JPH03183668A - Production of porous ceramics - Google Patents
Production of porous ceramicsInfo
- Publication number
- JPH03183668A JPH03183668A JP32058689A JP32058689A JPH03183668A JP H03183668 A JPH03183668 A JP H03183668A JP 32058689 A JP32058689 A JP 32058689A JP 32058689 A JP32058689 A JP 32058689A JP H03183668 A JPH03183668 A JP H03183668A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic particles
- particles
- porous ceramics
- alumina
- ceramic
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000002245 particle Substances 0.000 claims abstract description 57
- 239000010419 fine particle Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 29
- 239000011148 porous material Substances 0.000 abstract description 16
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052863 mullite Inorganic materials 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- -1 electrofused Chemical compound 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000084 colloidal system Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明はポーラスセラミックスの製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for manufacturing porous ceramics.
〔従来の技術及び発明が解決しようとする課題〕孔径２
０〜１００ｎ程度の孔径の大きいポーラスセラミックス
を製造する場合、粒径５０〜３００卸のセラミック粒子
が使用されている。この場合、粒径５０〜３００−のセ
ラミック粒子を単独で焼結させることは困難であるため
、従来は５ｉ０２、ＰｂＯなどのガラス相を介してセラ
ミック粒子を結合させていた。しかし、このようなポー
ラスセラミックスはガラス相が存在するため、耐食性及
び強度が低下するという問題があった。[Problems to be solved by conventional technology and invention] Pore diameter 2
When producing porous ceramics with a large pore size of about 0 to 100 nm, ceramic particles with a particle size of 50 to 300 nm are used. In this case, since it is difficult to sinter ceramic particles having a particle size of 50 to 300 mm alone, conventionally the ceramic particles have been bonded via a glass phase such as 5i02 or PbO. However, since such porous ceramics have a glass phase, there is a problem that corrosion resistance and strength are reduced.
本発明は前記課題を解決するためになされたものであり
、孔径が大きくかつ均一で、しかも耐食性及び強度に優
れたポーラスセラミックスを製造し得る方法を提供する
ことを目的とする。The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for producing porous ceramics having large and uniform pore diameters and excellent corrosion resistance and strength.
本発明のポーラスセラミックスの製造方法は、セラミッ
ク粒子及び該セラミック粒子と同一の組成を有するセラ
ミック微粒子のコロイド溶液とを混合した後、ｐＨを調
整する工程と、乾燥した後、仮焼する工程と、仮焼体を
解砕した後、成形し、焼成する工程とを具備したことを
特徴とするものである。The method for producing porous ceramics of the present invention includes a step of adjusting the pH after mixing ceramic particles and a colloidal solution of ceramic fine particles having the same composition as the ceramic particles, and a step of calcining after drying. The method is characterized by comprising a step of crushing the calcined body, then shaping and firing it.
以下、本発明を更に詳細に説明する。The present invention will be explained in more detail below.
本発明において、セラミック粒子はポーラスセラミック
スのマトリックスを構成するものである。In the present invention, the ceramic particles constitute a matrix of porous ceramics.
セラミック粒子の材質としては、アルミナ（電融アルミ
ナなど）、ムライト（電融ムライト、焼成ムライトなど
）、シリカ、ジルコニア（ＭｇＯ又はＣａＯ安定化電融
ジルコニアなど）が挙げられる。セラミック粒子の粒径
は、得ようとするポーラスセラミックスの孔径に応じて
異なる。ただし、本発明では主に孔径が５０μ以上のポ
ーラスセラミックスを対象としているので、セラミック
粒子は平均粒径が１００μｓ以上になるように粒度調整
することが望ましい。Examples of the material of the ceramic particles include alumina (eg, fused alumina), mullite (eg, fused mullite, fired mullite), silica, and zirconia (eg, MgO or CaO stabilized fused zirconia). The particle size of the ceramic particles varies depending on the pore size of the porous ceramic to be obtained. However, since the present invention is mainly aimed at porous ceramics with a pore size of 50 μm or more, it is desirable to adjust the particle size of the ceramic particles so that the average particle size is 100 μs or more.
