JPH07112532B2 - Method for manufacturing filtration membrane - Google Patents
Method for manufacturing filtration membraneInfo
- Publication number
- JPH07112532B2 JPH07112532B2 JP9049788A JP9049788A JPH07112532B2 JP H07112532 B2 JPH07112532 B2 JP H07112532B2 JP 9049788 A JP9049788 A JP 9049788A JP 9049788 A JP9049788 A JP 9049788A JP H07112532 B2 JPH07112532 B2 JP H07112532B2
- Authority
- JP
- Japan
- Prior art keywords
- filtration membrane
- treatment
- etching
- foil
- supporting
- 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.)
- Expired - Lifetime
Links
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- Separation Using Semi-Permeable Membranes (AREA)
- Filtering Materials (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 この発明は、気体や液体、あるいはそれらの混合物の浄
化、精製、もしくは固体との分離等の目的のために使用
される濾過膜、特にフィルター要素として多孔質の電解
エッチング箔を利用する濾過膜の製造方法に関する。TECHNICAL FIELD The present invention relates to a filtration membrane, particularly as a filter element, used for the purpose of purifying gas, liquid, or a mixture thereof, purification, separation from solids, or the like. The present invention relates to a method for manufacturing a filtration membrane using a porous electrolytic etching foil.
従来の技術 従来、耐熱性、耐薬品性、耐溶剤性、耐油性等に優れ、
しかも濾過特性に優れた濾過膜として、アルミニウム箔
を用いたものが提案されている。即ち、結晶方位を制御
して製作した高純度アルミニウム箔にエッチングを施す
ことにより、所要の孔径を有する貫通エッチングピット
を形成し、その後表面に陽極酸化皮膜あるいは水酸化皮
膜を形成してピット径の調整をはかったものが提案され
ている（例えば特開昭62−30510号、同62−30511号、同
62−30512号）。Conventional technology Conventionally, it has excellent heat resistance, chemical resistance, solvent resistance, oil resistance, etc.
Moreover, as a filtration membrane having excellent filtration characteristics, a membrane using aluminum foil has been proposed. That is, by etching a high-purity aluminum foil produced by controlling the crystal orientation, a through etching pit having a required pore size is formed, and then an anodic oxide film or a hydroxide film is formed on the surface to reduce the pit size. Some adjustments have been proposed (for example, Japanese Patent Laid-Open Nos. 62-30510, 62-30511, and 62-30511).
62-30512).
発明が解決しようとする課題 ところが、上記従来技術による濾過膜は、濾過機能を果
すために貫通孔を直流電解等によるエッチングの技法を
用いて形成するものであるため、第２図に示すように必
然的に箔（11）の表面が荒れ、貫通ピット（12）以外に
表面に粗大な凹凸（13）が形成されると共に、貫通ピッ
ト（12）が箔の表面部において拡大部（12a）に形成さ
れることを歪み得ない。このため、該濾過膜を微粒子の
分離目的に使用する場合、比較的早期に目づまり等を起
こし易いと共に、特に例えば空気中の酸素を分離濃縮す
るガス分離膜の支持基体として使用するような場合、分
離用担持膜（14）を均一に形成できないというような問
題があった。即ち、上記酸素分離用としては、多孔質基
体上に、例えばO2とN2の溶解速度がO2/N2≒2/1と報告さ
れているシロキサン系のポリマー単分子膜を累積、複合
化して使用するが、従来の上記エッチング箔では、エッ
チングピットの孔径が箔の表面部で大きく、しかも箔表
面に粗大な凹凸を有するため、その部分で上記単分子膜
の担持性が悪く、それを均一に形成できず欠陥となって
しまうため、分離機能が著しく損われるというような問
題があった。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention However, in the above-mentioned conventional filtration membrane, since the through-holes are formed by the etching technique such as direct current electrolysis in order to fulfill the filtration function, as shown in FIG. Inevitably, the surface of the foil (11) becomes rough, coarse irregularities (13) are formed on the surface other than the through pits (12), and the through pits (12) become enlarged portions (12a) on the surface of the foil. Can not be distorted to be formed. Therefore, when the filtration membrane is used for the purpose of separating fine particles, it is likely to cause clogging at a relatively early stage, and particularly when it is used as a supporting substrate for a gas separation membrane for separating and concentrating oxygen in the air. However, there is a problem that the separation supporting film (14) cannot be formed uniformly. That is, for the above-mentioned oxygen separation, a siloxane-based polymer monomolecular film whose dissolution rate of O 2 and N 2 is reported to be O 2 / N 2 ≈2 / 1, for example, is accumulated on a porous substrate to form a composite film. However, in the conventional etching foil, the pore size of the etching pit is large on the surface portion of the foil, and since the foil surface has coarse unevenness, the monomolecular film is poorly carried at that portion, which However, there is a problem that the separation function is significantly impaired because the defects cannot be formed uniformly.
