JP2008260645A - Black alumina sintered body and manufacturing method thereof - Google Patents
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 58
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 238000005452 bending Methods 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims description 27
- 239000002245 particle Substances 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 51
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000010304 firing Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000009694 cold isostatic pressing Methods 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000007088 Archimedes method Methods 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical class [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- -1 NbC Chemical class 0.000 description 2
- 102100025490 Slit homolog 1 protein Human genes 0.000 description 2
- 101710123186 Slit homolog 1 protein Proteins 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical class O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000010936 titanium Chemical class 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
【課題】大気中で焼成してもアルミナ本来の機械的特性を有し、かつ遮光性を有する黒色アルミナ焼結体とその製造方法の提供。
【解決手段】（ａ−１）Ａｌ２Ｏ３を主成分とし、ＴｉＯ２とＦｅ２Ｏ３を総量で２〜８重量％含有し、（ａ−２）かつＴｉＯ２／Ｆｅ２Ｏ３重量比が０．２０〜０．３５であり、（ｂ）かさ密度が３．８ｇ／ｃｍ３以上であり、（ｃ）平均結晶粒径が４０〜７０μｍであり、（ｄ）曲げ強さが２００ＭＰａ以上であることを特徴とする黒色アルミナ焼結体とその製造方法。
【選択図】なしDisclosed is a black alumina sintered body that has the mechanical properties inherent to alumina even when fired in the air and has a light shielding property, and a method for producing the same.
(A-1) Al 2 O 3 as a main component, TiO 2 and Fe 2 O 3 are contained in a total amount of 2 to 8 wt%, (a-2) and TiO 2 / Fe 2 O 3 wt. The ratio is 0.20 to 0.35, (b) the bulk density is 3.8 g / cm 3 or more, (c) the average crystal grain size is 40 to 70 μm, and (d) the bending strength is 200 MPa. A black alumina sintered body and a method for producing the same, which are described above.
[Selection figure] None
Description
本発明は、黒色アルミナ焼結体とその製造方法に関する。 The present invention relates to a black alumina sintered body and a method for producing the same.
従来、セラミックス素材に要求される特性としては、耐熱性等の熱的性質、強度等の機械的性質、耐食性等の化学的性質、導電性等の電磁気的性質がある。近年、電気部品、半導体製造用部品、各種測定装置等においては、光を反射しない事や製品との識別が可能である事が要求される場合が多く、黒色セラミックスが適用されるケースが増加している。黒色セラミックスのうち、特にレーザー装置や紫外線露光装置等の光関連装置では、その精密性から高剛性および大型化への対応としての軽量化が要求されるだけでなく、反射の問題から黒色系着色が求められており、黒色アルミナ焼結体がこれらの装置の部品として広く適用されている。 Conventionally, properties required for ceramic materials include thermal properties such as heat resistance, mechanical properties such as strength, chemical properties such as corrosion resistance, and electromagnetic properties such as conductivity. In recent years, electrical parts, semiconductor manufacturing parts, various measuring devices, etc. are often required not to reflect light or be distinguishable from products, and the number of cases where black ceramics are applied has increased. ing. Among black ceramics, especially in light-related devices such as laser devices and ultraviolet exposure devices, not only is the precision required to reduce the weight to cope with high rigidity and large size, but also black coloration due to reflection problems. Therefore, black alumina sintered bodies are widely applied as parts of these apparatuses.
従来、白色であるアルミナを黒色に着色する手段として、特許文献１〜３が挙げられる。
特許文献１には、黒色で高剛性なアルミナ焼結体の製造方法として、Ａｌ２Ｏ３を主成分とし、着色剤としてＴｉＣ、ＴｉＣ−ＴｉＮ固溶体、ＮｂＣ、ＺｒＣ、ＨｆＣ、ＴａＣ等の炭化物の１種または２種以上を０．２〜１０重量％含有することで、Ａｒ等の不活性ガス雰囲気中にて焼成する方法が開示されているが、不活性ガス雰囲気中による還元焼成を行うことが必要不可欠であるため、大気中焼成に比べて高コストであり、大型部材の製造を行うためには、大型の還元焼成炉が必要となるため、適用が困難である。
また、特許文献２には精密セラミックス素材としてＡｌ２Ｏ３を主成分とし、着色剤としてＭｎ２Ｏ３及びＦｅ２Ｏ３、Ｆｅ２Ｏ３及びＣｏＯ、Ｃｒ２Ｏ３、Ｍｎ２Ｏ３、Ｆｅ２Ｏ３、及びＣｏＯから選ばれる３種又は４種を２〜５重量％含有する黒色アルミナ焼結体が開示されているが、Ｍｎ２Ｏ３やＣｒ２Ｏ３は人体や環境に悪影響を与える恐れがあり、環境衛生上の観点から使用しない方が好ましい。
一方、特許文献３には黒色アルミナセラミックス組成物として、アルミナを主成分とし、着色剤としてＭｎＯ２、ＴｉＯ２及びＦｅ２Ｏ３を総量で５〜１０重量％添加し、かつ焼結助剤としてＳｉＯ２を１．５〜３．０重量％添加した黒色アルミナ焼結体が開示されているが、着色剤の総量についてＭｎＯ２、ＴｉＯ２及びＦｅ２Ｏ３の組成比は制御しておらず、焼結性の向上をはかるためにＳｉＯ２を１．５〜３．０重量％添加することが必須であり、ＳｉＯ２を添加することによって、アルミナ本来の機械的特性が失われており、黒色アルミナ焼結体部材を装置に組み込む時に割れや欠けが発生する危険性がある。
Conventionally, Patent Documents 1 to 3 are cited as means for coloring white alumina to black.