本発明において、コロイド溶液は、コロイド粒子が溶媒
中に均一に分散したものである。この場合、コロイド粒
子とは、セラミック粒子と同一の組成を有するセラミッ
ク分子が集合した形成されたセラミック微粒子で、電気
的に安定な状態にあるものをいう。すなわち、セラミッ
ク粒子がアルミナの場合にはアルミナゾル、ムライトの
場合にはアルミナゾル及びシリカゾル、ジルコニアの場
合にはジルコニアゾルが用いられる。In the present invention, a colloidal solution is one in which colloidal particles are uniformly dispersed in a solvent. In this case, colloidal particles are ceramic fine particles formed by aggregation of ceramic molecules having the same composition as ceramic particles, and are in an electrically stable state. That is, when the ceramic particles are alumina, alumina sol is used, when the ceramic particles are mullite, alumina sol and silica sol are used, and when the ceramic particles are zirconia, zirconia sol is used.
セラミック粒子とコロイド溶液との混合割合は、以下の
■式を満足するように決定することが望ましい。The mixing ratio of ceramic particles and colloidal solution is desirably determined so as to satisfy the following formula (1).
■式中、 ｒはコロイド粒子の平均粒子径 Ｈはセラミック粒子の比表面積 Ｗはセラミック粒子の添加量 Ｗはコロイド溶液の添加量 ｄはコロイド溶液の比重 ２はコロイド溶液中の固形分の重量％ である。■During the ceremony, r is the average particle diameter of colloidal particles H is the specific surface area of ceramic particles W is the amount of ceramic particles added W is the amount of colloid solution added d is the specific gravity of the colloidal solution 2 is the weight percent of solids in the colloidal solution It is.
この値が１未満では、結合力が充分でなくなり、ポーラ
スセラミックスの強度が低下する。この値が１．３を超
えると、セラミック粒子の表面に被覆されるセラミック
微粒子の層が厚くなり、膜厚にむらが生じるため、ポー
ラスセラミックスの孔径を精密に制御することができな
い。If this value is less than 1, the bonding force will not be sufficient and the strength of the porous ceramic will decrease. If this value exceeds 1.3, the layer of ceramic fine particles coated on the surface of the ceramic particles becomes thick and the film thickness becomes uneven, making it impossible to precisely control the pore diameter of the porous ceramic.
次に、セラミック粒子とコロイド溶液とを混合した後、
ｐ）ｆを調整する。この際、ｐＨを６以上にするとコロ
イド粒子のゲル化が起こり、セラミック粒子の表面に電
気的安定を失ったセラミック微粒子が付着する。Then, after mixing the ceramic particles and the colloidal solution,
p) Adjust f. At this time, when the pH is set to 6 or higher, gelation of the colloid particles occurs, and ceramic fine particles that have lost electrical stability adhere to the surfaces of the ceramic particles.
次に、この液は乾燥された後、その残渣が仮焼される。Next, this liquid is dried and the residue is calcined.
望ましい仮焼温度は材質によって異なる。The desired calcination temperature varies depending on the material.
例えば、アルミナの場合、仮焼温度は８００ 〜ｌｌ０
０℃であることが好ましい。これは、アルミナが以下の
ような相転移を示すことによる。For example, in the case of alumina, the calcination temperature is 800 to 100
Preferably it is 0°C. This is because alumina exhibits the following phase transition.
アルミナゲル→（約５００℃）→γ−アルミナ→（約１
０００℃）→θ−アルミナ→（約１２００℃）→α−ア
ルミナ
６００℃未満ではアルミナ粒子の表面にアルミナ微粒子
が強固に固着しておらず、この状態で焼成してもアルミ
ナ粒子を結合させる役割を果たさない。１１００℃を超
えるとアルミナ粒子の表面にアルミナ微粒子が強固に固
着しているが、アルミナ微粒子のα化が進むので、この
状態で焼成するとアルミナ微粒子どうしの結合強度が低
下する。Alumina gel → (about 500℃) → γ-alumina → (about 1
000℃) → θ-Alumina → (Approx. 1200℃) → α-Alumina Below 600℃, the alumina fine particles are not firmly attached to the surface of the alumina particles, and even if fired in this state, the role of binding the alumina particles is not fulfill the purpose. When the temperature exceeds 1100°C, the alumina fine particles are firmly fixed to the surface of the alumina particles, but since the alumina fine particles become alpha, the bonding strength between the alumina fine particles decreases when firing in this state.
