JP4773709B2 - Crusher parts - Google Patents
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- JP4773709B2 JP4773709B2 JP2004331162A JP2004331162A JP4773709B2 JP 4773709 B2 JP4773709 B2 JP 4773709B2 JP 2004331162 A JP2004331162 A JP 2004331162A JP 2004331162 A JP2004331162 A JP 2004331162A JP 4773709 B2 JP4773709 B2 JP 4773709B2
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 70
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 19
- 239000013078 crystal Substances 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000010987 cubic zirconia Substances 0.000 claims description 7
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 description 27
- 238000000034 method Methods 0.000 description 13
- 238000010298 pulverizing process Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 10
- 238000000465 moulding Methods 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- 230000005611 electricity Effects 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- -1 yttrium compound Chemical class 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010130 dispersion processing Methods 0.000 description 1
- 238000009837 dry grinding Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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Description
本発明はすぐれた耐摩耗性と静電除去能力をもった粉砕機用部材に関する。本明細書において、「粉砕機用部材」とは固体を乾式または湿式で粉砕、分散、混合あるいは解砕処理するために使用する器具、治具、機械装置などにおける固体と接触する部材の総称であり、粉砕・分散メディアも包含するものである。具体的には粉砕機、分散機、解砕機、混合機、造粒機、整粒機、攪拌機、乾燥機、運搬機などが含まれる。 The present invention relates to a pulverizer member having excellent wear resistance and electrostatic removal capability. In this specification, “member for pulverizer” is a general term for members that come into contact with a solid in tools, jigs, mechanical devices, etc. used for pulverizing, dispersing, mixing or crushing solids in a dry or wet manner. Yes, including pulverized / dispersed media. Specifically, a pulverizer, a disperser, a pulverizer, a mixer, a granulator, a granulator, a stirrer, a dryer, a transporter, and the like are included.
近年、電子材料等の高機能材料の製造には、微粉化と高純度化が要求され、使用される粉砕機は、従来のボールミルから高速で粉砕・分散メディアを撹拌することにより高い粉砕・分散効率を有する媒体撹拌型粉砕機が主流となっている。このような粉砕機は粉砕機用部材に加わる負荷がかなり大きいことから、被処理物が帯電し、その結果、粉体に強力な凝集が起こる。粉砕・分散処理時に非極性有機溶媒を用いて処理している場合には静電気放電が着火源となって爆発等の原因となる。一方、従来から行われている乾式粉砕においても粉砕により粉体表面に帯電が起こり、静電気による付着・凝集現象により粉砕の進行を阻害し、生産性の大きな低下をきたす。静電気を消失除去するために水蒸気の添加や適当な除電剤の添加等が行われているが、粉体表面を変質してしまうことや防爆装置が必要となるなどの問題点を有している。 In recent years, high-performance materials such as electronic materials have been required to be finely divided and highly purified, and the pulverizer used is highly pulverized / dispersed by stirring the pulverizing / dispersing media at high speed from a conventional ball mill. An efficient medium agitating pulverizer has become mainstream. In such a pulverizer, since the load applied to the pulverizer member is considerably large, the object to be processed is charged, and as a result, strong aggregation occurs in the powder. When processing is performed using a nonpolar organic solvent during pulverization / dispersion processing, electrostatic discharge becomes an ignition source and causes explosion. On the other hand, in the conventional dry pulverization, the powder surface is charged by the pulverization, and the progress of pulverization is hindered by the phenomenon of adhesion / aggregation due to static electricity, resulting in a significant decrease in productivity. In order to eliminate static electricity, the addition of water vapor or the addition of a suitable static neutralizer has been performed, but it has problems such as changing the surface of the powder and requiring an explosion-proof device. .
特許文献１には炭化ホウ素を主成分とする粉砕機用部材が開示されているが、高価であり、湿式には不向きであり、体積固有抵抗が小さすぎて静電除去材料としては不適当である。また、使用条件によっては粉砕機用部材が金属に見られる電食に似た腐食が起こるので好ましくない。
さらに、特許文献２〜４にはアルミナ質およびジルコニア質に導電性を付与した焼結体が開示されているが、導電性を付与するために電気導電性を発現させる成分が多量に添加されており、さらに該成分を多く添加しても焼結体のち密さに悪影響を与えないために焼成温度を高くする必要があり、その結果、結晶粒径が大きくなって硬度、強度の低下が起こり、耐摩耗性が低下する問題点があった。従って、従来の導電性を付与したアルミナ質およびジルコニア質焼結体は導電性を付与するがために本来の母剤の高特性を犠牲にした材料となっており、粉砕機用部材等の耐摩耗材料としては十分に満足して使用できるものではなかった。
Patent Document 1 discloses a pulverizer member mainly composed of boron carbide, but is expensive, unsuitable for wet use, and has a volume resistivity that is too small to be suitable as an electrostatic removal material. is there. Further, depending on the use conditions, the pulverizer member is not preferable because corrosion similar to electric corrosion observed in metal occurs.
