WO2012153645A1 - METHOD FOR PRODUCING HIGH-STRENGTH HIGH-TOUGHNESS ZrO2-Al2O3-BASED SOLID SOLUTION CERAMIC - Google Patents

METHOD FOR PRODUCING HIGH-STRENGTH HIGH-TOUGHNESS ZrO2-Al2O3-BASED SOLID SOLUTION CERAMIC Download PDF

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WO2012153645A1
WO2012153645A1 PCT/JP2012/061196 JP2012061196W WO2012153645A1 WO 2012153645 A1 WO2012153645 A1 WO 2012153645A1 JP 2012061196 W JP2012061196 W JP 2012061196W WO 2012153645 A1 WO2012153645 A1 WO 2012153645A1
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solid solution
zro
sintering
mol
temperature
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健 廣田
英行 佐藤
健伍 柴谷
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学校法人同志社
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Definitions

  • the present invention relates to a method for making high strength toughness ZrO 2 -Al 2 O 3 based solid solution ceramics.
  • Non-Patent Document 1 ZrO 2 -25 mol% Al 2 O 3 solid solution powder was prepared, solid solution ceramics of this system were prepared by HIP sintering, and the ceramic with a fracture toughness value K IC of 23 MPa ⁇ m 1/2 is an astonishing value. reported.
  • the bending strength ( ⁇ b ) remains at about 570 MPa, and it does not reach practical use where ⁇ b is 1 GPa or more, and simultaneously satisfies high strength ( ⁇ 1 GPa) and toughness ( ⁇ 15 MPa ⁇ m 1/2 ).
  • ⁇ b the bending strength
  • the present invention solves the above-mentioned problems in the prior art, and a high-strength toughness ZrO 2 -Al 2 O 3 system that simultaneously satisfies high strength ( ⁇ 1 GPa) and toughness ( ⁇ 15 MPa ⁇ m 1/2 ). It is an object of the present invention to provide a method capable of producing solid solution ceramics. As a result of various studies, the present inventors have found that ZrO 2 (98.5 mol% ZrO 2 -1.5 mol% Y) in which 1.5 mol% Y 2 O 3 is added to ZrO 2 using a sol-gel method.
  • ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution powder was prepared, and this solid solution was prepared.
  • a high strength toughness ZrO that satisfies the above-mentioned strength (bending strength) and fracture toughness values when the powder is calcined at a temperature higher than the crystallization temperature and then sintered under a certain condition.
  • the present inventors have found that 2- Al 2 O 3 based solid solution ceramics can be produced and studied the optimum range of the amount of Y 2 O 3 added, thereby completing the present invention.
  • the method for producing the high-strength toughness ZrO 2 -Al 2 O 3 solid solution ceramics of the present invention capable of solving the above-mentioned problems is the following steps A and B: Step A: Sol - to ZrO 2 using a gel method 0.3 ⁇ 1.7mol% Y 2 O 3 ZrO 2 was added (99.7 ⁇ 98.3mol% ZrO 2 -0.3 ⁇ 1.7mol % Y 2 O 3 ) -20-30 mol% Al 2 O 3 amorphous solid solution powder, and the resulting solid solution powder is calcined at a temperature equal to or higher than the crystallization temperature to obtain crystalline ZrO 2 solid solution powder.
  • step B forming the crystalline ZrO 2 solid solution powder obtained in the step A, and then heating in an inert gas atmosphere at a heating rate of 50 ° C./min or more and a pressure of 30 to 100 MPa. And a sintering step at a sintering temperature of 1250 to 1350 ° C. for 3 to 30 minutes.
  • the present invention performs the molding in the step B by cold isostatic pressing (CIP), and the sintering in the step B is performed by pulsed electric pressure sintering. It is also characterized by carrying out by a sintering method (Pulsed Electric-Current Pressure Sintering: PECPS) or a discharge plasma sintering method (Spark Plasma Sintering: SPS). Furthermore, the present invention is characterized in that, in the manufacturing method having the above characteristics, the sintering in the step B is mainly performed in an argon gas atmosphere or a nitrogen gas atmosphere.
  • Toughness is achieved by uniformly precipitating fine aluminum oxide Al 2 O 3 fine particles from the solid solution powder during sintering.
  • High strength toughness ZrO 2 -Al 2 O 3 system with bending strength ⁇ b ⁇ 1 GPa and fracture toughness value K IC ⁇ 15 MPa ⁇ m 1/2 by using the production method of the present invention.
  • Solid solution ceramics can be produced.
  • A is an XRD pattern of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics sintered at 1100 ° C.
  • B is a ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C.
  • (A) in (C) is an XRD pattern of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution powder calcined at 820 ° C.
  • (b), (c) ), (D), (e), and (f) are ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics sintered at 1100 ° C., 1200 ° C., 1250 ° C., 1300 ° C., and 1350 ° C., respectively. This is an XRD pattern.
  • (A) -1 is an SEM photograph of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramic powder calcined at 800 ° C.
  • (A) -2 is ZrO 2 -25 mol% Al sintered at 1200 ° C. It is a SEM photograph of a fracture surface of 2 O 3 solid solution ceramics.
  • (B) -1 is an SEM photograph of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramic powder calcined at 820 ° C.
  • (B) -2 is sintered at 1200 ° C.
  • FIG. 3 is a SEM photograph of the fracture surface of the ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics, and the average particle diameter of each is shown on the right side of the photograph.
  • A SEM photograph of fracture surface of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C.,
  • B 1250 ° C.,
  • C 1300 ° C. The diameter is also listed.
  • sintering temperature is a graph showing ZrO 2 (1.5Y) -25mol% Al 2 O 3 solid solution ceramics bending strength sigma b, fracture toughness K IC, the relationship between the Vickers hardness H v.
  • ZrO 2 was using a solid solution powder prepared at various sintering temperatures (1.5Y) -25mol% Al 2 O 3 solid solution ceramics and, ZrO 2 that by using the mixed powder was made in a variety of sintering temperatures (3.0Y) -25mol% Al 2 O 3 composite mechanical properties (flexural strength, Vickers hardness, fracture toughness value) of ceramics is a graph showing a. It is a graph which shows the change of the fracture toughness value and the Vickers hardness of the ceramic sintered at 1300 ° C. in which the amount of Y 2 O 3 added to ZrO 2 is changed in ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics.
  • Mechanical properties of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics prepared from raw materials obtained using the sol-gel method, and those obtained using water-soluble raw materials It is the table which compared.
  • Step A and Step B in the method of the present invention capable of producing a high-strength toughness ZrO 2 -Al 2 O 3 solid solution ceramic will be described.
  • step in the present invention A step Preparation of ZrO 2 solid solution powder
  • a solid solution powder prepared by adding 30 to 20 mol% of Al 2 O 3 is prepared.
  • such a solid solution powder is prepared by a process described in the flowchart shown in FIG. Done. However, it is not limited to the raw material and conditions used in the process shown in FIG.
  • the amount of Y 2 O 3 added to ZrO 2 is limited to 0.3 to 1.7 mol%, even if the amount added is less than 0.3 mol%, or conversely exceeds 1.7 mol%, This is because the bending strength ⁇ b at room temperature is smaller than 1000 Ma and the fracture toughness value K IC is smaller than 15 MPa ⁇ m 1/2 , and the addition amount of Al 2 O 3 is limited to 20 to 30 mol%. This is because even if the addition amount is less than 20 mol%, or conversely, the addition strength exceeds 30 mol%, the bending strength ⁇ b becomes less than 1000 MPa.
  • the temperature at which the solid solution powder is calcined to prepare a tetragonal ZrO 2 solid solution powder may be higher than the crystallization temperature, and preferably 700 ° C. to 900 ° C.
  • the crystalline ZrO 2 solid solution powder obtained in the step A is molded, and then the heating rate is 50 ° C./min or more in an inert gas atmosphere.
  • High strength toughness ZrO 2 -Al 2 O 3 based solid solution ceramics are produced by sintering at a pressure of 30 to 100 MPa and a sintering temperature of 1250 to 1350 ° C. for 3 to 30 minutes.
  • a cold isostatic press is suitable for forming a ZrO 2 solid solution powder, and a pulsed current pressure sintering method in an argon gas or nitrogen gas atmosphere is used to sinter the obtained molded body.
  • a discharge plasma sintering method is suitable.
  • the pulsed current pressure sintering method in which a pulsed direct current is applied at a low voltage under uniaxial pressure and high energy is instantaneously generated by the spark discharge phenomenon, is suitable for the rapid joule. This is because melting and high-speed diffusion occur by heating, and high-speed sintering can be achieved in a short time, so that a dense sintered body (relative density of 90% or more) with relatively suppressed grain growth can be obtained. The law is suitable for the same reason.
  • Particularly preferred conditions for pulsed current pressure sintering in the present invention are the conditions of a heating rate of 50 to 100 ° C./min, an applied pressure of 60 MPa, a sintering temperature of 1270 to 1330 ° C., and a holding time of 10 minutes in an argon gas atmosphere. .
  • a heating rate of 50 to 100 ° C./min
  • an applied pressure of 60 MPa
  • a sintering temperature of 1270 to 1330 ° C.