この発明はこのような課題を解決することを目的とす
る。The present invention aims to solve such problems.
課題を解決するための手段 この発明は、純度99.9％以上の高純度アルミニウム箔に
エッチング処理を施して多数の貫通ピットを形成したの
ち、このエッチング箔に表面平滑化処理を施すことを特
徴とする濾過膜の製造方法を要旨とする。Means for Solving the Problems This invention is characterized in that a high-purity aluminum foil having a purity of 99.9% or more is subjected to etching treatment to form a large number of through pits, and then the etching foil is subjected to surface smoothing treatment. The gist is a method of manufacturing a filtration membrane.
また、上記表面平滑化処理は、電解研摩または化学研摩
の方法を用いて行うものとし、処理後のアルミニウム箔
の表面の粗さが、JIS・B0601による粗さ曲線の測定値に
おいて、基準長さ0.25mmでRmaxが0.5μｍ以下、Raが２
μｍ以下となる状態にまで行うものとすることが望まし
い。このような表面平滑性を得るためには、例えば過塩
素酸とエタノールを混合比1:4の割合に含む浴を用いて
電解研摩する場合、液温３〜10℃、電圧25〜35V、処理
時間１〜10分の処理条件で行うのが好ましい。また化学
研摩による場合、例えば硝酸とリン酸を1:15の割合で含
む混合液を用い、液温９〜100℃、処理時間１〜10分の
処理条件で行うことが好ましい。Further, the surface smoothing treatment is to be performed using a method of electrolytic polishing or chemical polishing, the surface roughness of the aluminum foil after the treatment, in the measured value of the roughness curve according to JIS B0601, the reference length 0.25 mm, Rmax is 0.5 μm or less, Ra is 2
It is desirable to carry out the process to a state where the thickness is less than μm. In order to obtain such surface smoothness, for example, when electrolytic polishing is performed using a bath containing perchloric acid and ethanol in a mixing ratio of 1: 4, the liquid temperature is 3 to 10 ° C, the voltage is 25 to 35V, and the treatment is It is preferable to carry out the treatment under the treatment conditions of 1 to 10 minutes. Further, in the case of chemical polishing, for example, it is preferable to use a mixed solution containing nitric acid and phosphoric acid in a ratio of 1:15, and perform the treatment under the treatment conditions of a liquid temperature of 9 to 100 ° C. and a treatment time of 1 to 10 minutes.
表面平滑化処理後のアルミニウム箔は、従来のエッチン
グ箔による場合と同じく、表面に陽極強化皮膜を形成し
て表面の安定化とピット径の調整をはかるものとし、所
期する濾過膜とするものである。The aluminum foil after the surface smoothing treatment shall have an anode strengthening film on the surface to stabilize the surface and adjust the pit diameter in the same way as the conventional etching foil, and shall be the intended filtration film. Is.
また、上記によって得られる濾過膜は、これをガス分離
用のものとして使用する場合、表面平滑化処理及び陽極
酸化処理を施したエッチング箔を支持基体として、更に
その表面にガス分離用担持膜を被覆形成せしめるものと
する。When the filtration membrane obtained as described above is used for gas separation, an etching foil subjected to surface smoothing treatment and anodization treatment is used as a supporting substrate, and a gas separation supporting membrane is further provided on the surface thereof. A coating should be formed.
なお、素材のアルミニウム箔として、純度99.9％以上の
高純度のものを用いるのは、電解エッチングにより形成
されるエッチングピットが箔表面に体して垂直な方向に
形成されることを保証するためであり、不純物の存在に
よって該ピットの形成が妨げられあるいは成長を妨げら
れるのを回避するためである。最も好ましくは純度99.9
9％以上のものを用いるのが良い。また、その厚さは、
0.5mm以下のものを用いるのが好適であり、特に0.1mm程
度のものを用いるのが良い。It should be noted that the high-purity aluminum foil with a purity of 99.9% or more is used as the material aluminum foil in order to ensure that the etching pits formed by electrolytic etching are formed vertically on the foil surface. This is to prevent the formation of the pits or the growth from being hindered by the presence of impurities. Most preferably 99.9
It is better to use 9% or more. Also, its thickness is
It is preferable to use one having a thickness of 0.5 mm or less, and particularly about 0.1 mm.
この発明によって得られる濾過膜を示す第１図におい
て、（１）はアルミニウム箔、（２）はエッチング処理
によって形成された多数の貫通ピット、（３）はエッチ
ング後表面平滑化処理により平滑化された箔表面（４）
に担持されたガス分離用担持膜であり、平滑表面上に担
持処理を行うものであることにより、均一に欠陥のない
担持膜が形成される状態を示している。In FIG. 1 showing a filtration membrane obtained by the present invention, (1) is an aluminum foil, (2) is a large number of through pits formed by etching, and (3) is smoothed by surface smoothing after etching. Foil surface (4)
It is a supporting film for gas separation supported on the substrate, and shows a state where a supporting film is uniformly formed without defects by carrying out the supporting treatment on a smooth surface.
