the present invention, an oxidation heat treatment process is performed as a final step for regulating the brightness of the dark green ZrO 2 sintered body.
즉, HIP 처리한 녹색 ZrO2소결체를 1200 내지 1600℃에서 0.5 내지 2시간 동안 산화로에서 열처리하면, ZrO2이온이 Zr+2, Zr+3→Zr+4로 산화되면서 녹색 ZrO2소결체의 어두운 색상이 밝게 된다. 이때, 녹색 ZrO2소결체가 밝게 되는 정도는 산화 분위기의 정도에 따라 변하며, 이는 공정 변수의 측면에서 보면 산화로의 온도 조절에 의한 것이다.That is, when heat-treated in a HIP process for a green oxide ZrO 2 sintered body at 1200 to 1600 ℃ 0.5 to 2 hours, ZrO 2 +2 ion is Zr, Zr +4 +3 → Zr oxide as a dark green ZrO 2 sintered body The color becomes bright. At this time, the extent to which the green ZrO 2 sintered body is brightened varies depending on the degree of the oxidizing atmosphere, which is due to the temperature control of the oxidizing furnace in terms of process variables.
동일한 조성의 녹색 ZrO2소결체의 명도를 공정상으로 구분하여 보면 다음과 같다.The brightness of the green ZrO 2 sintered body having the same composition is classified as follows.
상기에서 알 수 있는 바와 같이, HIP 및 산화열처리 과정을 거침으로써 동일 조합의 원료로 5단계 이상의 명도를 갖는 녹색 ZrO2소결체는 제조할 수 있다.As can be seen from the above, a green ZrO 2 sintered body having a lightness of five or more steps can be produced from the same combination of raw materials by subjecting to HIP and oxidation heat treatment.
[실시예][Example]
이하, 본 발명을 실시예에 의해 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail with reference to the following examples.
본 발명에서 사용되는 ZrO2, Y2O3및 발색 조제의 분말을 900 내지 1300℃에서 산소를 유출하면서 1 내지 4시간 동안 열처리하였다. 이때 산소의 유출 속도는 0.1 내지 1ℓ/min 정도이다.The powders of ZrO 2 , Y 2 O 3 and coloring auxiliary used in the present invention were heat-treated at 900 to 1300 ° C for 1 to 4 hours while oxygen was flowing out. At this time, the outflow rate of oxygen is about 0.1 to 1 L / min.
열처리된 분말을 분쇄하여 0.2 내지 1㎛의 미세 분말을 얻은 후 ZrO2병에서 증류수를 혼합 용매로 사용하여 ZrO2: Y2O3: Cr2O3=92 내지 94.7 : 5 내지 6 : 0.3 내지 2 중량%, ZrO2: Y2O3: Cr2O3: Al2O3=91 내지 94.4 : 5 내지 6 : 0.3 내지 1.5 : 0.3 내지 1.5중량%, ZrO2: Y2O3: Cr2O3: Al2O3: CoO=90 내지 94.1 : 5 내지 6 : 0.3 내지 1.5 : 0.3 내지 1.5 : 0.3 내지 1.0중량% 또는 ZrO2: Y2O3: Cr2O3: Al2O3: CoO : MnO2: Fe2O3=87 내지 94.7 : 5 내지 6 : 0.3 내지 1.0 : 0.3 내지 1.0 : 0.3 내지 1.5 : 0.1 내지 0.8 : 0.1 내지 0.8중량%의 발색 조제를 24 내지 72시간 동안 혼합한 후 분쇄하였다.After the heat-treated powder obtained by pulverizing the fine powder of 0.2 to 1㎛ using distilled water in a bottle with a mixed solvent ZrO 2 ZrO 2: Y 2 O 3: Cr 2 O 3 = 92 to 94.7: 5 to 6: 0.3 to 2% by weight, ZrO 2: Y 2 O 3 : Cr 2 O 3: Al 2 O 3 = 91 to 94.4: 5 to 6: 0.3 to 1.5: 0.3 to 1.5% by weight, ZrO 2: Y 2 O 3 : Cr 2 Al 2 O 3 : Al 2 O 3 : CoO = 90 to 94.1: 5 to 6: 0.3 to 1.5: 0.3 to 1.5: 0.3 to 1.0 wt.% Or ZrO 2 : Y 2 O 3 : Cr 2 O 3 : Al 2 O 3 : Coating composition of CoO: MnO 2 : Fe 2 O 3 = 87 to 94.7: 5 to 6: 0.3 to 1.0: 0.3 to 1.0: 0.3 to 1.5: 0.1 to 0.8: 0.1 to 0.8% Followed by pulverization.
혼합된 슬러리를 충분히 건조시킨 후 분쇄하고, 분쇄한 미분을 사용하여 원하는 형상으로 일축 가압 건조성형을 한 후, 산화물로에서 1300 내지 1600℃에서 1 내지 4시간 동안 소결하여 98% 이상의 치밀화된 녹색 ZrO2소결체는 얻었다.The mixed slurry was thoroughly dried and then pulverized. The compacted powder was uniaxially pressed into a desired shape and sintered in an oxide furnace at 1300 to 1600 ° C for 1 to 4 hours to obtain a densified green ZrO 2 2 sintered bodies were obtained.
상기 소결체는 1200 내지 1550℃에서 500 내지 1000바아의 아르곤압으로 30 내지 60분간 HIP처리하여 녹색 ZrO2소결체의 색상을 어둡게 발현시켰다.The sintered body was subjected to HIP treatment at 1200 to 1550 ° C for 30 to 60 minutes under an argon pressure of 500 to 1000 bar to darken the color of the green ZrO 2 sintered body.
그 다음, 산화로를 이용하여 1200 내지 1600℃ 영역의 온도에서 0.5 내지 2시간동안 열처리하여 ZrO2소결체의 명도를 조절함으로써 밝은 녹색 내지 암녹색의 다양한 녹색을 내는 ZrO2소결체는 제조하였다.Then, the heat treatment using the oxidation at a temperature of 1200 to 1600 ℃ region for 0.5 to 2 hours ZrO 2 sintered body that a light green to dark green by adjusting the brightness of the green variety of ZrO 2 sintered body was prepared.
[발명의 효과][Effects of the Invention]
본 발명에 따라 제조된 녹색 ZrO2소결체는 투명도가 높으며, HIP 및 산화 열처리시의 온도에 따라 밝은 녹색 내지 암녹색의 다양한 녹색 ZrO2소결체는 시편간 편차 없이 대량 생산할 수 있다. 또한 고부가 가치 장식품에 적용할 수 있는 투명성이 좋은 미려한 암녹색 ZrO2소결체를 대량 생산할 수 있다.The green ZrO 2 sintered body produced according to the present invention has a high transparency and can be mass-produced in a variety of green ZrO 2 sintered bodies having a light green to dark green color depending on the temperature at the time of HIP and oxidation heat treatment. Also, it is possible to mass-produce beautiful dark green ZrO 2 sintered body with good transparency that can be applied to high value added ornaments.
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