  • a holding time 10 minutes in an argon gas atmosphere.
  • the applied pressure is less than 30 MPa
  • the sintering density is low, and conversely if it exceeds 100 MPa, the upper limit is imposed on the strength of the mold used for the electric current pressure sintering.
  • the rate of temperature increase if it is less than 50 ° C./minute, the heat treatment takes a long time and the manufacturing cost becomes high.
  • it exceeds 100 ° C./minute the microstructure inside the sintered body becomes uneven, resulting in a homogeneous and large Since preparation of a sample becomes difficult, it is not preferable.
  • the bending strength ⁇ b is a three-point bending strength value measured under the conditions of a span length of 8 mm and a crosshead feed of 0.5 mm / min
  • the fracture toughness value K IC is a load of 10 kg. (98N) Indentation (IF) method (K. Niihara et al., J. Master), in which a diamond indenter with a square pyramid is pushed into the ceramic surface for 5 seconds and evaluated from the length of cracks generated at the four corners Sci. Lett., 1, 13-16 (1982)).
  • the crystalline solid solution powder is sized and then molded (98 MPa), followed by cold isostatic pressing (245 MPa), and then a commercially available pulse current pressure sintering apparatus (SPS Syntex). (Uses Co., Ltd./SPS-510A) and pulsed energization under an argon gas atmosphere at a pressure of 60 MPa, a sintering temperature of 1100 to 1350 ° C., a holding time of 10 minutes, and a heating rate of 100 ° C./min. Pressure sintering was performed to obtain a sintered body (ZrO 2 (1.5Y) -Al 2 O 3 solid solution ceramics).
  • FIG. 2 shows an XRD pattern of the solid solution ceramic sintered body thus obtained.
  • (A) is an XRD of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramic sintered at 1100 ° C.
  • the pattern (B) is an XRD pattern of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C.
  • (A) in (C) is an XRD pattern of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution powder calcined at 820 ° C., and (b) to (f) are sintered An XRD pattern of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics obtained by changing the temperature from 1100 ° C.
  • FIG. 3 shows SEM photographs of the calcined powder thus obtained and the fracture surface of the solid solution ceramic sintered body.
  • A -1 is ZrO calcined at 800 ° C. a SEM photograph of 2 -25mol% Al 2 O 3 solid solution ceramic powder
  • (a) -2 is an SEM photograph of the fracture surface of the ZrO 2 -25mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C.
  • (B) -1 is an SEM photograph of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramic powder calcined at 820 ° C.
  • B) -2 is sintered at 1200 ° C.
  • FIG. 4 shows an SEM photograph of the fracture surface of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics when the firing temperature is changed, and (A) shows a firing temperature of 1200 ° C.
  • the firing temperature is 1250 ° C.
  • (C) is the case where the firing temperature is 1300 ° C. From these SEM photographs, it can be seen that the firing temperature is 1200 ° C. to 1300 ° C. and that the structure is denser. From the comparison of the respective average particle diameters, the firing temperature increases slightly from 180 to 200 nm. I understand that.
  • Tables 1 and 2 below show the squares of the ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics and the ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics prepared in the above experiment.
  • the volume ratio (t / m), theoretical density, bulk density and relative density of crystalline zirconium oxide (t-ZrO 2 ) / monoclinic zirconium oxide (m-ZrO 2 ) are summarized.
  • FIG. 5 shows the sintering temperature, bending strength ⁇ b , and fracture toughness value K IC for the ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramic when the firing temperature is changed. , the relationship of Vickers hardness H v is shown in a graph.
  • a bending strength ⁇ b of 1 GPa or higher can be achieved (1.33 GPa when the sintering temperature is 1300 ° C.), and the sintering temperature is about 1230 ° C.- in the case of 1360 ° C. 18 MPa ⁇ m 1/2 or more, 21.3MPa ⁇ in the case of about 1270 °C ⁇ 1330 °C 20MPa ⁇ m 1/2 or more fracture toughness K IC (sintering temperature 1300 ° C. in the case of m 1/2 ) can be achieved.
  • the Vickers hardness H v is the sintering temperature was above 13GPa to not less than about 1230 °C (13.4GPa when the sintering temperature is 1300 ° C.).
  • Comparative product 1 ZrO 2 (1.5Y-ZrO 2 ) powder added with commercially available 1.5 mol% Y 2 O 3 (98.5 mol% ZrO 2 -1.5 mol% Y 2 O 3 ) and commercially available Al 2 O 3 fine particles was mixed with a planetary ball mill to obtain a mixed powder (Z
  • High pressure sintering was performed under the conditions of 1 GPa, a sintering temperature of 900 ° C., and a holding time of 30 minutes to obtain a sintered body.
  • the bending strength ⁇ b was 1.125 GPa and the fracture toughness value K IC was 15.8 MPa ⁇ m 1/2 .
  • a forming process under a very high pressure, a cold isostatic press It was found that a treatment process and a sintering process are necessary.
  • Example 3 ZrO 2 (1.5Y) -25mol% Al 2 O 3 solid solution ceramics produced using the solid solution powder, ZrO 2 (3.0Y) produced by using the mixed powder -25mol% Al 2 Comparison of mechanical properties with O 3 composite ceramics ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics produced by using a solid solution powder by changing the sintering temperature in the range of 1100 to 1350 ° C., The mechanical properties (bending strength, Vickers hardness, fracture toughness value) of each of the ZrO 2 (3.0Y) -25 mol% Al 2 O 3 composite ceramics produced by sintering the mixed powder were measured.
  • the Vickers hardness increases (16 GPa or more), but the bending strength becomes 1000 MPa or less.
  • the fracture toughness value is 7 MPa ⁇ m 1/2 or less.
  • Example 4 Y 2 O 3 amount when changing the addition, when the amount of change Y 2 O 3 of fracture toughness and Vickers hardness was varied in the range of 0 ⁇ 3 mol%, the fracture toughness value and The change in Vickers hardness was measured.
  • the sintering conditions were a pressure of 50 to 60 MPa, a sintering temperature of 1300 ° C., and a holding time of 10 minutes.
  • the result is shown in FIG. From the graph of FIG. 7A, regarding the fracture toughness value K IC , the amount of Y 2 O 3 added is 15 MPa ⁇ m 1/2 or more in the range of 0.3 to 1.7 mol%, and 0.7 to 1.5 mol. % Range was found to be 18 MPa ⁇ m 1/2 or more.
  • the bending strength in the range of such addition amount is 1 GPa or more.
  • the Vickers hardness is 12 GPa or more when the Y 2 O 3 addition amount is in the range of 0.3 to 1.7 mol%, and 14 GPa in the range of 0.7 to 1.5 mol%. It turns out that it becomes the above. Therefore, the amount of Y 2 O 3 added for producing high strength toughness ZrO 2 —Al 2 O 3 based solid solution ceramics is in the range of 0.3 to 1.7 mol%, and a particularly preferable range is 0.8. It was found to be 7 to 1.5 mol%.
  • Example 5 Mechanical properties of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics (product of the present invention) prepared from raw materials obtained using the sol-gel method, and water-soluble raw materials Mechanical properties of the product obtained by using the three types of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics manufactured under the manufacturing conditions shown in FIG. 8 and measuring various mechanical properties for each. did. From the measurement results shown in FIG. 8, in the case of using the raw material by the sol-gel method (the manufacturing method of the present invention), the crystal structure of the produced solid solution ceramic is more tetragonal than monoclinic (m).
  • the ZrO 2 -Al 2 O 3 solid solution ceramics obtained using the production method of the present invention has a bending strength of 1 GPa or more and a fracture toughness value of 15 MPa ⁇ m 1/2 or more. It can be used for various applications that require toughness, such as ceramic machine parts, biological ceramics (artificial roots, artificial joints, artificial bones), household knives, cutting boards, and the like.

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Abstract

Provided is a method for producing a high-strength high-toughness ZrO2-Al2O3-based solid solution ceramic. Y2O3 in an amount of 0.3-1.7 mol% is added ZrO2 employing a sol-gel method to prepare an amorphous ZrO2-(20-30 mol% Al2O3) solid solution powder, and the resultant amorphous solid solution powder is pre-sintered at a temperature equal to or higher than a crystallization temperature, thereby preparing a crystalline ZrO2 solid solution powder (step A). The resultant crystalline ZrO2 solid solution powder is molded, and the molded product is then sintered in an inert gas atmosphere under the conditions of a temperature rising rate of 50ºC/min or more, a pressure of 30-100 MPa and a sintering temperature of 1250-1350˚C for 3-30 minutes (step B). In this process, it is preferred to perform the molding in the step B by means of cold isostatic press and perform the sintering by a pulse current pressure sintering method or a spark plasma sintering method in an argon or nitrogen gas atmosphere.

Description

高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスの作製法Fabrication method of high strength toughness ZrO2-Al2O3 solid solution ceramics
　本発明は、高強度強靱性のＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスを作製するための方法に関する。 The present invention relates to a method for making high strength toughness ZrO 2 -Al 2 O 3 based solid solution ceramics.