In Patent Document 1, as a method for producing a black and high-rigidity alumina sintered body, Al 2 O 3 is a main component, and TiC, TiC-TiN solid solution is used as a colorant, and carbides such as NbC, ZrC, HfC, and TaC are used. A method of firing in an inert gas atmosphere such as Ar by containing one or two or more of 0.2 to 10% by weight is disclosed, but reduction firing in an inert gas atmosphere is performed. Is indispensable, and therefore is more expensive than firing in the air, and a large reduction firing furnace is required to manufacture a large-sized member, which makes it difficult to apply.
Patent Document 2 includes Al 2 O 3 as a main component as a precision ceramic material, and Mn 2 O 3 and Fe 2 O 3 , Fe 2 O 3 and CoO, Cr 2 O 3 , Mn 2 O 3 , as colorants, A black alumina sintered body containing 2 to 5% by weight of 3 or 4 types selected from Fe 2 O 3 and CoO is disclosed, but Mn 2 O 3 and Cr 2 O 3 are harmful to the human body and the environment. It is preferable not to use from the viewpoint of environmental hygiene.
On the other hand, in Patent Document 3, as a black alumina ceramic composition, alumina is the main component, MnO 2 , TiO 2 and Fe 2 O 3 are added in a total amount of 5 to 10% by weight as colorants, and as a sintering aid. A black alumina sintered body to which 1.5 to 3.0 wt% of SiO 2 is added is disclosed, but the composition ratio of MnO 2 , TiO 2 and Fe 2 O 3 is not controlled with respect to the total amount of the colorant. In order to improve the sinterability, it is essential to add SiO 2 to 1.5 to 3.0% by weight, and by adding SiO 2 , the original mechanical properties of alumina are lost, There is a risk of cracking or chipping when the black alumina sintered body member is incorporated into the apparatus.
本発明の目的は、大気中で焼成してもアルミナ本来の機械的特性を有し、かつ遮光性を有する黒色アルミナ焼結体とその製造方法を提供することにある。 An object of the present invention is to provide a black alumina sintered body having mechanical properties inherent to alumina even when fired in the atmosphere and having a light shielding property, and a method for producing the same.
従来技術を用いてＡｌ２Ｏ３に少量のＴｉＯ２とＦｅ２Ｏ３の２成分のみを添加し、大気中焼成を行ってもアルミナ本来の機械的特性を有し、かつ黒色を有する緻密な焼結体を得ることは出来ない。
この理由は、従来は使用する原料粒度が粗いため、ただ単にアルミナにＴｉＯ２とＦｅ２Ｏ３を添加しただけでは、ＴｉＯ２とＦｅ２Ｏ３の化合物を形成してしまい、焼結体全体に均一な黒色の焼結体にすることは出来ず、そのため、ＭｎＯ２のような成分を添加してアルミナと固溶体を形成するような手段を用いないと黒色化は出来ない。例え、できても焼結性が悪いためＳｉＯ２等の焼結助剤を添加する必要があるが、ＭｎＯ２、ＴｉＯ２及びＭｎＯ２にさらにＳｉＯ２を添加することでアルミナ含有量が低下し、機械的特性、耐摩耗性、耐食性等の低下をきたし、半導体製造用部品や各種測定装置用部品としての使用は困難である。また、Ａｌ２Ｏ３とＴｉＯ２は反応してＡｌ２ＴｉＯ５を生成しやすく、機械的特性低下の要因となってしまう。
Even if only a small amount of two components of TiO 2 and Fe 2 O 3 is added to Al 2 O 3 using conventional technology, and it is fired in the air, it has the mechanical properties inherent to alumina and has a dense black color. A sintered body cannot be obtained.
The reason for this is that since the raw material particle size used in the past is coarse, simply adding TiO 2 and Fe 2 O 3 to alumina forms a compound of TiO 2 and Fe 2 O 3 , and the entire sintered body Therefore, it is impossible to make a black sintered body without using a means for adding a component such as MnO 2 to form a solid solution with alumina. Even if possible, it is necessary to add a sintering aid such as SiO 2 because the sinterability is poor. However, adding SiO 2 to MnO 2 , TiO 2 and MnO 2 reduces the alumina content. However, mechanical properties, wear resistance, corrosion resistance, and the like are lowered, and it is difficult to use them as semiconductor manufacturing parts and various measuring device parts. In addition, Al 2 O 3 and TiO 2 react with each other to easily generate Al 2 TiO 5, which causes a decrease in mechanical characteristics.