発明の効果 この発明によれば、エッチングによって多数の貫通ピッ
トを高密度に形成したアルミニウム箔を、更に表面平滑
化処理することにより、微粒子分離用に使用して目ずま
り等を起こし難いものとすることができるのはもとよ
り、ガス分離用の基体に使用して表面にシロキサン系ポ
リマー単分子膜等の担持膜を担持せしめるような場合、
該担持膜に下地面の凹凸による欠陥を生じることなく均
一な皮膜に形成しうる。従って、分離性能の良好なもの
とすることができ、従来の単なるエッチング箔では実利
用できなかったガス分離膜を工業製品として実際に好適
使用可能な製品を提供できる。EFFECTS OF THE INVENTION According to the present invention, an aluminum foil having a large number of through pits formed at high density by etching is further subjected to a surface smoothing treatment so that it can be used for separating fine particles and hardly cause clogging. Not only can it be used, but when it is used as a substrate for gas separation to support a supporting film such as a siloxane polymer monomolecular film on the surface,
It is possible to form a uniform film on the supporting film without causing defects due to the unevenness of the underlying surface. Therefore, it is possible to provide a product having good separation performance, and a product in which the gas separation membrane, which could not be practically used by the conventional mere etching foil, can be practically suitably used as an industrial product.
実施例 実施例１ 99.99％アルミニウム材からなる厚さ0.1mmの焼鈍アルミ
ニウム箔を材料として用い、これを下記の条件で電解エ
ッチング処理した。Example 1 An annealed aluminum foil having a thickness of 0.1 mm and made of a 99.99% aluminum material was used as a material, and this was electrolytically etched under the following conditions.
（電解エッチング） 電解液;5wt％塩酸 液温;70℃ 電解条件;DC,15A/dm2×100秒 次いで、得られたエッチング箔に、表面平滑化処理とし
て下記の電解研摩を施した。(Electrolytic Etching) Electrolyte solution; 5 wt% hydrochloric acid solution temperature; 70 ° C. Electrolysis conditions; DC, 15 A / dm 2 × 100 seconds Then, the obtained etching foil was subjected to the following electrolytic polishing as a surface smoothing treatment.
（電解研摩） 液組成；過塩素酸：メタノール＝1:4浴 液温;5℃ 電解条件;30V×３分 次いで更に、次の条件による陽極酸化処理を施して濾過
膜の試料を得た。(Electrolytic polishing) Liquid composition; perchloric acid: methanol = 1: 4 bath liquid temperature; 5 ° C. electrolysis conditions; 30 V × 3 minutes Then, anodization treatment was performed under the following conditions to obtain a sample of a filtration membrane.
（陽極酸化処理） 電解液;3wt％酒石酸アンモン 液温;30℃ 電解条件;100V×５分 実施例２ エッチング処理後の表面平滑化処理を、下記の条件によ
る化学研摩で行うものとしたほかは実施例１と同様に処
理して濾過膜の試料を得た。(Anodic oxidation treatment) Electrolyte solution; 3 wt% ammonium tartrate Solution temperature; 30 ° C Electrolysis conditions; 100 V x 5 minutes Example 2 Except that the surface smoothing treatment after etching treatment was performed by chemical polishing under the following conditions. A sample of the filtration membrane was obtained by treating in the same manner as in Example 1.
（化学研摩） 液組成；硝酸：リン酸＝1:15浴 液温;95℃ 処理時間;2分 比較例 実施例１と同様にエッチング処理したのち、表面平滑化
処理を施すことなくそのまゝ陽極酸化処理（実施例１と
同じ）したものを試料とした。(Chemical polishing) Liquid composition: nitric acid: phosphoric acid = 1: 15 bath Liquid temperature; 95 ° C. Treatment time: 2 minutes Comparative Example After etching as in Example 1, the surface was not smoothed. A sample subjected to anodizing treatment (the same as in Example 1) was used as a sample.
上記実施例１、２及び比較例の各試料に、ポリシロキサ
ン系ポリマー単分子膜の担持処理を行い、その担持処理
性を調べると共に、気体透過装置に組込んで上記担持処
理前と処理後の各試料の気体透過特性を調べた。また、
担持膜形成前の各試料につきそれらの表面粗さをJIS・B
0601によって測定し、基準長さ0.25mmの粗さ曲線の測定
におけるRmax及びRaを調べた。それらの結果を下記第１
表に示す。Each of the samples of Examples 1 and 2 and Comparative Example was subjected to a supporting treatment of a polysiloxane-based polymer monomolecular film, and the supporting treatment property was examined, and the sample was incorporated into a gas permeation device before and after the supporting treatment. The gas permeation characteristics of each sample were investigated. Also,
The surface roughness of each sample before forming the supporting film is measured according to JIS B
Rmax and Ra in the measurement of the roughness curve having a standard length of 0.25 mm were measured by measuring by 0601. The results are shown in the first section below.