　金属に比較して、化学的安定性、対腐食性、高温環境下での使用可能といった多くの特徴を有するセラミックス材料は、硬度や強度が高いが、靱性が低いという弱点のため、その応用が限定されてきた。
　セラミックスの強靱性、すなわち破壊靱性値（ＫＩＣ）向上のため現在まで多くの研究がなされてきており、特に、酸化イットリウム（Ｙ２Ｏ３）を２～３ｍｏｌ％添加固溶させた部分安定化ジルコニア（Partially stabilized zirconium, PSZ）に注目が集まり、熱間静水圧プレス（Hot isostatic pressing：HIP）焼結によるＹ２Ｏ３部分安定化ＺｒＯ２‐Ａｌ２Ｏ３複合材料の強靱性・高強度化が明らかになった。他方、ＺｒＯ２‐Ａｌ２Ｏ３系固溶体はあまり注目されていなかった。 Compared to metals, ceramic materials with many characteristics such as chemical stability, anti-corrosion properties, and use in high-temperature environments have high hardness and strength, but their weakness is low toughness. Limited.
Many studies have been made to improve the toughness of ceramics, that is, the fracture toughness value (K IC ), and in particular, partial stabilization by adding 2-3 mol% of yttrium oxide (Y 2 O 3 ) as a solid solution. Attention has been focused on zirconia (Partially stabilized zirconium, PSZ), and the toughness and high strength of Y 2 O 3 partially stabilized ZrO 2 -Al 2 O 3 composites by hot isostatic pressing (HIP) sintering It became clear. On the other hand, ZrO 2 -Al 2 O 3 based solid solution has not been much attention.
　そこで、本発明者等は、下記の非特許文献１において、ゾル‐ゲル法（金属の有機及び無機化合物の溶液をゲルとして固化し、ゲルの加熱によって酸化物の固体を作製する方法）を用いてＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体粉体を調製し、ＨＩＰ焼結によりこの系の固溶体セラミックスを作製し、破壊靱性値ＫＩＣが２３ＭＰａ・ｍ１／２というセラミックスでは驚異的な値を報告した。しかし、曲げ強度（σｂ）は約５７０ＭＰａに留まり、σｂが１ＧＰａ以上必要な実用化には及ばず、高強度（≧１ＧＰａ）と強靱性（≧１５ＭＰａ・ｍ１／２）を同時に満足する高強度強靱性のセラミックスが求められていた。 Therefore, the present inventors use the sol-gel method (a method of solidifying a solution of metal organic and inorganic compounds as a gel and producing an oxide solid by heating the gel) in Non-Patent Document 1 below. ZrO 2 -25 mol% Al 2 O 3 solid solution powder was prepared, solid solution ceramics of this system were prepared by HIP sintering, and the ceramic with a fracture toughness value K IC of 23 MPa · m 1/2 is an astonishing value. reported. However, the bending strength (σ b ) remains at about 570 MPa, and it does not reach practical use where σ b is 1 GPa or more, and simultaneously satisfies high strength (≧ 1 GPa) and toughness (≧ 15 MPa · m 1/2 ). There has been a demand for ceramics having high strength and toughness.
　本発明は、従来技術における前述の問題点を解決し、高強度（≧１ＧＰａ）と強靱性（≧１５ＭＰａ・ｍ１／２）を同時に満足する高強度強靱性のＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスを作製可能な方法を提供することを課題とする。
　本発明者等は、種々検討を行った結果、ゾル‐ゲル法を用いてＺｒＯ２に対し１．５ｍｏｌ％Ｙ２Ｏ３を添加したＺｒＯ２（９８．５ｍｏｌ％ＺｒＯ２‐１．５ｍｏｌ％Ｙ２Ｏ３）‐２５ｍｏｌ％Ａｌ２Ｏ３の非晶質の固溶体粉体（以下、「ＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体粉体」と表す）を調製し、この固溶体粉体を結晶化温度以上で仮焼した後に成形し、その後、一定条件下で焼結を行なった場合に、上記の強度（曲げ強度）及び破壊靱性値を同時に満足する高強度強靱性のＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスが作製できることを見出し、Ｙ２Ｏ３添加量の最適範囲を検討して本発明を完成した。 The present invention solves the above-mentioned problems in the prior art, and a high-strength toughness ZrO 2 -Al 2 O 3 system that simultaneously satisfies high strength (≧ 1 GPa) and toughness (≧ 15 MPa · m 1/2 ). It is an object of the present invention to provide a method capable of producing solid solution ceramics.
As a result of various studies, the present inventors have found that ZrO 2 (98.5 mol% ZrO 2 -1.5 mol% Y) in which 1.5 mol% Y 2 O 3 is added to ZrO 2 using a sol-gel method. 2 O 3 ) -25 mol% Al 2 O 3 amorphous solid solution powder (hereinafter referred to as “ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution powder”) was prepared, and this solid solution was prepared. A high strength toughness ZrO that satisfies the above-mentioned strength (bending strength) and fracture toughness values when the powder is calcined at a temperature higher than the crystallization temperature and then sintered under a certain condition. The present inventors have found that 2- Al 2 O 3 based solid solution ceramics can be produced and studied the optimum range of the amount of Y 2 O 3 added, thereby completing the present invention.
　上記の課題を解決可能な本発明の高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスの作製法は、以下の工程Ａ及びＢ：
　工程Ａ：ゾル‐ゲル法を用いてＺｒＯ２に対し０．３～１．７ｍｏｌ％Ｙ２Ｏ３を添加したＺｒＯ２（９９．７～９８．３ｍｏｌ％ＺｒＯ２‐０．３～１．７ｍｏｌ％Ｙ２Ｏ３）‐２０～３０ｍｏｌ％Ａｌ２Ｏ３の非晶質の固溶体粉体を調製し、得られた固溶体粉体を結晶化温度以上で仮焼して結晶質のＺｒＯ２固溶体粉体を調製する工程、及び
　工程Ｂ：前記工程Ａで得られた結晶質のＺｒＯ２固溶体粉体を成形し、次いで、不活性ガス雰囲気下、昇温速度５０℃／ｍｉｎ以上、圧力３０～１００ＭＰａ、焼結温度１２５０～１３５０℃で３～３０分の条件にて焼結する工程
を含むことを特徴とする。 The method for producing the high-strength toughness ZrO 2 -Al 2 O 3 solid solution ceramics of the present invention capable of solving the above-mentioned problems is the following steps A and B:
Step A: Sol - to ZrO 2 using a gel method 0.3 ~ 1.7mol% Y 2 O 3 ZrO 2 was added (99.7 ~ 98.3mol% ZrO 2 -0.3 ~ 1.7mol % Y 2 O 3 ) -20-30 mol% Al 2 O 3 amorphous solid solution powder, and the resulting solid solution powder is calcined at a temperature equal to or higher than the crystallization temperature to obtain crystalline ZrO 2 solid solution powder. A step of preparing the body, and step B: forming the crystalline ZrO 2 solid solution powder obtained in the step A, and then heating in an inert gas atmosphere at a heating rate of 50 ° C./min or more and a pressure of 30 to 100 MPa. And a sintering step at a sintering temperature of 1250 to 1350 ° C. for 3 to 30 minutes.
　又、本発明は、上記の特徴を有した作製法において、前記工程Ｂにおける成形を冷間静水圧プレス（cold isostatic pressing：CIP）にて行い、当該工程Ｂにおける焼結をパルス通電加圧焼結法（Pulsed Electric-Current Pressure Sintering：PECPS）又は、放電プラズマ焼結法（Spark Plasma Sintering: SPS）にて行うことを特徴とするものでもある。
　更に、本発明は、上記の特徴を有した作製法において、工程Ｂにおける焼結を主としてアルゴンガス雰囲気下又は窒素ガス雰囲気下で行うことを特徴とするものでもある。 Further, in the production method having the above-described features, the present invention performs the molding in the step B by cold isostatic pressing (CIP), and the sintering in the step B is performed by pulsed electric pressure sintering. It is also characterized by carrying out by a sintering method (Pulsed Electric-Current Pressure Sintering: PECPS) or a discharge plasma sintering method (Spark Plasma Sintering: SPS).
Furthermore, the present invention is characterized in that, in the manufacturing method having the above characteristics, the sintering in the step B is mainly performed in an argon gas atmosphere or a nitrogen gas atmosphere.
　固溶体粉体から、焼結時に微細な酸化アルミニウムＡｌ２Ｏ３微粒子を均一に析出させることで、強靱化が達成され、また、ゾル‐ゲル法を用いたナノ粒子を緻密化することで、高強度が得られ、本発明の作製法を用いることによって、曲げ強度σｂ≧１ＧＰａで、しかも、破壊靱性値ＫＩＣ≧１５ＭＰａ・ｍ１／２の高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスが作製できる。 Toughness is achieved by uniformly precipitating fine aluminum oxide Al 2 O 3 fine particles from the solid solution powder during sintering. In addition, by densifying the nanoparticles using the sol-gel method, High strength toughness ZrO 2 -Al 2 O 3 system with bending strength σ b ≧ 1 GPa and fracture toughness value K IC ≧ 15 MPa · m 1/2 by using the production method of the present invention. Solid solution ceramics can be produced.