Furthermore, Patent Documents 2 to 4 disclose a sintered body in which conductivity is imparted to alumina and zirconia. However, in order to impart conductivity, a large amount of a component that develops electrical conductivity is added. In addition, even if a large amount of the above components are added, it is necessary to increase the firing temperature in order not to adversely affect the compactness of the sintered body. As a result, the crystal grain size increases and the hardness and strength decrease. There was a problem that the wear resistance was lowered. Therefore, the conventional alumina and zirconia sintered bodies imparted with electrical conductivity are materials that sacrifice the high characteristics of the original base material to impart electrical conductivity. It was not a satisfactory wear material.
本発明の目的は、すぐれた耐摩耗性を有し、かつ湿式・乾式での粉砕・分散における粉体表面への帯電を抑制することを可能とする粉砕機用部材を提供する点にある。 An object of the present invention is to provide a member for a pulverizer that has excellent wear resistance and can suppress charging of the powder surface during pulverization / dispersion in a wet or dry manner.
本発明者は前記のような現状を鑑み鋭意研究を重ねてきた結果、ジルコニア質および／またはアルミナ質焼結体において、平均結晶粒径、気孔率及び固有抵抗を、さらにはジルコニア結晶相及びアルミナ含有量をある特定の範囲内に制御し、比摩耗量がある特定の範囲内にすることにより、乾式、湿式粉砕・分散においてすぐれた耐摩耗性と粉体表面に発生する静電気の除去が可能であることを見出し本発明を完成するに至った。 As a result of intensive studies in view of the above-mentioned present situation, the present inventor has found that in a zirconia and / or alumina sintered body, the average crystal grain size, the porosity and the specific resistance, and further the zirconia crystal phase and the alumina By controlling the content within a certain range and making the specific wear amount within a certain range, it has excellent wear resistance in dry and wet grinding / dispersion and can eliminate static electricity generated on the powder surface. As a result, the present invention has been completed.
即ち、本発明の第一は、炭化チタン、窒化チタン、炭化ケイ素のいずれかの一つを５〜２５ｗｔ％、または酸化チタンを２〜８ｗｔ％含有した、Ｙ２Ｏ３／ＺｒＯ２モル比が２／９８〜５／９５であるジルコニア質焼結体であり、平均結晶粒径が５μｍ以下、気孔率が１％以下、体積固有抵抗値が１×１０５〜１×１０１０Ω・ｃｍであり、比摩耗量が１０−５ｍｍ２／Ｎ以下であることを特徴とする粉砕機用部材を関する。
本発明の第二は、正方晶系ジルコニア単相もしくは７０容積％以上の正方晶系ジルコニアを含む正方晶系ジルコニアと立方晶系ジルコニアとの混合相であることを特徴とする請求項１記載の粉砕機用部材に関する。
以下に本発明の粉砕機用部材が充足すべき要件について詳細に説明する。
That is, the first aspect of the present invention, titanium carbide, titanium nitride, 5-25 wt% of one or silicon carbide, or titanium oxide containing 2~8wt%, Y 2 O 3 / ZrO 2 molar ratio Is a zirconia sintered body having an average crystal grain size of 5 μm or less, a porosity of 1% or less, and a volume resistivity of 1 × 10 5 to 1 × 10 10 Ω · cm. And the specific wear amount is 10 −5 mm 2 / N or less.
The second aspect of the present invention is a tetragonal zirconia single phase or a mixed phase of tetragonal zirconia containing 70% by volume or more of tetragonal zirconia and cubic zirconia. The present invention relates to a pulverizer member.
The requirements to be satisfied by the crusher member of the present invention will be described in detail below.
（１） アルミナを４０重量％以下含有する点。
本発明においてはジルコニア質焼結体中にアルミナを４０重量％以下、好ましくは３０重量％以下含有することが必要である。ジルコニア質焼結体中にアルミナを含有させることにより硬度の向上だけでなく、熱伝導率が大きくなって粉砕機用部材の冷却能力を高めることができる優位性がある。アルミナ含有量が４０重量％を越える場合にはジルコニアとアルミナの熱膨張差により焼結体内部に発生する歪みが大きくなり、衝撃等により微細クラックが発生し、耐摩耗性の低下をきたすので好ましくない。下限は０．１重量％程度である。
(1) The point which contains 40 weight% or less of alumina.
