WO2012153645A1 - PROCÉDÉ DE FABRICATION D'UNE CÉRAMIQUE EN SOLUTION SOLIDE À BASE DE ZrO2-Al2O3,À RÉSISTANCE ÉLEVÉE, À TÉNACITÉ ÉLEVÉE - Google Patents

PROCÉDÉ DE FABRICATION D'UNE CÉRAMIQUE EN SOLUTION SOLIDE À BASE DE ZrO2-Al2O3,À RÉSISTANCE ÉLEVÉE, À TÉNACITÉ ÉLEVÉE 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

L'invention concerne un procédé de fabrication d'une céramique en solution solide, à base de ZrO2-Al2O3, à résistance élevée, à ténacité élevée. Y2O3 dans une quantité de 0,3-1,7 % en moles est ajouté à ZrO2 à l'aide d'un procédé sol-gel pour préparer une poudre en solution solide de ZrO2 amorphe-(20-30 % en moles d'Al2O3), et la poudre en solution solide amorphe résultante est préfrittée à une température égale ou supérieure à une température de cristallisation, permettant ainsi de préparer une poudre de solution solide de ZrO2 cristallin (étape A). La poudre de solution solide de ZrO2 cristallin résultante est moulée, et le produit moulé est ensuite fritté dans une atmosphère de gaz inerte dans les conditions d'une allure de montée en température de 50ºC/min ou plus, une pression de 30-100 MPa et d'une température de frittage de 1250-1350˚C pendant 3-30 minutes (étape B). Dans ce procédé, on préfère effectuer le moulage dans l'étape B au moyen d'une presse isostatique à froid et effectuer le frittage par un procédé de frittage sous pression et courant pulsé ou un procédé de frittage à plasma d'étincelles dans une atmosphère d'argon ou azote gazeux.
PCT/JP2012/061196 2011-05-12 2012-04-26 PROCÉDÉ DE FABRICATION D'UNE CÉRAMIQUE EN SOLUTION SOLIDE À BASE DE ZrO2-Al2O3,À RÉSISTANCE ÉLEVÉE, À TÉNACITÉ ÉLEVÉE WO2012153645A1 (fr)

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JP2014189474A (ja) * 2013-03-28 2014-10-06 Doshisha 高強度強靱性ＺｒＯ２−Ａｌ２Ｏ３系固溶体セラミックスの作製法
KR20170039225A (ko) 2015-04-20 2017-04-10 스미토모덴키고교가부시키가이샤 소결체 및 그것을 포함하는 절삭 공구
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 (zh) * 2018-03-26 2018-08-17 淄博畅安陶瓷科技有限公司 对辊机筒体瓷件及其制备方法
US10532951B2 (en) 2016-05-27 2020-01-14 Sumitomo Electric Industries, Ltd. Sintered material and cutting tool including same
CN115819079A (zh) * 2022-12-02 2023-03-21 中南大学湘雅二医院 一种人造牙齿用材料及其制备方法
JP7438501B1 (ja) 2023-01-24 2024-02-27 学校法人 龍谷大学 アルミナ－ジルコニア混合材料及びその製造方法

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014189474A (ja) * 2013-03-28 2014-10-06 Doshisha 高強度強靱性ＺｒＯ２−Ａｌ２Ｏ３系固溶体セラミックスの作製法
KR20170039225A (ko) 2015-04-20 2017-04-10 스미토모덴키고교가부시키가이샤 소결체 및 그것을 포함하는 절삭 공구
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 (zh) * 2018-03-26 2018-08-17 淄博畅安陶瓷科技有限公司 对辊机筒体瓷件及其制备方法
CN115819079A (zh) * 2022-12-02 2023-03-21 中南大学湘雅二医院 一种人造牙齿用材料及其制备方法
JP7438501B1 (ja) 2023-01-24 2024-02-27 学校法人 龍谷大学 アルミナ－ジルコニア混合材料及びその製造方法

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