本発明の高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックス作製法における工程を示すフローチャートである。Is a flowchart illustrating steps in high strength toughness ZrO 2 -Al 2 O 3 solid solution ceramics production method of the present invention. （Ａ）は、１１００℃で焼結したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスのＸＲＤパターンであり、（Ｂ）は、１２００℃で焼結したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスのＸＲＤパターンであり、（Ｃ）中の（ａ）は、８２０℃で仮焼したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体粉末のＸＲＤパターンであり、（ｂ）、（ｃ）、（ｄ）、（ｅ）、（ｆ）はそれぞれ、１１００℃、１２００℃、１２５０℃、１３００℃、１３５０℃で焼結したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスのＸＲＤパターンである。(A) is an XRD pattern of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics sintered at 1100 ° C., and (B) is a ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C. (A) in (C) is an XRD pattern of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution powder calcined at 820 ° C., (b), (c) ), (D), (e), and (f) are ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics sintered at 1100 ° C., 1200 ° C., 1250 ° C., 1300 ° C., and 1350 ° C., respectively. This is an XRD pattern. （Ａ）－１は、８００℃で仮焼したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックス粉末のＳＥＭ写真であり、（Ａ）－２は、１２００℃で焼結したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの破面のＳＥＭ写真である。又、（Ｂ）－１は、８２０℃で仮焼したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックス粉末のＳＥＭ写真であり、（Ｂ）－２は、１２００℃で焼結したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの破面のＳＥＭ写真であり、写真の右側には、それぞれの平均粒径が記載されている。(A) -1 is an SEM photograph of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramic powder calcined at 800 ° C., and (A) -2 is ZrO 2 -25 mol% Al sintered at 1200 ° C. It is a SEM photograph of a fracture surface of 2 O 3 solid solution ceramics. (B) -1 is an SEM photograph of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramic powder calcined at 820 ° C., and (B) -2 is sintered at 1200 ° C. 3 is a SEM photograph of the fracture surface of the ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics, and the average particle diameter of each is shown on the right side of the photograph. （Ａ）１２００℃、（Ｂ）１２５０℃、（Ｃ）１３００℃で焼結したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの破面のＳＥＭ写真であり、それぞれの平均粒径も記載されている。(A) SEM photograph of fracture surface of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C., (B) 1250 ° C., (C) 1300 ° C. The diameter is also listed. 焼結温度と、ＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの曲げ強度σｂ、破壊靱性値ＫＩＣ、ビッカース硬度Ｈｖの関係を示すグラフである。And sintering temperature is a graph showing ZrO 2 (1.5Y) -25mol% Al 2 O 3 solid solution ceramics bending strength sigma b, fracture toughness K IC, the relationship between the Vickers hardness H v. 固溶体粉体を使用して種々の焼結温度で作製したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックス及び、混合粉体を使用して種々の焼結温度で作製したＺｒＯ２（３．０Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３コンポジットセラミックスの機械的特性（曲げ強度、ビッカース硬度、破壊靱性値）を示すグラフである。 ZrO 2 was using a solid solution powder prepared at various sintering temperatures (1.5Y) -25mol% Al 2 O 3 solid solution ceramics and, ZrO 2 that by using the mixed powder was made in a variety of sintering temperatures (3.0Y) -25mol% Al 2 O 3 composite mechanical properties (flexural strength, Vickers hardness, fracture toughness value) of ceramics is a graph showing a. ＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスにおいて，ＺｒＯ２に添加するＹ２Ｏ３量を変化させた１３００℃で焼結したセラミックスの、破壊靱性値及びビッカース硬度の変化を示すグラフである。It is a graph which shows the change of the fracture toughness value and the Vickers hardness of the ceramic sintered at 1300 ° C. in which the amount of Y 2 O 3 added to ZrO 2 is changed in ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics. ゾル‐ゲル法を用いて得られた原料から作製されたＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの機械的特性と、水溶性原料を用いて得られたものの機械的特性を比較した表である。Mechanical properties of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics prepared from raw materials obtained using the sol-gel method, and those obtained using water-soluble raw materials It is the table which compared.
　高強度強靱性のＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスを作製することが可能な本発明の方法における工程Ａ及び工程Ｂについて説明する。
　本発明における工程Ａ（ＺｒＯ２固溶体粉体の調製工程）では、ゾル‐ゲル法を用いてＺｒＯ２に対し０．３～１．７ｍｏｌ％Ｙ２Ｏ３を添加したＺｒＯ２７０～８０ｍｏｌ％に対して３０～２０ｍｏｌ％のＡｌ２Ｏ３を添加してなる固溶体粉体を調製するが、このような固溶体粉体の調製は、例えば、図１に示されるフローチャートに記載されるような工程により行われる。ただし、この図１に示された工程で使用されている原料及び条件に限定されるものではない。この際、ＺｒＯ２に対するＹ２Ｏ３の添加量が０．３～１．７ｍｏｌ％に限定されるのは、０．３ｍｏｌ％未満でも、逆に添加量が１．７ｍｏｌ％を超えても、室温における曲げ強度σｂが１０００Ｍａより小さく、又、破壊靭性値ＫＩＣが１５ＭＰａ・ｍ１／２より小さくなるからであり、又、Ａｌ２Ｏ３の添加量が２０～３０ｍｏｌ％に限定されるのは、２０ｍｏｌ％未満の添加量でも、逆に添加量が３０ｍｏｌ％を超えても、曲げ強度σｂが１０００ＭＰａ未満となるからである。
　尚、本発明において、固溶体粉体を仮焼して正方晶(tetragonal)のＺｒＯ２固溶体粉体を調製する際の温度は結晶化温度以上であれば良く、７００℃～９００℃が好ましい。 Step A and Step B in the method of the present invention capable of producing a high-strength toughness ZrO 2 -Al 2 O 3 solid solution ceramic will be described.
In step in the present invention A (step Preparation of ZrO 2 solid solution powder), sol - to ZrO 2 using gel method 0.3 ~ 1.7mol% Y 2 O 3 ZrO 2 70 ~ 80mol% with the addition of On the other hand, a solid solution powder prepared by adding 30 to 20 mol% of Al 2 O 3 is prepared. For example, such a solid solution powder is prepared by a process described in the flowchart shown in FIG. Done. However, it is not limited to the raw material and conditions used in the process shown in FIG. At this time, the amount of Y 2 O 3 added to ZrO 2 is limited to 0.3 to 1.7 mol%, even if the amount added is less than 0.3 mol%, or conversely exceeds 1.7 mol%, This is because the bending strength σ b at room temperature is smaller than 1000 Ma and the fracture toughness value K IC is smaller than 15 MPa · m 1/2 , and the addition amount of Al 2 O 3 is limited to 20 to 30 mol%. This is because even if the addition amount is less than 20 mol%, or conversely, the addition strength exceeds 30 mol%, the bending strength σ b becomes less than 1000 MPa.
In the present invention, the temperature at which the solid solution powder is calcined to prepare a tetragonal ZrO 2 solid solution powder may be higher than the crystallization temperature, and preferably 700 ° C. to 900 ° C.
　又、本発明における工程Ｂ（焼結工程）では、前記工程Ａで得られた結晶質のＺｒＯ２固溶体粉体を成形し、次いで、不活性ガス雰囲気下、昇温速度５０℃／ｍｉｎ以上、圧力３０～１００ＭＰａ、焼結温度１２５０～１３５０℃で３～３０分の条件にて焼結することによって、高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスを製造する。ＺｒＯ２固溶体粉体の成形を行うには冷間静水圧プレスが適しており、得られた成形体の焼結を行うには、アルゴンガス又は窒素ガス雰囲気下でのパルス通電加圧焼結法又は、放電プラズマ焼結法が適している。一軸加圧下において、低電圧でパルス状直流電流を流し、火花放電現象により瞬時に高エネルギーを発生させて試料の焼結を行うパルス通電加圧焼結法が適しているのは、急激なジュール加熱により溶解と高速拡散が起こり、短時間で高速焼結できるので、比較的粒成長を抑えた緻密な焼結体（相対密度９０％以上）を得ることができるからであり、放電プラズマ焼結法が適しているのも同様の理由による。
　本発明におけるパルス通電加圧焼結の特に好ましい条件は、アルゴンガス雰囲気下、昇温速度５０～１００℃／分、加圧力６０ＭＰａ、焼結温度１２７０～１３３０℃、保持時間１０分の条件である。この際、焼結温度が１２５０℃未満になると、高い曲げ強度（≧１ＧＰａ）が得られず、焼結温度が１３５０℃を超えると、高い破壊靱性値（≧１５ＭＰａ・ｍ１／２）が得られなくなるので好ましくない。保持時間については、３～３０分で充分緻密化するが、加圧力が３０ＭＰａ未満では焼結密度が低くなり、逆に１００ＭＰａを超えると通電加圧焼結に使用する金型の強度に上限があり使用出来なくなるという問題がある。昇温速度については、５０℃／分未満になると長時間の熱処理となり製造コストが高くなり、逆に１００℃／分を超えると、焼結体内部の微細構造にムラが生じ、均質で大型の試料の作製が困難となるので好ましくない。
　尚、本発明において、曲げ強度σｂは、スパン長さ８ｍｍ、クロスヘッドの送り０．５ｍｍ/ｍｉｎの条件で測定された三点曲げ強度の値であり、破壊靱性値ＫＩＣは、荷重１０ｋｇ（９８Ｎ）で５秒間正四角錐のダイヤモンド圧子をセラミックス表面に押し込み、形成された圧痕の四隅に発生するクラックの長さから評価するインデンテーション（ＩＦ）法（K. Niihara et al., J. Master. Sci. Lett., 1, 13-16 (1982)）に従って測定された値である。 Further, in the step B (sintering step) in the present invention, the crystalline ZrO 2 solid solution powder obtained in the step A is molded, and then the heating rate is 50 ° C./min or more in an inert gas atmosphere. High strength toughness ZrO 2 -Al 2 O 3 based solid solution ceramics are produced by sintering at a pressure of 30 to 100 MPa and a sintering temperature of 1250 to 1350 ° C. for 3 to 30 minutes. A cold isostatic press is suitable for forming a ZrO 2 solid solution powder, and a pulsed current pressure sintering method in an argon gas or nitrogen gas atmosphere is used to sinter the obtained molded body. Alternatively, a discharge plasma sintering method is suitable. The pulsed current pressure sintering method, in which a pulsed direct current is applied at a low voltage under uniaxial pressure and high energy is instantaneously generated by the spark discharge phenomenon, is suitable for the rapid joule. This is because melting and high-speed diffusion occur by heating, and high-speed sintering can be achieved in a short time, so that a dense sintered body (relative density of 90% or more) with relatively suppressed grain growth can be obtained. The law is suitable for the same reason.