In the present invention, the zirconia sintered body must contain 40 wt% or less, preferably 30 wt% or less of alumina. By including alumina in the zirconia sintered body, there is an advantage that not only the hardness is improved, but also the thermal conductivity is increased and the cooling capacity of the pulverizer member can be increased. When the alumina content exceeds 40% by weight, the strain generated inside the sintered body increases due to the difference in thermal expansion between zirconia and alumina, and fine cracks are generated due to impacts, etc. Absent. The lower limit is about 0.1% by weight.
（２）Ｙ２Ｏ３／ＺｒＯ２モル比が２／９８〜５／９５である点。
本発明における、Ｙ２Ｏ３／ＺｒＯ２モル比は２／９８〜５／９５、好ましくは２．５／９７．５〜４／９６であることが必要である。
通常ＺｒＯ２原料中に少量含有することのあるＨｆＯ２が混入していても良く、このＨｆＯ２量を含めたＺｒＯ２とＨｆＯ２の合量をＺｒＯ２量とする。
Ｙ２Ｏ３／ＺｒＯ２モル比が２／９８未満の場合には焼結体中の単斜晶系ＺｒＯ２量が増加し、焼結体内部にクラックが発生して、粉砕機用部材として負荷のかかる状態ではクラックが進展し、割れや欠けが発生し、その結果、耐摩耗性の低下をきたすので好ましくない。一方、Ｙ２Ｏ３／ＺｒＯ２モル比が５／９５を越えると正方晶系ＺｒＯ２量が低下し、立方晶系ＺｒＯ２量が増加し、機械的特性が低下するので好ましくない。
なお、Ｙ２Ｏ３添加量の３０モル％まで他の稀土類酸化物の１種または２種以上で置換したものも用いることができる。このような稀土類酸化物としては、ＣｅＯ２、Ｎｄ２Ｏ３、Ｙｂ２Ｏ３、Ｄｙ２Ｏ３等が安価な点で好ましい。
(2) The point that Y 2 O 3 / ZrO 2 molar ratio is 2/98 to 5/95.
In the present invention, the Y 2 O 3 / ZrO 2 molar ratio needs to be 2/98 to 5/95, preferably 2.5 / 97.5 to 4/96.
Usually, HfO 2 that may be contained in a small amount in the ZrO 2 raw material may be mixed, and the total amount of ZrO 2 and HfO 2 including the amount of HfO 2 is defined as the amount of ZrO 2 .
When the Y 2 O 3 / ZrO 2 molar ratio is less than 2/98, the amount of monoclinic ZrO 2 in the sintered body increases, cracks are generated inside the sintered body, In a state where a load is applied, cracks develop, cracks and chips occur, and as a result, wear resistance is lowered, which is not preferable. On the other hand, if the molar ratio of Y 2 O 3 / ZrO 2 exceeds 5/95, the amount of tetragonal ZrO 2 decreases, the amount of cubic ZrO 2 increases, and the mechanical properties decrease, which is not preferable.
Also it is possible to use those substituted with one or more other rare earth oxides up to 30 mol% of Y 2 O 3 amount. As such rare earth oxides, CeO 2 , Nd 2 O 3 , Yb 2 O 3 , Dy 2 O 3 and the like are preferable from the viewpoint of inexpensiveness.
（３）平均結晶粒径が５μｍ以下である点。
本発明における焼結体の平均結晶粒径は５μｍ以下、好ましくは３μｍ以下であることが必要である。平均結晶粒径が５μｍを越えると硬度の低下が起こり、耐摩耗性が低下するので好ましくない。下限では０．３μｍ程度である。なお、本発明において平均結晶粒径は焼結体を鏡面仕上げし、熱エッチングを施し、走査電子顕微鏡にて観察し、インターセプト法により１０点平均から求める。算出式としては、
The average crystal grain size of the sintered body in the present invention is required to be 5 μm or less, preferably 3 μm or less. When the average crystal grain size exceeds 5 μm, the hardness is lowered and the wear resistance is lowered, which is not preferable. The lower limit is about 0.3 μm. In the present invention, the average grain size is obtained from an average of 10 points by the intercept method after mirror-finishing the sintered body, applying thermal etching, and observing with a scanning electron microscope. As a formula,
（４）気孔率が１％以下である点。
本発明において気孔率は１％以下、好ましくは０．５％以下である。気孔率が１％を越える場合には、曲げ強さ等の機械的特性の低下が起こり、耐摩耗性が低下するので好ましくない。下限は０％である。
なお、本発明の気孔率はアルキメデス法により測定する。
(4) The porosity is 1% or less.