本発明者らは鋭意研究を重ねてきた結果、Ａｌ２Ｏ３、ＴｉＯ２及びＦｅ２Ｏ３の使用原料粒度をある特定の範囲に制御し、ＴｉＯ２及びＦｅ２Ｏ３含有量、重量比を制御し、均一分散することでＴｉＯ２及びＦｅ２Ｏ３の２成分の添加でありながら、高密度、高強度かつ黒色のアルミナ焼結体を得ることを見出した。 As a result of intensive studies, the present inventors have controlled the raw material particle sizes of Al 2 O 3 , TiO 2, and Fe 2 O 3 to a specific range, TiO 2 and Fe 2 O 3 content, weight ratio It was found that high-density, high-strength, and black alumina sintered body can be obtained by adding two components of TiO 2 and Fe 2 O 3 by controlling and uniformly dispersing.
すなわち、本発明の第１は、（ａ−１）Ａｌ２Ｏ３を主成分とし、ＴｉＯ２とＦｅ２Ｏ３を総量で２〜８重量％含有し、（ａ−２）かつＴｉＯ２／Ｆｅ２Ｏ３重量比が０．２０〜０．３５であり、（ｂ）かさ密度が３．８ｇ／ｃｍ３以上であり、（ｃ）平均結晶粒径が４０〜７０μｍであり、（ｄ）曲げ強さが２００ＭＰａ以上であることを特徴とする優れた機械的特性及び遮光性を有する黒色アルミナ焼結体に関する。
本発明の第２は、粒子径が１μｍ以下である純度９９．８重量％以上のＡｌ２Ｏ３粉体と粒子径が０．５μｍ以下である純度９９重量％以上のＴｉＯ２及び粒子径が１μｍ以下である純度９９重量％以上のＦｅ２Ｏ３をＴｉＯ２とＦｅ２Ｏ３の総量で２〜８重量％含有し、ＴｉＯ２／Ｆｅ２Ｏ３重量比が０．２０〜０．３５になるように配合し、平均粒子径が０．８μｍ以下になるように湿式で混合・粉砕・分散し、乾燥し、成形後、１４００〜１７００℃で焼成することを特徴とする請求項１記載の黒色アルミナ焼結体の製造方法に関する。
That is, the first of the present invention includes (a-1) Al 2 O 3 as a main component, TiO 2 and Fe 2 O 3 in a total amount of 2 to 8% by weight, (a-2) and TiO 2 / Fe 2 O 3 weight ratio is 0.20 to 0.35, (b) bulk density is 3.8 g / cm 3 or more, (c) average crystal grain size is 40 to 70 μm, (d) The present invention relates to a black alumina sintered body having excellent mechanical properties and light-shielding properties, characterized by a bending strength of 200 MPa or more.
A second aspect of the present invention is an Al 2 O 3 powder having a particle size of 1 μm or less and a purity of 99.8% by weight or more, TiO 2 having a particle size of 0.5 μm or less and a purity of 99% by weight or more, and a particle size of Fe 2 O 3 having a purity of 99% by weight or more which is 1 μm or less is contained in a total amount of TiO 2 and Fe 2 O 3 in an amount of 2 to 8% by weight, and the TiO 2 / Fe 2 O 3 weight ratio is 0.20 to 0.35. The mixture is mixed so that the average particle size is 0.8 μm or less, mixed, pulverized and dispersed by wet, dried, molded, and fired at 1400 to 1700 ° C. 2. This invention relates to a method for producing a black alumina sintered body.
以下に本発明の黒色アルミナ焼結体が充足すべき各要件について詳細に説明する。
（ａ−１）Ａｌ２Ｏ３を主成分とし、ＴｉＯ２とＦｅ２Ｏ３を総量で２〜８重量％含有している点について。
本発明においては、Ａｌ２Ｏ３（不可避不純物を含む）を主成分とし、ＴｉＯ２とＦｅ２Ｏ３を総量で２〜８重量％、好ましくは３〜５重量％、より好ましくは３．５〜４．５重量％であることが必要である。ＴｉＯ２とＦｅ２Ｏ３を総量で２重量％未満の場合は遮光性を有する黒色が得られないので好ましくない。一方、ＴｉＯ２とＦｅ２Ｏ３を総量で８重量％を越える場合はＡｌ２Ｏ３とＴｉＯ２の反応化合物の生成並びにＦｅ２Ｏ３のＡｌ２Ｏ３に固溶する量が多くなるために結晶が異常粒成長するだけでなく、耐食性の低下をきたし、曲げ強さ等の機械的特性が低下するので好ましくない。なお、Ａｌ２Ｏ３とＴｉＯ２の反応化合物であるＡｌ２ＴｉＯ５生成の有無は以下の方法でＸ線回折により求めた。即ち、焼結体を乳鉢等により粒子径を１０μｍ程度に粉砕した粉体をサンプルとし、Ｘ線回折にてＸ線源ＣｕＫα、管電圧４０ｋＶ、管電流４０ｍＡ、発散スリット１°、散乱スリット１°、受光スリット０．１５ｍｍ、走査軸２θ／θ、走査範囲１０〜７０°の条件で測定し、回折角２０〜２８°の範囲において、Ａｌ２ＴｉＯ５回折ピークに相当する（２００）のピーク及び（１０１）のピーク検出の有無により、Ａｌ２ＴｉＯ５生成の有無を求めた。
Each requirement to be satisfied by the black alumina sintered body of the present invention will be described in detail below.