また、ムライトの場合、仮焼温度は９００〜１３００℃
であることが好ましい。９００℃未満ではアルミナゲル
とシリカゲルとが反応していないので、この状態で焼成
してもムライト粒子を結合させる役割を果たさない。１
３００℃を超え・るとゲルのムライト化が進みすぎるの
で、この状態で焼成するとムライト微粒子どうしの結合
強度が低下する。In addition, in the case of mullite, the calcination temperature is 900 to 1300℃
It is preferable that Since alumina gel and silica gel do not react at temperatures below 900°C, firing in this state does not serve to bind mullite particles. 1
If the temperature exceeds 300°C, the gel becomes too mullite, so if it is fired in this state, the bonding strength between fine mullite particles will decrease.
更に、仮焼体を解砕した後、成形し、セラミック粒子の
表面にセラミック微粒子の被覆層が存在する状態で焼成
すると、セラミック微粒子の被覆層を介してセラミック
粒子が結合し、孔径が大きくかつ均一で、しかも耐食性
及び強度に優れたポーラスセラミックスを得ることがで
きる。Furthermore, if the calcined body is crushed, shaped, and fired with a coating layer of fine ceramic particles on the surface of the ceramic particles, the ceramic particles will bond through the coating layer of fine ceramic particles, resulting in large pores and Porous ceramics that are uniform and have excellent corrosion resistance and strength can be obtained.
以下、本発明の詳細な説明する。 The present invention will be explained in detail below.
実施例１．２及び比較例１．２
予め電融アルミナを平均粒径が３００μｍとなるように
粒度調整しておいた。このアルミナ粒子の比表面積を比
表面積測定装置により測定したところ、１００００ｃｍ
／ｇであった。また、市販のアルミナコロイド溶液（Ａ
ＳＫ−１２０、住友化学工業■製；固形分１０％、比重
１．１ｇ／ｃｍ３ コロイド粒子の平均粒子径２０μ
、安定化剤−酢酸）を用意した。そして前記■式の値が
１．１となるように、電融アルミナ粒子の添加量に対す
るアルミナコロイド溶液の添加量を算出した。Example 1.2 and Comparative Example 1.2 The particle size of fused alumina was adjusted in advance so that the average particle size was 300 μm. When the specific surface area of these alumina particles was measured using a specific surface area measuring device, it was found to be 10,000 cm.
/g. In addition, a commercially available alumina colloid solution (A
SK-120, manufactured by Sumitomo Chemical ■; solid content 10%, specific gravity 1.1 g/cm3, average particle size of colloidal particles 20 μ
, stabilizer-acetic acid) were prepared. Then, the amount of the alumina colloid solution added to the amount of the fused alumina particles was calculated so that the value of the equation (1) was 1.1.
電融アルミナ粒子１重量部とアルミナコロイド溶液２４
．２５重量部とを混合した後、アンモニアを添加して、
ｐＨを６．５以上に調整した。この液を乾燥した後、そ
れぞれ５００℃（比較例１） 、７５０℃（実施例１
） 、１０００℃（実施例２） 、１２００℃（比較例
２）で２時間仮焼した。各仮焼体を解砕し、板状に成形
した後、１６００℃で２時間焼成してポーラスセラミッ
クスを製造した。1 part by weight of fused alumina particles and 24 parts by weight of alumina colloid solution
．． After mixing with 25 parts by weight, ammonia is added,
The pH was adjusted to 6.5 or higher. After drying this liquid, the temperature was 500°C (Comparative Example 1) and 750°C (Example 1), respectively.