Particularly preferred conditions for pulsed current pressure sintering in the present invention are the conditions of a heating rate of 50 to 100 ° C./min, an applied pressure of 60 MPa, a sintering temperature of 1270 to 1330 ° C., and a holding time of 10 minutes in an argon gas atmosphere. . At this time, when the sintering temperature is less than 1250 ° C., a high bending strength (≧ 1 GPa) cannot be obtained, and when the sintering temperature exceeds 1350 ° C., a high fracture toughness value (≧ 15 MPa · m 1/2 ) is obtained. It is not preferable because it is not possible. The holding time is sufficiently densified in 3 to 30 minutes. However, if the applied pressure is less than 30 MPa, the sintering density is low, and conversely if it exceeds 100 MPa, the upper limit is imposed on the strength of the mold used for the electric current pressure sintering. There is a problem that it can not be used. As for the rate of temperature increase, if it is less than 50 ° C./minute, the heat treatment takes a long time and the manufacturing cost becomes high. Conversely, if it exceeds 100 ° C./minute, the microstructure inside the sintered body becomes uneven, resulting in a homogeneous and large Since preparation of a sample becomes difficult, it is not preferable.
In the present invention, the bending strength σ b is a three-point bending strength value measured under the conditions of a span length of 8 mm and a crosshead feed of 0.5 mm / min, and the fracture toughness value K IC is a load of 10 kg. (98N) Indentation (IF) method (K. Niihara et al., J. Master), in which a diamond indenter with a square pyramid is pushed into the ceramic surface for 5 seconds and evaluated from the length of cracks generated at the four corners Sci. Lett., 1, 13-16 (1982)).
実施例１：高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスの製造条件の検討
　ゾル‐ゲル法を用いてＺｒＯ２に対して、１．５ｍｏｌ％Ｙ２Ｏ３を添加（９８．５ｍｏｌ％ＺｒＯ２‐１．５ｍｏｌ％Ｙ２Ｏ３）したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体粉体（ＺｒＯ２（１．５Ｙ）／Ａｌ２Ｏ３＝７５／２５mol比）を調製し（この段階では粉体は非結晶）、この粉体を８２０℃で空気中１時間仮焼して結晶質のＺｒＯ２固溶体粉体を得た。そして、この結晶質の固溶体粉体を整粒した後、金型成形（９８ＭＰａ）し、ついで冷間静水圧（２４５ＭＰａ）プレス処理し、その後、市販のパルス通電加圧焼結装置（SPSシンテックス（株）／SPS-510Aを使用）を用いて、アルゴンガス雰囲気下、加圧圧力６０ＭＰａ、焼結温度１１００～１３５０℃、保持時間１０分、昇温速度１００℃／分の条件でパルス通電加圧焼結を行い、焼結体（ＺｒＯ２（１．５Ｙ）‐Ａｌ２Ｏ３固溶体セラミックス）を得た。
　一方、Ｙ２Ｏ３を添加せずにゾル‐ゲル法を用いてＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３の非晶質の固溶体粉体（ＺｒＯ２／Ａｌ２Ｏ３＝７５／２５mol比）を調製し、同様の条件にて仮焼を行い、結晶質のＺｒＯ２固溶体粉体を得た。そして、この結晶質の固溶体粉体を用いて、上記と同様にして金型成形、冷間静水圧プレス処理を行い、焼結温度１１００℃及び１２００℃において同様のパルス通電加圧焼結を行い、焼結体（ＺｒＯ２‐Ａｌ２Ｏ３固溶体セラミックス）を得た。 Example 1: Examination of production conditions of high strength toughness ZrO 2 -Al 2 O 3 based solid solution ceramics 1.5 mol% Y 2 O 3 was added to ZrO 2 using a sol-gel method (98.5 mol) % ZrO 2 -1.5 mol% Y 2 O 3 ) ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution powder (ZrO 2 (1.5Y) / Al 2 O 3 = 75/25 mol ratio) (At this stage, the powder was amorphous), and this powder was calcined in the air at 820 ° C. for 1 hour to obtain a crystalline ZrO 2 solid solution powder. The crystalline solid solution powder is sized and then molded (98 MPa), followed by cold isostatic pressing (245 MPa), and then a commercially available pulse current pressure sintering apparatus (SPS Syntex). (Uses Co., Ltd./SPS-510A) and pulsed energization under an argon gas atmosphere at a pressure of 60 MPa, a sintering temperature of 1100 to 1350 ° C., a holding time of 10 minutes, and a heating rate of 100 ° C./min. Pressure sintering was performed to obtain a sintered body (ZrO 2 (1.5Y) -Al 2 O 3 solid solution ceramics).
On the other hand, an amorphous solid solution powder of ZrO 2 -25 mol% Al 2 O 3 (ZrO 2 / Al 2 O 3 = 75/25 mol ratio) was prepared using a sol-gel method without adding Y 2 O 3. It was prepared and calcined under the same conditions to obtain a crystalline ZrO 2 solid solution powder. Then, using this crystalline solid solution powder, die molding and cold isostatic pressing are performed in the same manner as described above, and the same pulse current pressure sintering is performed at sintering temperatures of 1100 ° C. and 1200 ° C. A sintered body (ZrO 2 -Al 2 O 3 solid solution ceramics) was obtained.
　図２には、このようにして得られた固溶体セラミックス焼結体のＸＲＤパターンが示されており、（Ａ）は、１１００℃で焼結したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスのＸＲＤパターン、（Ｂ）は、１２００℃で焼結したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスのＸＲＤパターンである。（Ｃ）中の（ａ）は、８２０℃で仮焼したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体粉末のＸＲＤパターンであり、（ｂ）～（ｆ）には、焼結温度を１１００℃～１３５０℃に変化させて得られたＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスのＸＲＤパターンが示されている。
　この図２の（Ａ）～（Ｃ）より、酸化イットリウム（Ｙ２Ｏ３）が添加されていない（Ａ）と（Ｂ）の場合（仮焼温度７００～９００℃、焼結温度１１００℃及び１２００℃）には、単斜晶の酸化ジルコニウム（ｍ－ＺｒＯ２）及び、正方晶の酸化ジルコニウム（ｔ－ＺｒＯ２）の両回折ピークが存在しているのに対し、酸化イットリウム（Ｙ２Ｏ３）が１．５ｍｏｌ％添加された（Ｃ）の場合には、仮焼により得られた粉末（ａ）においても、焼結により得られた固溶体セラミックス（ｂ）～（ｆ）においても、主として正方晶の酸化ジルコニウムである酸化イットリウムジルコニウムの回折ピークが存在していることがわかった。 FIG. 2 shows an XRD pattern of the solid solution ceramic sintered body thus obtained. (A) is an XRD of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramic sintered at 1100 ° C. The pattern (B) is an XRD pattern of ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C. (A) in (C) is an XRD pattern of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution powder calcined at 820 ° C., and (b) to (f) are sintered An XRD pattern of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics obtained by changing the temperature from 1100 ° C. to 1350 ° C. is shown.
From (A) to (C) of FIG. 2, in the case of (A) and (B) to which yttrium oxide (Y 2 O 3 ) is not added (calcination temperature 700 to 900 ° C., sintering temperature 1100 ° C. and At 1200 ° C., both diffraction peaks of monoclinic zirconium oxide (m-ZrO 2 ) and tetragonal zirconium oxide (t-ZrO 2 ) exist, whereas yttrium oxide (Y 2 O 3 ) In the case of (C) to which 1.5 mol% is added, both in the powder (a) obtained by calcination and in the solid solution ceramics (b) to (f) obtained by sintering, It was found that there is a diffraction peak of yttrium zirconium oxide, which is tetragonal zirconium oxide.