(A-1) the Al 2 O 3 as a main component, the points containing 2-8 wt% of TiO 2 and Fe 2 O 3 in total.
In the present invention, Al 2 O 3 (including inevitable impurities) is a main component, and TiO 2 and Fe 2 O 3 are 2 to 8 wt% in total, preferably 3 to 5 wt%, more preferably 3.5. It must be ˜4.5% by weight. When the total amount of TiO 2 and Fe 2 O 3 is less than 2% by weight, a black color having a light shielding property cannot be obtained, which is not preferable. On the other hand, when the total amount of TiO 2 and Fe 2 O 3 exceeds 8% by weight, the amount of the reaction compound of Al 2 O 3 and TiO 2 generated and the amount of Fe 2 O 3 dissolved in Al 2 O 3 increase. In addition to abnormal grain growth, the corrosion resistance is lowered, and the mechanical properties such as bending strength are lowered. Incidentally, Al 2 O 3 and the presence of Al 2 TiO 5 generates a reaction compound of TiO 2 was determined by X-ray diffraction in the following manner. Specifically, a powder obtained by pulverizing a sintered body with a mortar or the like to a particle size of about 10 μm is used as a sample. , Measured under the conditions of a light receiving slit of 0.15 mm, a scanning axis 2θ / θ, a scanning range of 10 to 70 °, and a (200) peak corresponding to the Al 2 TiO 5 diffraction peak in a diffraction angle range of 20 to 28 ° and The presence or absence of Al 2 TiO 5 production was determined based on the presence or absence of peak detection in (101).
（ａ−２）ＴｉＯ２／Ｆｅ２Ｏ３重量比が０．２０〜０．３５である点について。
本発明においては、ＴｉＯ２／Ｆｅ２Ｏ３重量比が０．２０〜０．３５、好ましくは０．２２〜０．３１であることが必要である。
ＴｉＯ２とＦｅ２Ｏ３の２成分だけであってもＴｉＯ２とＦｅ２Ｏ３の総量だけではなく、ＴｉＯ２／Ｆｅ２Ｏ３重量比を制御することにより高密度でかつ機械的特性に優れた黒色アルミナ焼結体とすることができる。ＴｉＯ２／Ｆｅ２Ｏ３重量比が０．２０未満の場合はＦｅ２Ｏ３が過剰となり、黒色とならないため好ましくない。一方、ＴｉＯ２／Ｆｅ２Ｏ３重量比が０．３５を越える場合は、焼結体中にＦｅ２Ｏ３量に対するＴｉＯ２量が過剰となり、ＴｉＯ２とＡｌ２Ｏ３が反応することによって、アルミナ結晶粒界に第２相を形成し、機械的特性が低下するだけでなく、白色度が高くなるため好ましくない。
(A-2) TiO 2 / Fe 2 O 3 weight ratio of the points is 0.20 to 0.35.
In the present invention, the TiO 2 / Fe 2 O 3 weight ratio needs to be 0.20 to 0.35, preferably 0.22 to 0.31.
Not only the total amount of TiO 2 and Fe 2 O 3 even if only two components of TiO 2 and Fe 2 O 3, the high density and mechanical properties by controlling the TiO 2 / Fe 2 O 3 weight ratio It can be set as the outstanding black alumina sintered compact. When the weight ratio of TiO 2 / Fe 2 O 3 is less than 0.20, Fe 2 O 3 is excessive and not black, which is not preferable. On the other hand, when the weight ratio of TiO 2 / Fe 2 O 3 exceeds 0.35, the amount of TiO 2 with respect to the amount of Fe 2 O 3 in the sintered body becomes excessive, and TiO 2 and Al 2 O 3 react with each other. This is not preferable because a second phase is formed at the alumina crystal grain boundary, and not only the mechanical properties are deteriorated but also the whiteness is increased.