), 1000°C (Example 2) and 1200°C (Comparative Example 2) for 2 hours. Each calcined body was crushed and formed into a plate shape, and then fired at 1600° C. for 2 hours to produce porous ceramics.
比較例３
電融アルミナ粒子８７重量部及び５ｉ０２１２重量部を
混合し、板状に成形した後、１８５０℃で２時間焼成し
てポーラスセラミックスを製造した。Comparative Example 3 87 parts by weight of fused alumina particles and 212 parts by weight of 5i0 were mixed, formed into a plate shape, and fired at 1850° C. for 2 hours to produce porous ceramics.
得られた各ポーラスセラミックスについて、かさ密度、
室温及び８００℃における曲げ強さ、通気率、１０００
℃における熱間線膨張率を測定した結果を第１表に示す
。For each porous ceramic obtained, the bulk density,
Bending strength at room temperature and 800°C, air permeability, 1000
Table 1 shows the results of measuring the hot linear expansion coefficient at °C.
また、実施例１及び比較例３のポーラスセラミックスに
ついて、
細孔分布を測定した結果を第１
図に示す。Furthermore, the results of measuring the pore distribution of the porous ceramics of Example 1 and Comparative Example 3 are shown in FIG.
第
表
第１表から明らかなように、実施例１．２のポーラスセ
ラミックスは、比較例１〜３のものより曲げ強さが著し
く向上している。また、第１図から明らかなように、実
施例１のポーラスセラミックスは３０〜４０μの孔径を
有する細孔が非常に多く、比較例３のものより孔径が均
一である。As is clear from Table 1, the porous ceramics of Example 1.2 have significantly improved bending strength than those of Comparative Examples 1-3. Moreover, as is clear from FIG. 1, the porous ceramic of Example 1 has a large number of pores having a pore diameter of 30 to 40 μm, and the pore diameter is more uniform than that of Comparative Example 3.
以上詳述したように本発明の方法を用いれば、孔径が大
きくかつ均一で、しかも耐食性及び強度に優れたポーラ
スセラミックスを製造することができ、その工業的価値
は極めて大きい。As described in detail above, by using the method of the present invention, it is possible to produce porous ceramics having large and uniform pore diameters and excellent corrosion resistance and strength, and its industrial value is extremely large.
第１図は本発明の実施例１及び比較例３の方法で製造さ
れたポーラスセラミックスの細孔分布を示す特性図であ
る。FIG. 1 is a characteristic diagram showing the pore distribution of porous ceramics manufactured by the methods of Example 1 and Comparative Example 3 of the present invention.
Claims (1)
有するセラミック微粒子のコロイド溶液とを混合した後
、ｐＨを調整する工程と、乾燥した後、仮焼する工程と
、仮焼体を解砕した後、成形し、焼成する工程とを具備
したことを特徴とするポーラスセラミックスの製造方法
。After mixing the ceramic particles and a colloidal solution of ceramic fine particles having the same composition as the ceramic particles, a step of adjusting the pH, a step of drying and calcining, and a step of crushing the calcined body and forming it. 1. A method for producing porous ceramics, comprising the steps of: and firing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32058689A JPH03183668A (en) | 1989-12-12 | 1989-12-12 | Production of porous ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32058689A JPH03183668A (en) | 1989-12-12 | 1989-12-12 | Production of porous ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03183668A true JPH03183668A (en) | 1991-08-09 |
Family
ID=18123074
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32058689A Pending JPH03183668A (en) | 1989-12-12 | 1989-12-12 | Production of porous ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03183668A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006124256A (en) * | 2004-10-29 | 2006-05-18 | Noritake Co Ltd | Zirconia porous body and its manufacturing method |
-
1989
- 1989-12-12 JP JP32058689A patent/JPH03183668A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006124256A (en) * | 2004-10-29 | 2006-05-18 | Noritake Co Ltd | Zirconia porous body and its manufacturing method |
| JP4580729B2 (en) * | 2004-10-29 | 2010-11-17 | 株式会社ノリタケカンパニーリミテド | Zirconia porous body and method for producing the same |
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