　又、図３には、このようにして得られた仮焼粉末及び、固溶体セラミックス焼結体の破面のＳＥＭ写真が示されており、（Ａ）－１は、８００℃で仮焼したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックス粉末のＳＥＭ写真であり、（Ａ）－２は、１２００℃で焼結したＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの破面のＳＥＭ写真である。又、（Ｂ）－１は、８２０℃で仮焼したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックス粉末のＳＥＭ写真であり、（Ｂ）－２は、１２００℃で焼結したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの破面のＳＥＭ写真である。
　この図３のＳＥＭ写真から、酸化イットリウム（Ｙ２Ｏ３）が添加されていない（Ａ）－１及び（Ａ）－２の場合には、仮焼後の粒（子）径は１１０ｎｍ、１２００℃で焼結したセラミックスの結晶粒（子）径は２００ｎｍと約２倍粒成長していることがわかり、酸化イットリウム（Ｙ２Ｏ３）が１．５ｍｏｌ％添加された（Ｂ）－１及び（Ｂ）－２の場合には、粒子径はそれぞれ１００及び１８０ｎｍで、やや酸化イットリウムを添加し固溶させると粒成長が抑制されることがわかった。
　そして、平均粒径の比較から、Ｙ２Ｏ３を１．５ｍｏｌ％添加したセラミックスの方が結晶粒（子）径が小さくなることがわかった。 FIG. 3 shows SEM photographs of the calcined powder thus obtained and the fracture surface of the solid solution ceramic sintered body. (A) -1 is ZrO calcined at 800 ° C. a SEM photograph of 2 -25mol% Al 2 O 3 solid solution ceramic powder, (a) -2 is an SEM photograph of the fracture surface of the ZrO 2 -25mol% Al 2 O 3 solid solution ceramics sintered at 1200 ° C.. (B) -1 is an SEM photograph of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramic powder calcined at 820 ° C., and (B) -2 is sintered at 1200 ° C. it is a SEM photograph of the fracture surface of the ZrO 2 (1.5Y) -25mol% Al 2 O 3 solid solution ceramics.
From the SEM photograph of FIG. 3, in the case of (A) -1 and (A) -2 to which yttrium oxide (Y 2 O 3 ) was not added, the grain (child) diameter after calcination was 110 nm, 1200 It can be seen that the crystal grain (child) diameter of ceramics sintered at 200 ° C. is about 200 nm, growing about twice as large, and 1.5 mol% of yttrium oxide (Y 2 O 3 ) was added (B) -1 and In the case of (B) -2, the particle diameters were 100 and 180 nm, respectively, and it was found that when yttrium oxide was slightly added and dissolved, grain growth was suppressed.
From the comparison of the average particle diameter, it was found that the crystal grain (child) diameter was smaller in the ceramic added with 1.5 mol% of Y 2 O 3 .
　図４には、焼成温度を変えた際の、ＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスの破面のＳＥＭ写真が示されており、（Ａ）は焼成温度が１２００℃の場合、（Ｂ）は焼成温度が１２５０℃の場合、（Ｃ）は焼成温度が１３００℃の場合である。これらのＳＥＭ写真から、焼成温度が１２００℃～１３００℃になるとともに組織が緻密になっていることがわかり、それぞれの平均粒径の比較から、焼成温度の上昇とともに１８０から２００ｎｍへと少し大きくなることがわかる。 FIG. 4 shows an SEM photograph of the fracture surface of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics when the firing temperature is changed, and (A) shows a firing temperature of 1200 ° C. In the case of (B), the firing temperature is 1250 ° C., and (C) is the case where the firing temperature is 1300 ° C. From these SEM photographs, it can be seen that the firing temperature is 1200 ° C. to 1300 ° C. and that the structure is denser. From the comparison of the respective average particle diameters, the firing temperature increases slightly from 180 to 200 nm. I understand that.
　以下の表１及び表２には、上記実験にて作製されたＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックス及び、ＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスについての、正方晶酸化ジルコニウム（ｔ－ＺｒＯ２）／単斜晶酸化ジルコニウム（ｍ－ＺｒＯ２）の体積比率（ｔ／ｍ）、理論密度、かさ密度、相対密度が要約されている。 Tables 1 and 2 below show the squares of the ZrO 2 -25 mol% Al 2 O 3 solid solution ceramics and the ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics prepared in the above experiment. The volume ratio (t / m), theoretical density, bulk density and relative density of crystalline zirconium oxide (t-ZrO 2 ) / monoclinic zirconium oxide (m-ZrO 2 ) are summarized.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記表１及び表２から、焼成温度が１３００℃の場合に得られたＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスが、かさ密度、相対密度の点において最も良好な結果を示すことがわかった。 From Table 1 and Table 2 above, ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics obtained when the firing temperature is 1300 ° C. shows the best results in terms of bulk density and relative density. I found out.
　又、図５には、焼成温度を変化させた際の、ＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスについての、焼結温度と、曲げ強度σｂ、破壊靱性値ＫＩＣ、ビッカース硬度Ｈｖの関係がグラフにより示されている。 FIG. 5 shows the sintering temperature, bending strength σ b , and fracture toughness value K IC for the ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramic when the firing temperature is changed. , the relationship of Vickers hardness H v is shown in a graph.
　図５のグラフから、焼結温度が約１２５０℃以上の場合に１ＧＰａ以上の曲げ強度σｂが達成でき（焼結温度が１３００℃の場合に１．３３ＧＰａ）、焼結温度が約１２３０℃～１３６０℃の場合に１８ＭＰａ・ｍ１／２以上、約１２７０℃～１３３０℃の場合に２０ＭＰａ・ｍ１／２以上の破壊靱性値ＫＩＣ（焼結温度が１３００℃の場合に２１．３ＭＰａ・ｍ１／２）が達成できることがわかる。尚、ビッカース硬度Ｈｖは、焼結温度が約１２３０℃以上の場合に１３ＧＰａ以上（焼結温度が１３００℃の場合に１３．４ＧＰａ）であった。 From the graph of FIG. 5, when the sintering temperature is about 1250 ° C. or higher, a bending strength σ b of 1 GPa or higher can be achieved (1.33 GPa when the sintering temperature is 1300 ° C.), and the sintering temperature is about 1230 ° C.- in the case of 1360 ° C. 18 MPa · m 1/2 or more, 21.3MPa · in the case of about 1270 ℃ ~ 1330 ℃ 20MPa · m 1/2 or more fracture toughness K IC (sintering temperature 1300 ° C. in the case of m 1/2 ) can be achieved. Incidentally, the Vickers hardness H v is the sintering temperature was above 13GPa to not less than about 1230 ℃ (13.4GPa when the sintering temperature is 1300 ° C.).
実施例２：本発明により作製されたＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスと、他の方法により作製されたＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスとの特性比較
（比較品１）
　市販の１．５ｍｏｌ％Ｙ２Ｏ３を添加（９８．５ｍｏｌ％ＺｒＯ２‐１．５ｍｏｌ％Ｙ２Ｏ３）したＺｒＯ２（１．５Ｙ－ＺｒＯ２）粉体と市販のＡｌ２Ｏ３微粒子を、遊星ボールミルを用いて混合して得られた混合粉体（ＺｒＯ２／Ａｌ２Ｏ３＝７５／２５mol比）を、前記実施例１と同様に、金型成形（９８ＭＰａ）し、ついで冷間静水圧（２４５ＭＰａ）プレス処理し、その後、市販のパルス通電加圧焼結装置を用いてパルス通電加圧焼結（焼結温度１３００℃）して焼結体を得た。
　このような混合により作製されたＺｒＯ２（１．５Ｙ）‐Ａｌ２Ｏ３系コンポジットセラミックスの特性値を測定したところ、曲げ強度σｂは１．１１ＧＰａであったが、破壊靱性値ＫＩＣは９．０８ＭＰａ・ｍ１／２であり、１５ＭＰａ・ｍ１／２以上の破壊靱性値を達成することはできなかった。 Example 2: Comparison of characteristics between ZrO 2 -Al 2 O 3 based solid solution ceramics produced according to the present invention and ZrO 2 -Al 2 O 3 based solid solution ceramics produced by other methods (Comparative product 1)
ZrO 2 (1.5Y-ZrO 2 ) powder added with commercially available 1.5 mol% Y 2 O 3 (98.5 mol% ZrO 2 -1.5 mol% Y 2 O 3 ) and commercially available Al 2 O 3 fine particles Was mixed with a planetary ball mill to obtain a mixed powder (ZrO 2 / Al 2 O 3 = 75/25 mol ratio) in the same manner as in Example 1 (98 MPa), followed by cooling. An intermediate hydrostatic pressure (245 MPa) press treatment was performed, and then, pulsed current pressure sintering (sintering temperature 1300 ° C.) was performed using a commercially available pulse current pressure sintering apparatus to obtain a sintered body.
When the characteristic value of the ZrO 2 (1.5Y) -Al 2 O 3 composite ceramics produced by such mixing was measured, the bending strength σ b was 1.11 GPa, but the fracture toughness value K IC was is 9.08MPa · m 1/2, it has not been possible to achieve a 15MPa · m 1/2 or more of the fracture toughness value.