（ｂ）かさ密度が３．８ｇ／ｃｍ３以上である点について。
本発明においては、かさ密度が３．８ｇ／ｃｍ３以上、好ましくは３．８５ｇ／ｃｍ３以上であることが必要である。かさ密度が３．８ｇ／ｃｍ３未満である場合は焼結体内部に気孔を多く含有するため機械的特性が低く、黒色度が低くなるため好ましくない。かさ密度はＪＩＳ Ｒ １６３４に準じたアルキメデス法により測定する。
(B) About the point whose bulk density is 3.8 g / cm 3 or more.
In the present invention, the bulk density needs to be 3.8 g / cm 3 or more, preferably 3.85 g / cm 3 or more. A bulk density of less than 3.8 g / cm 3 is not preferable because it contains many pores inside the sintered body, resulting in low mechanical properties and low blackness. The bulk density is measured by the Archimedes method according to JIS R 1634.
（ｃ）平均結晶粒径が４０〜７０μｍである点について。
本発明においては、平均結晶粒径が４０〜７０μｍ、好ましくは４５〜６５μｍであることが必要である。平均結晶粒径が４０μｍ未満の場合は、研削加工時にチッピング等が生じ、加工性が低下するため好ましくなく、７０μｍを超える場合には、曲げ強さの低下及び加工時に脱粒等が発生し、加工面の表面粗さが粗くなるので好ましくない。
なお、本発明における平均結晶粒径の測定は、焼結体表面を鏡面仕上げし、熱エッチングした面を走査電子顕微鏡にて観察し、インターセプト法により１０点平均から下式により算出する。
Ｄ＝１．５×５０／１５＝５
となり、平均結晶粒径は５μｍとなる。
(C) About the point whose average crystal grain diameter is 40-70 micrometers.
In the present invention, it is necessary that the average crystal grain size is 40 to 70 μm, preferably 45 to 65 μm. When the average crystal grain size is less than 40 μm, chipping or the like occurs during grinding and the workability deteriorates. This is not preferable, and when it exceeds 70 μm, bending strength decreases and shedding occurs during processing. Since the surface roughness of the surface becomes rough, it is not preferable.
The average crystal grain size in the present invention is measured by mirror finishing the sintered body surface, observing the thermally etched surface with a scanning electron microscope, and calculating from the average of 10 points by the intercept method using the following formula.
D = 1.5 × 50/15 = 5
Thus, the average crystal grain size is 5 μm.
（ｄ）曲げ強さが２００ＭＰａ以上である点について。
本発明において曲げ強さは２００ＭＰａ以上、好ましくは２５０ＭＰａ以上であることが必要である。曲げ強さが２００ＭＰａ未満の場合は、例えば半導体製造装置用部材とした場合に加工により、かけや割れ等が発生しやすくなり高精度の表面状態が得られないだけでなく、ハンドリング時に割れ発生の危険性があるので好ましくない。曲げ強さは３×４×５０ｍｍに切断・加工した焼結体をＪＩＳ Ｒ １６０１に準じて測定する。
(D) About the point whose bending strength is 200 MPa or more.
In the present invention, the bending strength needs to be 200 MPa or more, preferably 250 MPa or more. When the bending strength is less than 200 MPa, for example, when a member for a semiconductor manufacturing apparatus is used, not only a crack or crack is likely to occur due to processing, and a high-accuracy surface state cannot be obtained. Because there is a danger, it is not preferable. The bending strength is measured according to JIS R 1601 for a sintered body cut and processed to 3 × 4 × 50 mm.
本発明の黒色アルミナ焼結体の製造方法を下記に示す。 The manufacturing method of the black alumina sintered body of the present invention is shown below.
Ａｌ２Ｏ３粉体は純度９９．８重量％以上、平均粒子径が１μｍ以下、好ましくは０．８μｍ以下であることが必要である。Ａｌ２Ｏ３純度が９９．８重量％未満である場合、含有する不純物成分が焼結体の色調に影響し、遮光性を有する黒色を得るのが困難になるだけでなく、機械的特性の低下をきたすので好ましくない。平均粒子径が１μｍを超える場合は、焼結性が低下するだけでなく、ＴｉＯ２及びＦｅ２Ｏ３との均一分散ができないため均一な黒色が得られないので好ましくない。 The Al 2 O 3 powder needs to have a purity of 99.8% by weight or more and an average particle size of 1 μm or less, preferably 0.8 μm or less. When the Al 2 O 3 purity is less than 99.8% by weight, not only does the impurity component contained affect the color tone of the sintered body, it becomes difficult to obtain a black color having a light shielding property, but also mechanical properties. Since it causes a decrease, it is not preferable. When the average particle diameter exceeds 1 μm, not only the sinterability is lowered but also uniform dispersion with TiO 2 and Fe 2 O 3 is not possible, so that a uniform black color cannot be obtained.