In the present invention, the porosity is 1% or less, preferably 0.5% or less. When the porosity exceeds 1%, mechanical properties such as bending strength are deteriorated, and wear resistance is deteriorated. The lower limit is 0%.
In addition, the porosity of this invention is measured by the Archimedes method.
（５）体積固有抵抗値が１×１０５〜１×１０１０Ω・ｃｍである点。
本発明においては、体積固有抵抗値は１×１０５〜１×１０１０Ω・ｃｍ、好ましくは１×１０６〜１×１０９Ω・ｃｍである。体積固有抵抗値が１×１０５Ω・ｃｍ未満の場合は、静電気が流れすぎ、電食が発生し、粉砕機用部材の損傷が大きくなるので好ましくなく、１×１０１０Ω・ｃｍを越える場合には静電気除去能力が低下し、粉体表面の帯電を抑えることができなくなる。また、使用条件によっては粉砕機用部材が金属に見られる電食に似た腐食が発生するので好ましくない。
なお、本発明における体積固有抵抗値の測定はφ２０×２ｔｍｍ（直径２０ｍｍ、肉厚２ｍｍのこと）に加工した焼結体の両面に電極を施し、測定サンプルとする。測定は高抵抗計を用いて極性反転法により、バイアス電圧５０Ｖ、バイアス電圧印可時間１５秒／サイクル（プラス方向に電圧を１５秒間、マイナス方向に電圧を１５秒間かける操作を１サイクルとする）、極性反転サイクル４回／測定の条件で測定する。抵抗値の読み取りは、電圧をかけて１５秒後の抵抗の絶対値を読み取り、１サイクル当たりプラス方向とマイナス方向に２回抵抗の絶対値が読み取れるので２回×４サイクル＝８回で、８個の抵抗の絶対値を平均してその平均値から体積固有抵抗を算出する。
(5) The volume resistivity value is 1 × 10 5 to 1 × 10 10 Ω · cm.
In the present invention, the volume resistivity value is 1 × 10 5 to 1 × 10 10 Ω · cm, preferably 1 × 10 6 to 1 × 10 9 Ω · cm. When the volume resistivity is less than 1 × 10 5 Ω · cm, it is not preferable because static electricity flows too much, galvanic corrosion occurs, and damage to the pulverizer member increases, which exceeds 1 × 10 10 Ω · cm. In such a case, the ability to remove static electricity is lowered, and charging of the powder surface cannot be suppressed. Further, depending on the use conditions, the pulverizer member is not preferable because corrosion similar to the electric corrosion observed in metal occurs.
The measurement of volume resistivity in the present invention is an electrode applied on both surfaces of the sintered body was processed into a φ20 × 2 t mm (diameter 20 mm, that the wall thickness of 2 mm), a measurement sample. Measurement is performed by polarity reversal using a high resistance meter, bias voltage 50V, bias voltage application time 15 seconds / cycle (the operation in which the voltage is applied for 15 seconds in the positive direction and the voltage is applied for 15 seconds in the negative direction is one cycle), Measured under conditions of 4 polarity reversal cycles / measurement. The resistance value can be read by reading the absolute value of the resistance 15 seconds after applying the voltage, and the absolute value of the resistance can be read twice in the positive and negative directions per cycle. The absolute value of each resistance is averaged, and the volume specific resistance is calculated from the average value.
（６）比摩耗量が１０−５ｍｍ２／Ｎ以下である点。
本発明における比摩耗量は１０−５ｍｍ２／Ｎ以下、好ましくは１０−６ｍｍ２／Ｎ以下であることが必要である。比摩耗量が１０−５ｍｍ２／Ｎを超える場合には粉砕機用部材とした場合の摩耗が大きくなり、被処理粉体中への摩耗粉の混入量が多くなり好ましくない。
なお、本発明における比摩耗量の測定はボールオンディスク式摩耗試験機により、ボールは（株）ニッカトー製ＹＴＺφ１０ｍｍボールを用い、応力２４．５Ｎ、摺動半径φ２５ｍｍ、摺動距離１０８ｍ、摺動速度０．１８ｍ／ｓｅｃ、温度２０〜２５℃、湿度３０〜４０％の条件で行う。なお、試験サンプルは□３０×１０ｔｍｍ（一辺３０ｍｍの正方形で、肉厚１０ｍｍのもの）で摩耗試験面は鏡面仕上げとした。比摩耗量の算出は下式により行う。
The specific wear amount in the present invention is required to be 10 −5 mm 2 / N or less, preferably 10 −6 mm 2 / N or less. When the specific wear amount exceeds 10 −5 mm 2 / N, wear in the case of a pulverizer member increases, and the amount of wear powder mixed into the powder to be treated increases, which is not preferable.
