WO1993023347A1 - Produit fritte a la zircone resistant a l'usure et procede de production correspondant - Google Patents

Produit fritte a la zircone resistant a l'usure et procede de production correspondant Download PDF

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Publication number
WO1993023347A1
WO1993023347A1 PCT/JP1993/000627 JP9300627W WO9323347A1 WO 1993023347 A1 WO1993023347 A1 WO 1993023347A1 JP 9300627 W JP9300627 W JP 9300627W WO 9323347 A1 WO9323347 A1 WO 9323347A1
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WO
WIPO (PCT)
Prior art keywords
sintered body
powder
zirconia
wear
monoclinic
Prior art date
Application number
PCT/JP1993/000627
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English (en)
Japanese (ja)
Inventor
Hiroshi Ohnishi
Toshio Kawanami
Original Assignee
Nikkato Corp.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nikkato Corp. filed Critical Nikkato Corp.
Publication of WO1993023347A1 publication Critical patent/WO1993023347A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/486—Fine ceramics

Definitions

  • the present invention relates to a wear-resistant zirconia sintered body and a method for producing the same.
  • Jirukonia (Z r 0 2) is heat-resistant member, oxygen sensors, it is widely used we as a raw material of Serra mission-box product heater first class.
  • pure Jirukonia (Z r 0 2) is tetragonal from monoclinic when heated, transforms into cubic to the al, have the property that when this is cooling the reverse transformation occurs.
  • the transformation from tetragonal to monoclinic involves a large volume expansion, and the sintered body is destroyed when cooled to room temperature.
  • stabilized zirconia or partially stabilized zirconia is adopted in the above various products.
  • Stabilized zirconia is obtained by adding oxides such as calcia (Ca0), yttria (Y ⁇ 0), and magnesia (Mg0) to zirconia, and is cubic even at room temperature.
  • Consists of The partially stabilized zirconia has a higher thermal shock resistance than the above-mentioned stabilized zirconia by allowing cubic and monoclinic to coexist.
  • these stabilized or partially stabilized zirconia A sintered body made of a material has good thermal shock resistance, heat resistance, etc., but has a relatively large porosity and a crystal grain size of more than 20 m. However, it has the drawback of poor abrasion resistance.
  • the high-strength zirconia sintered body has a problem that the production cost is extremely high.
  • High-strength zirconia sintered compacts of the Mg0 type require firing at 170 ° C or higher, and require a lot of time to control the cooling rate, heat treatment after firing, and so on an industrial scale. Not suitable for production at In addition, its wear resistance is excellent for some applications such as wire drawing dies, but it is not sufficient for all applications.
  • the object of the present invention is achieved as follows.
  • the present inventor has focused on research.
  • a specific amount of magnesia, calcia and yttria is added to and mixed with the zirconia, and the raw material for molding is crushed to form a monoclinic crystal of zirconia. It was found that the amount, bulk density, and crystal grain size could be controlled, and further, it was found that a zirconia sintered body in which these values were controlled within a specific range exhibited excellent wear resistance. Completed the invention.
  • the present invention provides the following wear-resistant zirconia sintered body and a method for producing the same;
  • Abrasion resistance Jirukonia sintered body of the present invention (i) M g O to 6 ⁇ : L 0 contains mol%, (ii) C a 0 and Y Q 0 ⁇ least 0.1 2 one of 2 containing mol%, (iii) monoclinic Z r 0 2 content is 5 0% by volume or less, there is (iv) a bulk density of 5. 5 5 g cm 3 or more, (V) grain It has the feature that the diameter is 4 m or less.
  • MgO is a component necessary for imparting wear resistance to the sintered body of the present invention. Therefore, when the above content is less than 6 mol%, the proportion of monoclinic zirconia increases, and a large number of microcracks due to transformation from tetragonal to monoclinic during the cooling process during firing occur. As a result, the wear resistance is reduced due to the presence of the microcracks, even if the collapse of the sintered body does not occur. On the other hand, if it exceeds 10 mol%, the proportion of cubic zirconia increases, and the crystal grain size increases. In this case, the wear resistance also decreases.
  • the proportion (monoclinic amount) of monoclinic zirconia is less than 50% by volume.
  • the monoclinic zirconia particles in the sintered body of the present invention are present at the grain boundaries and in the grains, and the monoclinic zirconia particles that have undergone volume expansion generate a compressive stress inside the sintered body. Contributes to the improvement of wear resistance. If the amount of monoclinic crystal is more than 50% by volume, the volume expansion will be excessive, and micro cracks will occur, reducing wear resistance.
  • the zirconia other than the monoclinic crystal is preferably 80% by volume or less of cubic zirconia and 70% by volume or less of tetragonal zirconia in the sintered body of the present invention. The amount of the monoclinic zirconia was determined by polishing the surface of the obtained sintered body to a mirror surface and then performing X-ray diffraction analysis at a diffraction angle of 27 to
  • T l 00-MC (volume 3 ⁇ 4)
  • the bulk density is 5.55 g Zcm 3 or more, preferably 5.60 g / cm 3 or more. If the bulk density is less than 5. 5 5 g Xcm u, correspondingly increases the number of pores, not properly desirable because tuna want to decrease the abrasion resistance.
  • the crystal grain size shall be 4 m or less. During cooling from the sintering temperature, volume expansion occurs due to the transformation from tetragonal to monoclinic, and a crack at the mouth is formed.However, when the crystal grain size exceeds 4 m, the microcrack density increases. It is not preferable because particles are detached on the surface of the sintered body due to impact or sliding, thereby reducing wear resistance.