（比較品２）
　ゾル‐ゲル法を用いて、Ｙ２Ｏ３が添加されていないＺｒＯ２‐２５ｍｏｌ％Ａｌ２Ｏ３の非晶質固溶体粉体を調製し、この粉体を１０００℃で空気中１時間仮焼して結晶質のＺｒＯ２固溶体粉体を得た。そして、この結晶質の固溶体粉体を整粒した後、成形（１９６ＭＰａ）し、ついで冷間静水圧（３９２ＭＰａ）プレス処理し、その後、市販のピストンシリンダー型高圧発生装置を用いて、加圧圧力１ＧＰａ、焼結温度９００℃、保持時間３０分の条件下で高圧焼結を行い、焼結体を得た。
　このようにして作製されたＺｒＯ２‐Ａｌ２Ｏ３固溶体セラミックスの特性値を測定したところ、曲げ強度σｂが１．１２５ＧＰａで、破壊靱性値ＫＩＣが１５．８ＭＰａ・ｍ１／２であることが確認されたが、１ＧＰａ以上の曲げ強度と、１５ＭＰａ・ｍ１／２以上の破壊靱性値を達成するには、上記の如く、非常に高い圧力下での成形工程、冷間静水圧プレス処理工程、焼結工程が必要であることがわかった。 (Comparative product 2)
Using a sol-gel method, an amorphous solid solution powder of ZrO 2 -25 mol% Al 2 O 3 to which Y 2 O 3 was not added was prepared, and this powder was calcined in air at 1000 ° C. for 1 hour. Thus, a crystalline ZrO 2 solid solution powder was obtained. Then, the crystalline solid solution powder is sized, molded (196 MPa), then subjected to cold isostatic pressing (392 MPa), and then subjected to a pressurized pressure using a commercially available piston cylinder type high pressure generator. High pressure sintering was performed under the conditions of 1 GPa, a sintering temperature of 900 ° C., and a holding time of 30 minutes to obtain a sintered body.
When the characteristic values of the ZrO 2 —Al 2 O 3 solid solution ceramics thus produced were measured, the bending strength σ b was 1.125 GPa and the fracture toughness value K IC was 15.8 MPa · m 1/2 . However, in order to achieve a bending strength of 1 GPa or more and a fracture toughness value of 15 MPa · m 1/2 or more, as described above, a forming process under a very high pressure, a cold isostatic press It was found that a treatment process and a sintering process are necessary.
実施例３：固溶体粉体を用いて作製したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスと、混合粉体を用いて作製したＺｒＯ２（３．０Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３コンポジットセラミックスとの機械的特性比較
　焼結温度を１１００～１３５０℃の範囲で変化させ、固溶体粉体を用いて作製したＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスと、混合粉体を焼結して作製したＺｒＯ２（３．０Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３コンポジットセラミックスについて、それぞれの機械的特性（曲げ強度、ビッカース硬度、破壊靱性値）を測定した。図６には、その結果が示されており、（ａ）は曲げ強度σｂの変化、（ｂ）はビッカース硬度Ｈｖの変化、（ｃ）は破壊靱性値ＫＩＣの変化を示すグラフであり、○は固溶体粉体を使用した場合、□は混合粉体を使用した場合である。
　図６のグラフから、固溶体粉体を使用し、かつ、焼結温度が１２５０～１３５０℃の範囲において、曲げ強度σｂ１０００ＭＰａ以上、破壊靭性値ＫＩＣ１８ＭＰａ・ｍ１／２以上のＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスが作製できることがわかった。尚、混合粉体を焼結して作製したＺｒＯ２（３．０Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３コンポジットセラミックスの場合には、ビッカース硬度は大きくなる（１６ＧＰａ以上）が、曲げ強度が１０００ＭＰａ以下となり、破破壊靭性値が７ＭＰａ・ｍ１／２以下となる。 Example 3: ZrO 2 (1.5Y) -25mol% Al 2 O 3 solid solution ceramics produced using the solid solution powder, ZrO 2 (3.0Y) produced by using the mixed powder -25mol% Al 2 Comparison of mechanical properties with O 3 composite ceramics ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics produced by using a solid solution powder by changing the sintering temperature in the range of 1100 to 1350 ° C., The mechanical properties (bending strength, Vickers hardness, fracture toughness value) of each of the ZrO 2 (3.0Y) -25 mol% Al 2 O 3 composite ceramics produced by sintering the mixed powder were measured. FIG. 6 shows the results, where (a) is a change in bending strength σ b , (b) is a change in Vickers hardness H v , and (c) is a graph showing a change in fracture toughness value K IC. Yes, ○ is when solid solution powder is used, and □ is when mixed powder is used.
From the graph of FIG. 6, when solid solution powder is used and the sintering temperature is in the range of 1250 to 1350 ° C., ZrO 2 (with bending strength σ b of 1000 MPa or more and fracture toughness value K IC 18 MPa · m 1/2 or more. It was found that 1.5Y) -25 mol% Al 2 O 3 solid solution ceramics can be produced. In the case of ZrO 2 (3.0Y) -25 mol% Al 2 O 3 composite ceramics produced by sintering the mixed powder, the Vickers hardness increases (16 GPa or more), but the bending strength becomes 1000 MPa or less. The fracture toughness value is 7 MPa · m 1/2 or less.
実施例４：Ｙ２Ｏ３添加量を変化させた際の、破壊靱性値及びビッカース硬度の変化
　Ｙ２Ｏ３の添加量を０～３ｍｏｌ％の範囲で変化させた際の、破壊靱性値及びビッカース硬度の変化を測定した。尚、焼結条件は、圧力５０～６０ＭＰａ、焼結温度１３００℃、保持時間１０分とした。その結果を図７に示す。
　図７（ａ）のグラフから、破壊靱性値ＫＩＣに関して、Ｙ２Ｏ３添加量が０．３～１．７ｍｏｌ％の範囲において１５ＭＰａ・ｍ１／２以上となり、０．７～１．５ｍｏｌ％の範囲では１８ＭＰａ・ｍ１／２以上となることがわかった。又、このような添加量の範囲における曲げ強度は１ＧＰａ以上であることが確認された。尚、図７（ｂ）のグラフから、ビッカース硬度に関しては、Ｙ２Ｏ３添加量が０．３～１．７ｍｏｌ％の範囲において１２ＧＰａ以上となり、０．７～１．５ｍｏｌ％の範囲では１４ＧＰａ以上となることがわかった。
　このことから、高強度強靱性のＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスを作製するためのＹ２Ｏ３添加量は０．３～１．７ｍｏｌ％の範囲であり、特に好ましい範囲は０．７～１．５ｍｏｌ％であることがわかった。 Example 4: Y 2 O 3 amount when changing the addition, when the amount of change Y 2 O 3 of fracture toughness and Vickers hardness was varied in the range of 0 ~ 3 mol%, the fracture toughness value and The change in Vickers hardness was measured. The sintering conditions were a pressure of 50 to 60 MPa, a sintering temperature of 1300 ° C., and a holding time of 10 minutes. The result is shown in FIG.
From the graph of FIG. 7A, regarding the fracture toughness value K IC , the amount of Y 2 O 3 added is 15 MPa · m 1/2 or more in the range of 0.3 to 1.7 mol%, and 0.7 to 1.5 mol. % Range was found to be 18 MPa · m 1/2 or more. Moreover, it was confirmed that the bending strength in the range of such addition amount is 1 GPa or more. From the graph of FIG. 7B, the Vickers hardness is 12 GPa or more when the Y 2 O 3 addition amount is in the range of 0.3 to 1.7 mol%, and 14 GPa in the range of 0.7 to 1.5 mol%. It turns out that it becomes the above.
Therefore, the amount of Y 2 O 3 added for producing high strength toughness ZrO 2 —Al 2 O 3 based solid solution ceramics is in the range of 0.3 to 1.7 mol%, and a particularly preferable range is 0.8. It was found to be 7 to 1.5 mol%.
実施例５：ゾル‐ゲル法を用いて得られた原料から作製されたＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックス（本発明品）の機械的特性と、水溶性原料を用いて得られたものの機械的特性
　図８に記載した製造条件にて、３種類のＺｒＯ２（１．５Ｙ）‐２５ｍｏｌ％Ａｌ２Ｏ３固溶体セラミックスを製造し、それぞれについて各種機械的特性を測定した。
　図８に示された測定結果から、ゾル‐ゲル法による原料を用いた場合（本発明の製法）の場合には、作製された固溶体セラミックスの結晶構造において単斜晶（ｍ）よりも正方晶（ｔ）の割合が高くなり、１０００ＭＰａ以上の曲げ強度を有し、１５ＭＰａ・ｍ１／２以上の破壊靱性値を有した固溶体セラミックスが得られるが、ゾル‐ゲル法を用いない場合には、本発明の製法にて得られる固溶体セラミックスのような優れた機械的特性を有するものが作製できないことが確認された。 Example 5: Mechanical properties of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics (product of the present invention) prepared from raw materials obtained using the sol-gel method, and water-soluble raw materials Mechanical properties of the product obtained by using the three types of ZrO 2 (1.5Y) -25 mol% Al 2 O 3 solid solution ceramics manufactured under the manufacturing conditions shown in FIG. 8 and measuring various mechanical properties for each. did.