ＴｉＯ２粉体の平均粒子径は０．５μｍ以下、好ましくは０．３μｍ以下であり、純度９９重量％以上であることが必要である。ＴｉＯ２の平均粒子径が０．５μｍを越える場合は、Ａｌ２Ｏ３焼結体中でのＴｉＯ２の不均一性が大きくなり、Ａｌ２Ｏ３と第２相を形成しやすくなり、焼結性が低下し、機械的特性が低下するだけでなく、焼結体の所々で黒色の斑点が生じ、焼結体全体で均一な黒色を有するアルミナ焼結体が得られないので好ましくない。 The average particle diameter of the TiO 2 powder is 0.5 μm or less, preferably 0.3 μm or less, and the purity needs to be 99% by weight or more. When the average particle diameter of TiO 2 exceeds 0.5 μm, the non-uniformity of TiO 2 in the Al 2 O 3 sintered body increases, and it becomes easier to form a second phase with Al 2 O 3 , This is not preferable because not only the cohesiveness is lowered and the mechanical properties are lowered, but also black spots are generated in various places of the sintered body, and an alumina sintered body having a uniform black color cannot be obtained throughout the sintered body.
ＴｉＯ２粉体はＴｉＯ２、Ｔｉ２Ｏ３、ＴｉＯ等のチタン酸化物の形態だけでなく、ゾルや熱分解により酸化物となるＴｉＯ２化合物の形態で使用できる。 The TiO 2 powder can be used not only in the form of a titanium oxide such as TiO 2 , Ti 2 O 3 , TiO, but also in the form of a TiO 2 compound that becomes an oxide by sol or thermal decomposition.
Ｆｅ２Ｏ３粉体の平均粒子径は１μｍ以下、好ましくは０．８μｍ以下であり、純度９９重量％以上であることが必要である。Ｆｅ２Ｏ３の平均粒子径が１μｍを越える場合は、Ａｌ２Ｏ３焼結体中でのＦｅ２Ｏ３の不均一性が大きくなり、機械的特性が低下するだけでなく、ＴｉＯ２とＦｅ２Ｏ３との反応が不均一となり、焼結体の所々で黒色の斑点が生じ、焼結体全体で均一な黒色を有するアルミナ焼結体が得られないので好ましくない。 The average particle size of the Fe 2 O 3 powder is 1 μm or less, preferably 0.8 μm or less, and the purity needs to be 99% by weight or more. When the average particle diameter of Fe 2 O 3 exceeds 1 μm, the non-uniformity of Fe 2 O 3 in the Al 2 O 3 sintered body becomes large and not only the mechanical properties are deteriorated, but also TiO 2 and The reaction with Fe 2 O 3 becomes non-uniform, black spots are generated in places of the sintered body, and an alumina sintered body having a uniform black color cannot be obtained in the entire sintered body.
Ｆｅ２Ｏ３粉体はＦｅ２Ｏ３、Ｆｅ３Ｏ４等の鉄酸化物の形態や熱分解より酸化物となる化合物（例えばクエン酸鉄など）等の形態で使用できる。
Ａｌ２Ｏ３、ＴｉＯ２及びＦｅ２Ｏ３粉体を所定量となるように配合し、湿式で水及び有機溶媒を用いて混合・粉砕・分散する。混合・粉砕・分散後の混合粉体の平均粒子径は０．８μｍ以下、好ましくは０．５μｍ以下とする必要がある。平均粒子径が０．８μｍを超える場合は、焼結性が低下するだけでなく、ＴｉＯ２及びＦｅ２Ｏ３粉体の均一混合・分散ができていないので機械的特性の低下や均一な黒色とすることができないので好ましくない。また、ＴｉＯ２とＦｅ２Ｏ３はあらかじめＴｉＯ２及びＦｅ２Ｏ３粉体を混合し、大気中１０００〜１２００℃で仮焼合成してＴｉＯ２とＦｅ２Ｏ３の化合物の形態で使用することも可能である。
The Fe 2 O 3 powder can be used in the form of an iron oxide such as Fe 2 O 3 or Fe 3 O 4 or a compound that becomes an oxide by thermal decomposition (for example, iron citrate).
Al 2 O 3 , TiO 2, and Fe 2 O 3 powders are blended so as to have a predetermined amount, and are mixed, pulverized, and dispersed in a wet manner using water and an organic solvent. The average particle size of the mixed powder after mixing, pulverization, and dispersion needs to be 0.8 μm or less, preferably 0.5 μm or less. When the average particle diameter exceeds 0.8 μm, not only the sinterability is deteriorated but also the TiO 2 and Fe 2 O 3 powders are not uniformly mixed and dispersed, so that the mechanical properties are deteriorated and the black color is uniform. This is not preferable. In addition, TiO 2 and Fe 2 O 3 are mixed in advance with TiO 2 and Fe 2 O 3 powders, and calcined at 1000 to 1200 ° C. in the atmosphere and used in the form of a compound of TiO 2 and Fe 2 O 3. It is also possible.
混合・粉砕・分散したスラリーは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（成形条件によっては成形助剤を添加しなくても成形可能）、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。 If necessary, a known molding aid (wax emulsion, PVA, acrylic resin, etc.) can be added to the mixed, pulverized, and dispersed slurry (can be molded without adding a molding aid depending on molding conditions), and spray dryers, etc. A molded powder is obtained by drying by a known method.