In the present invention, the specific wear amount was measured by a ball-on-disk type wear tester. The ball used was a YTZ φ10 mm ball manufactured by Nikkato Co., Ltd., a stress of 24.5 N, a sliding radius of φ25 mm, a sliding distance of 108 m, and a sliding speed. It is performed under the conditions of 0.18 m / sec, temperature 20 to 25 ° C., and humidity 30 to 40%. The test sample was □ 30 × 10 t mm (a square with a side of 30 mm and a thickness of 10 mm), and the abrasion test surface was mirror finished. The specific wear amount is calculated by the following formula.
（７）正方晶系ジルコニア単相もしくは７０容積％以上の正方晶系ジルコニアを含む正方晶系ジルコニアと立方晶系ジルコニアとの混合相である点。
本発明においては、正方晶系ジルコニア量が７０容積％以上、好ましくは８０容積％以上であることが必要である。正方晶系ジルコニアの含有量が７０容積％未満の場合は、正方晶から単斜晶への応力誘起相変態効果が少なくなり、靭性の低下を生じ、負荷応力によってクラックが生成しやすくなり、耐摩耗性の低下をきたすので好ましくない。
本発明においては、正方晶系ジルコニア７０容積％以上を含む正方晶系ジルコニアと立方晶系ジルコニアとの混合相であってもよい。従って、Ｘ線回折から求まる立方晶系ジルコニアは３０容積％を上限としてその存在が許容され、また、単斜晶系ジルコニアは正方晶系ジルコニアが７０容積％以上を含むことを前提とした場合５容積％までは許容することができる。
(7) A tetragonal zirconia single phase or a mixed phase of tetragonal zirconia containing 70% by volume or more of tetragonal zirconia and cubic zirconia.
In the present invention, the tetragonal zirconia amount needs to be 70% by volume or more, preferably 80% by volume or more. When the content of tetragonal zirconia is less than 70% by volume, the effect of stress-induced phase transformation from tetragonal to monoclinic crystal is reduced, resulting in a decrease in toughness, and cracks are likely to be generated due to load stress. This is not preferable because it causes a decrease in wear.
In the present invention, a mixed phase of tetragonal zirconia and cubic zirconia containing 70% by volume or more of tetragonal zirconia may be used. Therefore, cubic zirconia obtained from X-ray diffraction is allowed to exist up to 30% by volume, and monoclinic zirconia is premised on the assumption that tetragonal zirconia contains 70% by volume or more. Up to volume percent is acceptable.
尚、本発明ではジルコニアの結晶相である単斜晶系ジルコニア（Ｍ）の存在の有無及び含有量、正方晶系ジルコニア（Ｔ）及び立方晶系ジルコニア（Ｃ）の量については以下の方法でＸ線回折により求める。
即ち、焼結体及び加工した焼結体製品の表面は応力誘起相変態により正方晶から単斜晶に変態しており、真の結晶相を同定することができないので、焼結体表面を鏡面にまで研磨し、Ｘ線回折により回折角２７〜３４度の範囲で測定し、単斜晶系ジルコニアの有無及び含有量を次式から求める。
That is, the surface of the sintered body and the processed sintered body product are transformed from tetragonal to monoclinic by stress-induced phase transformation, and the true crystalline phase cannot be identified. And the presence and content of monoclinic zirconia are determined from the following equation by X-ray diffraction and measuring within a diffraction angle range of 27 to 34 degrees.
Ｘ線回折条件はＸ線源：ＣｕＫα、出力：４０ｋＶ／４０ｍＡ、発散スリット：１／２゜、散乱スリット：１／２゜、受光スリット：０．１５ｍｍ、モノクロメータ受光スリット：０．８ｍｍ、カウンタ：シンチレーションカウンタ、モノクロメータ：湾曲型モノクロメータにより行う。 X-ray diffraction conditions are as follows: X-ray source: CuKα, output: 40 kV / 40 mA, divergence slit: 1/2 °, scattering slit: 1/2 °, light receiving slit: 0.15 mm, monochromator light receiving slit: 0.8 mm, counter : Scintillation counter, monochromator: Curved monochromator.