From the measurement results shown in FIG. 8, in the case of using the raw material by the sol-gel method (the manufacturing method of the present invention), the crystal structure of the produced solid solution ceramic is more tetragonal than monoclinic (m). When the ratio of (t) is increased, a solid solution ceramic having a bending strength of 1000 MPa or more and a fracture toughness value of 15 MPa · m 1/2 or more is obtained, but when the sol-gel method is not used, It was confirmed that a product having excellent mechanical properties such as solid solution ceramics obtained by the production method of the present invention could not be produced.
　本発明の作製法を用いて得られるＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスは、１ＧＰａ以上の曲げ強度と、１５ＭＰａ・ｍ１／２以上の破壊靱性値を有しているので、高強度及び強靱性が求められる各種用途、例えばセラミックス製機械部品、生体用セラミックス（人工歯根、人工関節、人工骨）、家庭用包丁、まな板等に利用可能である。 The ZrO 2 -Al 2 O 3 solid solution ceramics obtained using the production method of the present invention has a bending strength of 1 GPa or more and a fracture toughness value of 15 MPa · m 1/2 or more. It can be used for various applications that require toughness, such as ceramic machine parts, biological ceramics (artificial roots, artificial joints, artificial bones), household knives, cutting boards, and the like.

Claims (3)

  1. 　高強度強靱性のＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスを作製することが可能な方法であって、当該方法が、
    　工程Ａ：ゾル‐ゲル法を用いてＺｒＯ２に対し０．３～１．７ｍｏｌ％Ｙ２Ｏ３を添加したＺｒＯ２（９９．７～９８．３ｍｏｌ％ＺｒＯ２‐０．３～１．７ｍｏｌ％Ｙ２Ｏ３）‐２０～３０ｍｏｌ％Ａｌ２Ｏ３の非晶質固溶体粉体を調製し、得られた非晶質固溶体粉体を結晶化温度以上で仮焼して結晶質のＺｒＯ２固溶体粉体を調製する工程、及び
    　工程Ｂ：前記工程Ａで得られた結晶質のＺｒＯ２固溶体粉体を成形し、次いで、不活性ガス雰囲気下、昇温速度５０℃／ｍｉｎ以上、圧力３０～１００ＭＰａ、焼結温度１２５０～１３５０℃で３～３０分の条件にて焼結する工程
    を含むことを特徴とする高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスの作製法。     A method capable of producing a high strength toughness ZrO 2 -Al 2 O 3 solid solution ceramics, the method comprising
    Step A: Sol - to ZrO 2 using a gel method 0.3 ~ 1.7mol% Y 2 O 3 ZrO 2 was added (99.7 ~ 98.3mol% ZrO 2 -0.3 ~ 1.7mol % Y 2 O 3 ) -20-30 mol% Al 2 O 3 amorphous solid solution powder is prepared, and the obtained amorphous solid solution powder is calcined at a temperature equal to or higher than the crystallization temperature to obtain crystalline ZrO 2 Step of preparing solid solution powder, and Step B: Forming the crystalline ZrO 2 solid solution powder obtained in Step A, and then heating at a rate of temperature rise of 50 ° C./min or more under an inert gas atmosphere at a pressure of 30 A method for producing a high-strength toughness ZrO 2 -Al 2 O 3 solid solution ceramic, comprising a step of sintering at a sintering temperature of 1 to 100 MPa and a sintering temperature of 1250 to 1350 ° C. for 3 to 30 minutes.
  2. 　上記工程Ｂにおける成形を冷間静水圧プレスに行い、当該工程Ｂにおける焼結をパルス通電加圧焼結法又は、放電プラズマ焼結法にて行うことを特徴とする請求項１に記載の高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスの作製法。 The forming in the step B is performed by cold isostatic pressing, and the sintering in the step B is performed by a pulse current pressure sintering method or a discharge plasma sintering method. A method for producing a strong toughness ZrO 2 —Al 2 O 3 solid solution ceramics.
  3. 　上記工程Ｂにおける焼結をアルゴンガス雰囲気下又は窒素ガス雰囲気下で行うことを特徴とする請求項１又は２に記載の高強度強靱性ＺｒＯ２‐Ａｌ２Ｏ３系固溶体セラミックスの作製法。 High strength toughness ZrO 2 -Al 2 method of producing O 3 solid solution ceramics according to claim 1 or 2 sintering and performing under an atmosphere of argon gas atmosphere or nitrogen gas in the step B.
PCT/JP2012/061196 2011-05-12 2012-04-26 METHOD FOR PRODUCING HIGH-STRENGTH HIGH-TOUGHNESS ZrO2-Al2O3-BASED SOLID SOLUTION CERAMIC WO2012153645A1 (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014189474A (en) * 2013-03-28 2014-10-06 Doshisha METHOD OF MANUFACTURING HIGH STRENGTH HIGH TOUGHNESS ZrO2-Al2O3-BASED SOLID SOLUTION CERAMIC
KR20170039225A (en) 2015-04-20 2017-04-10 스미토모덴키고교가부시키가이샤 Sintered body and cutting tool including same
US9902654B2 (en) 2016-06-20 2018-02-27 The Doshisha ZrO2-Al2O3-based ceramic sintered compact and production method thereof
US9988314B2 (en) 2015-05-29 2018-06-05 Sumitomo Electric Hardmetal Corp. Sintered compact and cutting tool
CN108409312A (en) * 2018-03-26 2018-08-17 淄博畅安陶瓷科技有限公司 Two pairs of rollers machine drum body porcelain piece and preparation method thereof
US10532951B2 (en) 2016-05-27 2020-01-14 Sumitomo Electric Industries, Ltd. Sintered material and cutting tool including same
CN115819079A (en) * 2022-12-02 2023-03-21 中南大学湘雅二医院 Material for artificial teeth and preparation method thereof
JP7438501B1 (en) 2023-01-24 2024-02-27 学校法人 龍谷大学 Alumina-zirconia mixed material and its manufacturing method

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06306352A (en) * 1993-04-27 1994-11-01 Tosoh Corp Zirconia grit and its production
JPH11147762A (en) * 1997-11-11 1999-06-02 Fine Ceramics Gijutsu Kenkyu Kumiai Zirconium dioxide-based sintered product and its production
JP2002255642A (en) * 2001-03-02 2002-09-11 National Institute Of Advanced Industrial & Technology High density yttria-stabilized zirconia sintered body and production method therefor
JP2004075532A (en) * 2002-08-01 2004-03-11 Kobe Steel Ltd High strength / high toughness zirconia sintered material and biomaterial using the same
JP2006225205A (en) * 2005-02-17 2006-08-31 Osaka Univ Conductive zirconia sintered compact and method of manufacturing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06306352A (en) * 1993-04-27 1994-11-01 Tosoh Corp Zirconia grit and its production
JPH11147762A (en) * 1997-11-11 1999-06-02 Fine Ceramics Gijutsu Kenkyu Kumiai Zirconium dioxide-based sintered product and its production
JP2002255642A (en) * 2001-03-02 2002-09-11 National Institute Of Advanced Industrial & Technology High density yttria-stabilized zirconia sintered body and production method therefor
JP2004075532A (en) * 2002-08-01 2004-03-11 Kobe Steel Ltd High strength / high toughness zirconia sintered material and biomaterial using the same
JP2006225205A (en) * 2005-02-17 2006-08-31 Osaka Univ Conductive zirconia sintered compact and method of manufacturing the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
O. YAMAGUCHI ET AL.: "Fabrication and mechanical properties of Zr02 solid solution and composite ceramics in the system ZrO2 (Y203)-A1203.", ADVANCED SYNTHESIS AND PROCESSING OF COMPOSITES AND ADVANCED CERAMICS, 1995, pages 353 - 360 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014189474A (en) * 2013-03-28 2014-10-06 Doshisha METHOD OF MANUFACTURING HIGH STRENGTH HIGH TOUGHNESS ZrO2-Al2O3-BASED SOLID SOLUTION CERAMIC
KR20170039225A (en) 2015-04-20 2017-04-10 스미토모덴키고교가부시키가이샤 Sintered body and cutting tool including same
US9988315B2 (en) 2015-04-20 2018-06-05 Sumitomo Electric Industries, Ltd. Sintered body and cutting tool including the same
US9988314B2 (en) 2015-05-29 2018-06-05 Sumitomo Electric Hardmetal Corp. Sintered compact and cutting tool
US10532951B2 (en) 2016-05-27 2020-01-14 Sumitomo Electric Industries, Ltd. Sintered material and cutting tool including same
US9902654B2 (en) 2016-06-20 2018-02-27 The Doshisha ZrO2-Al2O3-based ceramic sintered compact and production method thereof
CN108409312A (en) * 2018-03-26 2018-08-17 淄博畅安陶瓷科技有限公司 Two pairs of rollers machine drum body porcelain piece and preparation method thereof
CN115819079A (en) * 2022-12-02 2023-03-21 中南大学湘雅二医院 Material for artificial teeth and preparation method thereof
JP7438501B1 (en) 2023-01-24 2024-02-27 学校法人 龍谷大学 Alumina-zirconia mixed material and its manufacturing method

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