  • the above-mentioned predetermined amounts of powder of magnesium, yttria, and potassium lucia are added to the zirconia powder.
  • the type of zirconia powder is not particularly limited, and for example, zirconia purified from zircon sand can be used.Battery ore or its refined raw material can be used from the viewpoint of cost. More preferred. It is preferable that the particle size of the zirconia powder is usually about l to 5 wm. Further, as magnesia powder, powder of magnesium hydroxide, magnesium carbonate, magnesium salt, etc. may be used in addition to magnesia.
  • the magnesia powder preferably has a particle size of usually about 0.5 to 2 am.
  • powders of hydroxide and carbonate of yttrium and calcium can be used in addition to yttria and lucia. It is preferable that the particle size of the Italian powder and the raw lucia powder is usually about 0.5 to 2 m.
  • mixing and pulverization may be performed in accordance with a conventional method, for example, pot milling or abrasion in water or an organic solvent by a wet method. This can be performed using a pulverizer such as a mill. In this case, if necessary, after drying, it may be calcined at about 110 to 140 ° C., pulverized again, dispersed, and dried to obtain a powder for molding.
  • the powder for molding has a specific surface area of 3 m 2 Zg or more. If the specific surface area is less than 3 m "Zg, the sinterability deteriorates, which is not preferable.
  • the above-mentioned molding powder is molded into a predetermined shape.
  • various known molding methods such as, for example, injection molding, injection molding, extrusion molding, and press molding (CIP, HIP) can be employed as they are.
  • the obtained molded body is fired according to a conventional method.
  • the sintering temperature is usually about 140 to 170 ° C, preferably about 150 to 160 ° C.
  • the wear-resistant zirconia sintered body of the present invention is obtained.
  • a zirconium sintered body having a specific structure can be obtained relatively easily.
  • the zirconia sintered body having a specific structure can exhibit excellent wear resistance in practically all uses.
  • (a) It has excellent wear resistance under high load due to its excellent strength, toughness and impact resistance, and (mouth) It has excellent wear resistance under high-speed conditions because of its excellent thermal shock resistance. .
  • it has a low elastic modulus compared to aluminum etc., so it does not easily damage the mating material.
  • the sintered body of the present invention is used as a pulverizer member, there is almost no mixing of abrasion powder, and even if the abrasion powder mixes with the material to be pulverized, the generated abrasion powder is generated. Since they are very fine, they do not substantially impair the uniformity of the material to be ground.
  • the abrasion-resistant zirconia sintered body of the present invention which can exhibit such excellent effects, is most suitable for various uses such as crushing balls, lining materials, crushing containers, nozzles, rollers, gauges, dies, and the like. .
  • Zirconia raw material with an average particle size of 1.0 m, magnesia or magnesium carbonate with an average particle size of 0.5 // m, and calcium or yttria or its salt are shown in Table 1.
  • the resulting mixture was mixed into a pot mill, and the mixture was pulverized until the specific surface area became 8 m / g to obtain a molding powder.
  • the molding powder is formed into a ball having a diameter of 15 mm at a pressure of 1 ton / cm 2 by an isostatic press molding method (CIP), and the formed body is heated at a temperature of 1450 to 170 ° C. Fired.
  • CIP isostatic press molding method
  • the ball was barrel-polished to obtain a ball made of the wear-resistant zirconia sintered body of the present invention.
  • This sintered body, a bulk density (g ZCM u) were examined for grain size (fi m), monoclinic Akiraryou (volume) and wear rate (%). The results are shown in Table 1.
  • the wear rate was measured by the following method.
  • Table 1 shows that the wear-resistant zirconia sintered body of the present invention exhibits excellent wear resistance due to the structure unique to the present invention.
  • Comparative Examples 1 to 7 Sintered balls were manufactured in the same manner as in the example except that the compositions were as shown in Table 2, and the characteristics were examined. The results are shown in Table 2. Incidentally, Jirukonia raw material, Comparative Example 1, 3, 5 and 7 Batterai you for the other (Z r ⁇ 2 9 9. 5%, S i 0 9 0. 2%, A 1 2 0 3 0. 0 1%) The other materials used were zirconia raw materials purified from zircon sand.
  • each ball of the comparative example has a raw material composition out of the range of the present invention, and thus does not have a sintered body characteristic peculiar to the present invention and is inferior in wear resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention se rapporte à un produit fritté à la zircone résistant à l'usure, qui est constitué par un frittage de ZrO2-MgO où: (i) la teneur en MgO est de 6 à 10 % en mole; (ii) la teneur en CaO et/ou en Y2O3 est de 0,2 à 2 % en mole; (iii) la teneur en ZrO2 monoclinique est de 50 % en volume au maximum; (iv) la masse volumique en vrac est de 5,55 g/cm3 au minimum; et (v) le diamètre des grains cristallins est de 4 νm au maximum. La présente invention permet d'obtenir un produit fritté à la zircone qui est comparativement peu coûteux et qui possède une excellente résistance à l'usure dans toutes ses utilisations.
PCT/JP1993/000627 1992-05-14 1993-05-12 Produit fritte a la zircone resistant a l'usure et procede de production correspondant WO1993023347A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4120963A JP2676008B2 (ja) 1992-05-14 1992-05-14 耐摩耗性ジルコニア焼結体及びその製造方法
JP4/120963 1992-05-14