本発明において絶縁体であるジルコニア質焼結体に導電性を付与するためには、炭化チタン、窒化チタン、酸化チタン、炭化ケイ素を体積固有抵抗値が１×１０５〜１×１０１０Ω・ｃｍになるように所定量添加する必要がある。なお、本発明においては炭化チタン、窒化チタン、炭化ケイ素を添加する場合は５〜２５ｗｔ％を、酸化チタンを添加する場合は２〜８ｗｔ％を添加することが必要である。 In order to impart conductivity to the zirconia sintered body is an insulator in the present invention, titanium carbide, titanium nitride, titanium oxide, the volume resistivity of the silicon carbide is 1 × 10 5 ~1 × 10 10 Ω It is necessary to add a predetermined amount so that it becomes cm. In the present invention the titanium carbide, titanium nitride, and 5 to 25 wt% when the addition of silicon carbide, when adding titanium oxide it is necessary to added pressure to 2 to 8 wt%.
以下に本発明の粉砕機用部材は種々の方法で製造できる。下記にその一例を示すが、この方法に限定されるものでない。
本発明では、ジルコニア質粉体は液相法により精製した粉体を使用することが必要である。即ち、ＺｒＯ２とＹ２Ｏ３の含有量が所定のモル比となるようにジルコニウム化合物（例えばオキシ塩化ジルコニウム）の水溶液とイットリウム化合物（例えば塩化イットリウム）の水溶液を均一に混合し、加水分解し、水和物を得、脱水し、乾燥後、４００〜１２５０℃で仮焼し、Ｙ２Ｏ３、Ａｌ２Ｏ３以外の不純物の少ないジルコニア質粉体を得る方法が採用される。
Below, the member for crushers of this invention can be manufactured by various methods. One example is shown below, but is not limited to this method.
In the present invention, it is necessary to use a powder purified by a liquid phase method as the zirconia powder. That is, an aqueous solution of a zirconium compound (for example, zirconium oxychloride) and an aqueous solution of an yttrium compound (for example, yttrium chloride) are uniformly mixed and hydrolyzed so that the content of ZrO 2 and Y 2 O 3 is a predetermined molar ratio. Thus, a method is employed in which a hydrate is obtained, dehydrated, dried, and calcined at 400 to 1250 ° C. to obtain a zirconia powder with less impurities other than Y 2 O 3 and Al 2 O 3 .
ＳｉＯ２は３重量％まで許容でき、ＳｉＯ２が含有していることにより焼結性の向上に効果がある。 SiO 2 can be tolerated up to 3% by weight, and the inclusion of SiO 2 is effective in improving the sinterability.
Ａｌ２Ｏ３成分の添加はジルコニウム化合物とイットリウム化合物の水溶液の混合物に塩の水溶液として所定量添加しても良いし、後記する仮焼粉体の粉砕・分散時に水酸化物、炭酸化物、酸化物等の形態で添加しても良く、導電性成分としてＴｉＯ２を添加する場合はＡｌ２Ｏ３成分の添加と同方法で添加する。 The Al 2 O 3 component may be added in a predetermined amount as an aqueous salt solution to a mixture of an aqueous solution of a zirconium compound and an yttrium compound, or during the pulverization / dispersion of the calcined powder described later, hydroxide, carbonate, oxidation It may be added in the form of a product or the like. When TiO 2 is added as a conductive component, it is added in the same manner as the addition of the Al 2 O 3 component.
また、導電性成分として炭化チタン、窒化チタン、炭化ケイ素、炭化タングステン粉体等を添加する場合はジルコニア仮焼粉体の粉砕・分散時に所定量添加する方法が採用されるが、ジルコニア粉体中にこれらの導電性成分を均一に分散させることが重要で媒体撹拌型粉砕機等の高分散機を用いた処理をすることが好ましい。 In addition, when adding titanium carbide, titanium nitride, silicon carbide, tungsten carbide powder or the like as a conductive component, a method of adding a predetermined amount at the time of pulverizing / dispersing zirconia calcined powder is adopted. In addition, it is important to uniformly disperse these conductive components, and it is preferable to perform treatment using a high disperser such as a medium agitating pulverizer.
なお、用いるＡｌ２Ｏ３及び導電性成分となる粉体はそれぞれ平均粒子径が０．５μｍ、好ましくは０．３μｍ以下であることが必要である。特に導電性成分の平均粒子径が０．５μｍを超える場合には導電性が発現できても耐摩耗性が低下するので好ましくない。 The Al 2 O 3 and the powder serving as the conductive component to be used must each have an average particle size of 0.5 μm, preferably 0.3 μm or less. In particular, when the average particle size of the conductive component exceeds 0.5 μm, even if the conductivity can be exhibited, the wear resistance is lowered, which is not preferable.