得られた成形粉体を用いて、公知の成形方法、例えばプレス成形、ラバープレス成形、ＣＩＰ（冷間等方圧成形）等の方法により、所定の形状の成形体を得る。
また、乾燥した粉体に公知の押出成形助剤（メチルセルロース等）を添加混合し、混練し、押出成形により所定の形状の成形体を得る。
作製した成形体を大気中（Ｎ２やＡｒなどの不活性雰囲気中でもよいが、コストが上昇する）１４００〜１７００℃、好ましくは１５００〜１６５０℃で焼成して黒色アルミナ焼結体を得る。焼成温度が１４００℃より低いと緻密化が十分ではなく、焼結体の気孔率が大きくなり、機械的特性の低下を招くだけでなく、彩度が低く遮光性を有する黒色が得られないため、好ましくない。一方、焼成温度が１７００℃を越えると結晶粒径が大きくなり、機械的特性の低下を招くため、好ましくない。
Using the obtained molded powder, a molded body having a predetermined shape is obtained by a known molding method such as press molding, rubber press molding, CIP (cold isostatic pressing) or the like.
Also, a known extrusion aid (such as methyl cellulose) is added to the dried powder, mixed and kneaded, and a molded body having a predetermined shape is obtained by extrusion.
The produced molded body is fired at 1400 to 1700 ° C., preferably 1500 to 1650 ° C. in the air (which may be in an inert atmosphere such as N 2 or Ar, but the cost increases) to obtain a black alumina sintered body. If the firing temperature is lower than 1400 ° C., the densification is not sufficient, the porosity of the sintered body is increased, and not only mechanical properties are deteriorated, but also black color with low chroma and light shielding properties cannot be obtained. It is not preferable. On the other hand, when the firing temperature exceeds 1700 ° C., the crystal grain size becomes large, and the mechanical characteristics are deteriorated, which is not preferable.
本発明の黒色アルミナ焼結体は、人体や環境に悪影響を与える恐れのないＴｉＯ２とＦｅ２Ｏ３の２成分の総量及びＴｉＯ２／Ｆｅ２Ｏ３重量比を特定の範囲に制御し、大気中で焼成しても、アルミナ本来の機械的特性を有し、かつ遮光性を有する黒色が得られるため、従来の黒色アルミナ焼結体に比べ、低コストで製造することができ、焼結体が含有する成分によって人体や環境に悪影響を及ぼす危険性がなく、優れた機械的特性を有していることから、半導体製造装置用部材、精密測定用治具等の産業用構造部材の用途として広く利用できるものである。 The black alumina sintered body of the present invention controls the total amount of the two components of TiO 2 and Fe 2 O 3 and the TiO 2 / Fe 2 O 3 weight ratio within a specific range, which do not adversely affect the human body and the environment, Even when fired in the air, it has the original mechanical properties of alumina and has a light-shielding black color, so it can be manufactured at a lower cost than conventional black alumina sintered bodies. There is no risk of adversely affecting the human body and the environment due to the components contained in the body, and it has excellent mechanical properties, so it is used for industrial structural members such as semiconductor manufacturing equipment members and precision measurement jigs. Can be widely used.
以下に実施例および比較例により本発明を具体的に説明するが、本発明はこれらの実施例により何ら限定されるものでない。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
実施例１〜１１、比較例１〜１１
純度９９．９重量％のＡｌ２Ｏ３原料粉体を用い、ＴｉＯ２及びＦｅ２Ｏ３含有量が表１の組成となるようにＡｌ２Ｏ３、ＴｉＯ２及びＦｅ２Ｏ３粉体を配合し、水を用いて湿式によりボールミルで混合・粉砕・分散した。混合・粉砕・分散したスラリーの平均粒子径を表１に示す。なお、実施例Ｎｏ．４と６はＴｉＯ２とＦｅ２Ｏ３粉体をＡｌ２Ｏ３原料粉体と混合・粉砕・分散する前に、予めＴｉＯ２とＦｅ２Ｏ３を水を用いて湿式で混合・粉砕・分散し、乾燥し、１０００℃で合成した粉体をさらに水で湿式で粉砕してＡｌ２Ｏ３原料粉体と混合・粉砕・分散した。用いたＴｉＯ２及びＦｅ２Ｏ３は純度９９重量％の酸化物粉体で用いた。混合・粉砕・分散したスラリーにバインダーとしてＰＶＡ（ポリビニルアルコール）を粉体に対して２重量％添加し、スプレードライヤーで乾燥して成形用粉体を作製した。また、なお、比較例Ｎｏ．３は平均粒子径が１．４μｍのＡｌ２Ｏ３原料粉体を用い、比較例Ｎｏ．２は平均粒子径０．８μｍのＴｉＯ２粉体を用い、比較例Ｎｏ．９は平均粒子径が１．６μｍのＦｅ２Ｏ３粉体を用いた。また、比較例Ｎｏ．４と８はＳｉＯ２を２重量％、比較例Ｎｏ．４はＭｎＯ２を１．２重量％を混合・粉砕・分散する際に添加した。
作製した成形用粉体を金型を用いて２０ＭＰａの予備成形後ＣＩＰ（冷間等方圧成形）により１００ＭＰａの圧力で成形して成形体を得、電気炉で１３８０〜１７５０℃にて大気中２時間保持で焼成した。得られた焼結体のかさ密度は水を用いてアルキメデス法により測定し、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た後、走査電子顕微鏡で観察して、インターセプト法により算出した。曲げ強さは焼結体からＪＩＳ Ｒ １６０１に準じて３×４×５０ｍｍに切断、研削加工したテストピースを用いて測定した。