Publications (1)

Publication Number Publication Date
WO1993023347A1 true WO1993023347A1 (fr) 1993-11-25

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JP (1) JP2676008B2 (fr)
WO (1) WO1993023347A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6267807B1 (en) 1996-06-20 2001-07-31 Lexmark International, Inc. Method for grinding colorants

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6093228B2 (ja) * 2013-04-09 2017-03-08 曙ブレーキ工業株式会社 摩擦材
JP6772592B2 (ja) * 2016-06-30 2020-10-21 東ソー株式会社 透光性ジルコニア焼結体及びその製造方法並びにその用途

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4918906A (fr) * 1972-04-11 1974-02-19
JPS6031796B2 (ja) * 1981-09-14 1985-07-24 東レ株式会社 ジルコニア焼結体
JPS63103864A (ja) * 1986-10-10 1988-05-09 シユトーラ　フエルトミユーレ　アクチエンゲゼルシヤフト 部分安定化された酸化ジルコニウムからなる焼結成形体およびその製造法
JPS63277560A (ja) * 1987-05-11 1988-11-15 Toshiba Ceramics Co Ltd ＺｒＯ↓２−ＭｇＯ−Ｙ↓２Ｏ↓３系セラミックスとその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4918906A (fr) * 1972-04-11 1974-02-19
JPS6031796B2 (ja) * 1981-09-14 1985-07-24 東レ株式会社 ジルコニア焼結体
JPS63103864A (ja) * 1986-10-10 1988-05-09 シユトーラ　フエルトミユーレ　アクチエンゲゼルシヤフト 部分安定化された酸化ジルコニウムからなる焼結成形体およびその製造法
JPS63277560A (ja) * 1987-05-11 1988-11-15 Toshiba Ceramics Co Ltd ＺｒＯ↓２−ＭｇＯ−Ｙ↓２Ｏ↓３系セラミックスとその製造方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6267807B1 (en) 1996-06-20 2001-07-31 Lexmark International, Inc. Method for grinding colorants

Also Published As

Publication number Publication date
JP2676008B2 (ja) 1997-11-12
JPH05319923A (ja) 1993-12-03

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