得られた仮焼粉体を湿式により粉砕、分散し、必要により公知の成形助剤（ワックスエマルジョン、ＰＶＡ、アクリル系樹脂等）を加え、スプレードライヤー等の公知の方法で乾燥させて成形粉体を得る。得られた成形粉体粒度は平均粒子径０．５μｍ以下、より好ましくは０．４μｍ以下であることが必要である。平均粒子径が０．５μｍを越える場合には焼結性の低下や焼結体に耐久性および機械的性質の低下を招く欠陥が多く含有するので好ましくない。 The obtained calcined powder is pulverized and dispersed by a wet process, and if necessary, a known molding aid (wax emulsion, PVA, acrylic resin, etc.) is added and dried by a known method such as a spray dryer to form a molded powder. Get. The obtained molded powder particle size needs to have an average particle size of 0.5 μm or less, more preferably 0.4 μm or less. When the average particle diameter exceeds 0.5 μm, it is not preferable because many defects that cause a decrease in sinterability and a decrease in durability and mechanical properties are contained in the sintered body.
得られた成形粉体は、公知の成形方法、例えばプレス成形、ラバープレス成形等の方法による成形方法で本発明の焼結体を得ることができる。また、鋳込成形法を採用する場合には、粉砕・分散スラリーに必要により公知のバインダー（例えばワックスエマルジョン、アクリル系樹脂等）を加え、石膏型あるいは樹脂型を用いて排泥鋳込、充填鋳込、加圧鋳込法により成形する。さらに、押出成形法を採用する場合には、粉砕・分散したスラリーを乾燥させ、整粒し、混合機を用いて水、バインダー（例えばメチルセルロース等）、可塑剤（例えばポリエチレングリコール等）、滑剤（例えばステアリン酸等）を混合して坏土を作製し、押出成形する。
次いで得られた成形体を不活性ガス雰囲気下、真空下、Ｎ２雰囲気下等の雰囲気下において１３００〜１７００℃、好ましくは１３５０〜１６５０℃で焼成することによって焼結体を得、所望の形状に加工して粉砕機用部材が得られる。さらに、必要に応じて加工前にＨＩＰ処理を施すことにより摩擦、衝撃等に対する抵抗性を高くすることができ、機械的性質の向上、さらには耐久性の向上ができる。ＨＩＰ処理は常圧焼結後、Ａｒなどの不活性雰囲気、またはＮ２もしくはＯ２雰囲気下で１３００〜１７００℃で行うことが好ましい。
From the obtained molded powder, the sintered body of the present invention can be obtained by a known molding method, for example, a molding method such as press molding or rubber press molding. In addition, when adopting the casting method, a known binder (for example, wax emulsion, acrylic resin, etc.) is added to the pulverized / dispersed slurry as required, and the waste mud is cast and filled using a gypsum mold or a resin mold. Molded by casting or pressure casting. Furthermore, when adopting an extrusion molding method, the pulverized / dispersed slurry is dried, sized, and mixed with water, a binder (for example, methylcellulose), a plasticizer (for example, polyethylene glycol), a lubricant (for example). For example, stearic acid or the like is mixed to prepare a clay, and extrusion molding is performed.
Next, the obtained compact is fired at 1300 to 1700 ° C., preferably 1350 to 1650 ° C. in an atmosphere such as an inert gas atmosphere, a vacuum, or an N 2 atmosphere to obtain a sintered body having a desired shape. To obtain a pulverizer member. Furthermore, by performing HIP treatment before processing as required, resistance to friction, impact, etc. can be increased, and mechanical properties and durability can be improved. The HIP treatment is preferably performed at 1300 to 1700 ° C. in an inert atmosphere such as Ar, or an N 2 or O 2 atmosphere after atmospheric pressure sintering.
本発明の粉砕機用部材は、優れた耐摩耗性を有するだけでなく、湿式・乾式での粉砕・分散における粉体表面への帯電を抑制することが可能であり、粉体を扱う機器類の部品としても有効である。 The pulverizer member of the present invention not only has excellent wear resistance, but also can suppress charging of the powder surface during pulverization / dispersion in wet and dry processes, and equipment for handling powder. It is also effective as a part.
以下に実施例を挙げて本発明を説明するが、本発明はこれにより何ら限定されるものでない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.