また、Ａｌ２ＴｉＯ５生成の有無は以下の方法でＸ線回折により求めた。即ち、焼結体を乳鉢等により粒子径を１０μｍ程度に粉砕した粉体をサンプルとし、Ｘ線回折にてＸ線源ＣｕＫα、管電圧４０ｋＶ、管電流４０ｍＡ、発散スリット１°、散乱スリット１°、受光スリット０．１５ｍｍ、走査軸２θ／θ、走査範囲１０〜７０°の条件で測定し、回折角２０〜２８°の範囲において、Ａｌ２ＴｉＯ５回折ピークに相当する（２００）のピーク及び（１０１）のピーク検出の有無により、Ａｌ２ＴｉＯ５生成の有無を求めた。その結果を表２に示す。
これにより本発明の黒色アルミナ焼結体は、高密度で曲げ強さが従来の黒色アルミナ焼結体に比べて高い優れた特性を有していることが明らかとなった。
Examples 1-11, Comparative Examples 1-11
With purity of 99.9 wt% Al 2 O 3 raw material powder, the Al 2 O 3, TiO 2 and Fe 2 O 3 powder as TiO 2 and Fe 2 O 3 content is the composition of Table 1 The resulting mixture was mixed, pulverized, and dispersed by a ball mill using water. Table 1 shows the average particle size of the mixed, pulverized and dispersed slurry. In addition, Example No. 4 and 6 of TiO 2 and Fe 2 O 3 powder before Al 2 O 3 raw material powder mixture, grinding and dispersing the material, and mixed and ground by the wet with the previously TiO 2 and Fe 2 O 3 water The powder dispersed, dried, and synthesized at 1000 ° C. was further wet pulverized with water and mixed, pulverized, and dispersed with the Al 2 O 3 raw material powder. The TiO 2 and Fe 2 O 3 used were oxide powders having a purity of 99% by weight. 2% by weight of PVA (polyvinyl alcohol) as a binder was added to the mixed, pulverized, and dispersed slurry, and dried with a spray dryer to prepare a molding powder. In addition, Comparative Example No. 3 is an Al 2 O 3 raw material powder having an average particle diameter of 1.4 μm. 2 uses TiO 2 powder having an average particle diameter of 0.8 μm. For No. 9, Fe 2 O 3 powder having an average particle diameter of 1.6 μm was used. Comparative Example No. Nos. 4 and 8 contain 2 % by weight of SiO 2 and Comparative Example No. No. 4 was added when 1.2% by weight of MnO 2 was mixed, ground and dispersed.
The molding powder thus prepared was preformed at 20 MPa using a mold and then molded at a pressure of 100 MPa by CIP (cold isostatic pressing) to obtain a molded body. Firing was carried out for 2 hours. The bulk density of the obtained sintered body was measured by the Archimedes method using water, and the average crystal grain size was obtained by intercepting the sintered body with a mirror finish, applying thermal etching, and observing with a scanning electron microscope. Calculated by The bending strength was measured using a test piece cut and ground from a sintered body to 3 × 4 × 50 mm according to JIS R 1601.
Also, the presence of Al 2 TiO 5 product was determined by X-ray diffraction in the following manner. That is, a powder obtained by pulverizing a sintered body with a mortar or the like to a particle size of about 10 μm is used as a sample, and X-ray diffraction is performed using an X-ray source CuKα, tube voltage 40 kV, tube current 40 mA, divergence slit 1 °, scattering slit 1 °. , Measured under the conditions of a light receiving slit of 0.15 mm, a scanning axis 2θ / θ, a scanning range of 10 to 70 °, and a (200) peak corresponding to the Al 2 TiO 5 diffraction peak in a diffraction angle range of 20 to 28 ° and The presence or absence of Al 2 TiO 5 production was determined based on the presence or absence of peak detection in (101). The results are shown in Table 2.
This revealed that the black alumina sintered body of the present invention has excellent characteristics with high density and high bending strength compared to the conventional black alumina sintered body.
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| WO2024225475A1 (en) * | 2023-04-28 | 2024-10-31 | 京セラ株式会社 | Ceramic sintered body |
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