実施例１〜５、比較例１〜５
純度９９．６％のオキシ塩化ジルコニウムと純度９９．９％の硝酸イットリウムを表のＹ２Ｏ３／ＺｒＯ２モル比の組成となるように水溶液にして混合した。次に、この水溶液を加熱環流下で加水分解し、Ｙ２Ｏ３が固溶した水和ジルコニウムの沈殿物を生成させ、脱水、乾燥し、４００〜１０００℃で１時間仮焼し、得られたジルコニア粉体を湿式にて粉砕した。なお、Ａｌ２Ｏ３及び導電性成分については、平均粒子径０．３μｍの粉体を用い、粉砕・分散時に所定量添加混合した。得られた粉砕スラリーにバインダーを添加しスプレードライヤーで乾燥させ成形用粉体とした。この成形用粉体を用いてＣＩＰ成形（冷間等方圧縮成形）により成形し、Ａｒ雰囲気下１３００〜１８５０℃で焼成して焼結体を得た。また、一部の焼結体についてはＡｒ雰囲気下でＨＩＰ処理した。得られた焼結体特性を表に示す。
Examples 1-5, Comparative Examples 1-5
Zirconium oxychloride having a purity of 99.6% and yttrium nitrate having a purity of 99.9% were mixed in an aqueous solution so as to have a composition having a molar ratio of Y 2 O 3 / ZrO 2 in the table. Next, this aqueous solution is hydrolyzed under heating reflux to produce a precipitate of hydrated zirconium in which Y 2 O 3 is dissolved, dehydrated and dried, and calcined at 400 to 1000 ° C. for 1 hour. The zirconia powder was pulverized wet. Note that the Al 2 O 3 and the conductive component, using a powder having an average particle diameter of 0.3 [mu] m, was mixed predetermined amounts added during pulverization and dispersion. A binder was added to the obtained pulverized slurry and dried with a spray dryer to obtain a powder for molding. Using this molding powder, molding was performed by CIP molding (cold isotropic compression molding) and fired at 1300 to 1850 ° C. in an Ar atmosphere to obtain a sintered body. Some sintered bodies were HIP-treated in an Ar atmosphere. The obtained sintered body characteristics are shown in the table.
また、同時にシンマルエンタープライゼス社製ダイノーミル：ＫＤＬ−ＰＩＬＯＴ用ディスク（φ８０×４ｔｍｍ）を作製し、図１に示す装置を用いて下記に示す条件でＢａＴｉＯ３粉体を粉砕したときの耐摩耗性のテストを行った。
ボールミル：ＫＤＬ−ＰＩＬＯＴ（シンマルエンタープライゼス製）
セラミックベッセル：ＹＴＺ（株式会社ニッカトー）
ディスク：５枚装着
メディア：ＹＴＺφ１ｍｍ（株式会社ニッカトー製） １２００ｃｃ
ディスク周速：８ｍ／ｓｅｃ
被粉砕物：ＢａＴｉＯ３（比表面積：１．５ｍ２／ｇ、平均粒子径：１．５μｍ）
粉砕スラリー濃度：２０ｗｔ％〔粉末２０ｗｔ％、水８０ｗｔ％〕
スラリー温度：２０℃
粉砕時間：２ｈ×２サイクル
At the same time, Dynomill manufactured by Shinmaru Enterprises Co., Ltd .: KDL-PILOT disk (φ80 × 4 t mm) was prepared, and the BaTiO 3 powder was crushed under the conditions shown below using the apparatus shown in FIG. Abrasion test was performed.
Ball mill: KDL-PILOT (Shinmaru Enterprises)
Ceramic vessel: YTZ (Nikkato Corporation)
Disc: 5 sheets mounted Media: YTZφ1mm (made by Nikkato Corporation) 1200cc
Disk peripheral speed: 8m / sec
Object to be crushed: BaTiO 3 (specific surface area: 1.5 m 2 / g, average particle size: 1.5 μm)
Grinding slurry concentration: 20 wt% [powder 20 wt%, water 80 wt%]
Slurry temperature: 20 ° C
Grinding time: 2h x 2 cycles
摩耗率は下式により算出した。
以上の結果から明らかなように本発明の粉砕機用部材は静電気除去が可能なレベルの体積固有抵抗を有し、かつ耐摩耗性に優れることが明らかである。
The wear rate was calculated by the following formula.
As is clear from the above results, it is clear that the pulverizer member of the present invention has a volume specific resistance capable of removing static electricity and is excellent in wear resistance.
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| JPH0825798B2 (en) * | 1991-03-29 | 1996-03-13 | 株式会社 ニッカトー | Abrasion resistant zirconia sintered body |
| JP2532024B2 (en) * | 1993-07-09 | 1996-09-11 | 株式会社ニッカトー | Abrasion resistant zirconia sintered body |
| JP2860953B2 (en) * | 1995-06-12 | 1999-02-24 | 株式会社ニッカトー | Components for zirconia dispersing and crushing machines |
| JP2000167431A (en) * | 1998-11-30 | 2000-06-20 | Kyocera Corp | Member for pulverizer |
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