Shown in the table.
第１表に示されるように、エッチング処理後表面平滑処
理を施した実施例のエッチング箔は、該平滑処理をしな
い比較例のものに較べ表面が平滑であることから単分子
膜の担持処理性に優れ、皮膜欠陥を有しないものとなし
うると共に、その結果担持後のガス透過速度が比較例に
較べて顕著に小さいものとなり、良好な分離性能を発揮
し得られるものであることを確認し得た。 As shown in Table 1, the etching foils of the examples subjected to the surface smoothing treatment after the etching treatment had a smoother surface than those of the comparative examples which did not carry out the smoothing treatment, and therefore the monomolecular film carrying processability was improved. It was confirmed that it is possible to achieve excellent separation performance and to have no film defects, and as a result, the gas permeation rate after loading becomes significantly smaller than that of the comparative example, and that good separation performance can be exhibited. Obtained.
第１図はこの発明によって得られる濾過膜の模式断面
図、第２図は従来法による濾過膜の模式断面図である。 （１）……アルミニウム箔、（２）……貫通ピット、
（３）……担持膜。FIG. 1 is a schematic sectional view of a filtration membrane obtained by the present invention, and FIG. 2 is a schematic sectional view of a filtration membrane according to a conventional method. (1) …… Aluminum foil, (2) …… Penetration pit,
(3) ... Supporting membrane.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 長谷川 実 大阪府堺市海山町６丁224番地 昭和アル ミニウム株式会社内 (56)参考文献 特開 昭60−235609（ＪＰ，Ａ) 特開 昭61−71804（ＪＰ，Ａ) 特開 平１−63005（ＪＰ，Ａ) 特開 平１−75016（ＪＰ，Ａ) 特開 平１−262904（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Minoru Hasegawa 6-224 Kaiyamacho, Sakai City, Osaka Prefecture Showa Aluminum Co., Ltd. (56) References JP-A-60-235609 (JP, A) JP-A-61 -71804 (JP, A) JP-A-1-63005 (JP, A) JP-A-1-75016 (JP, A) JP-A-1-262904 (JP, A)
Claims (4)
エッチング処理を施して多数の貫通ピットを形成したの
ち、このエッチング箔に表面平滑化処理を施すことを特
徴とする濾過膜の製造方法。1. A method for producing a filtration membrane, which comprises subjecting a high-purity aluminum foil having a purity of 99.9% or more to an etching treatment to form a large number of through pits, and then subjecting the etching foil to a surface smoothing treatment.
摩のうちのいずれかによって行う請求項（１）に記載の
濾過膜の製造方法。2. The method for producing a filtration membrane according to claim 1, wherein the surface smoothing treatment is performed by either electrolytic polishing or chemical polishing.
箔の表面粗さが、JIS・B0601による粗さ曲線の測定値に
おいて、基準長さ0.25mmでRmaxが5.0μｍ以下、Raが２
μｍ以下となる状態に行う請求項（１）または（２）に
記載の濾過膜の製造方法。3. The surface smoothing treatment is such that the surface roughness of the treated aluminum foil is a standard length of 0.25 mm, Rmax is 5.0 μm or less, and Ra is 2 in the measured value of the roughness curve according to JIS B0601.
The method for producing a filtration membrane according to claim (1) or (2), wherein the method is performed in a state of being not more than μm.
し、更にその表面にガス分離用担持膜を被覆形成する請
求項（１）ないし（３）いずれか１に記載の濾過膜の製
造方法。4. The production of a filtration membrane according to any one of claims (1) to (3), wherein the filtration membrane according to claim (1) is used as a supporting substrate, and a supporting membrane for gas separation is formed on the surface of the support membrane. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9049788A JPH07112532B2 (en) | 1988-04-13 | 1988-04-13 | Method for manufacturing filtration membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9049788A JPH07112532B2 (en) | 1988-04-13 | 1988-04-13 | Method for manufacturing filtration membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01262903A JPH01262903A (en) | 1989-10-19 |
| JPH07112532B2 true JPH07112532B2 (en) | 1995-12-06 |
Family
ID=14000141
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9049788A Expired - Lifetime JPH07112532B2 (en) | 1988-04-13 | 1988-04-13 | Method for manufacturing filtration membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07112532B2 (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL9401260A (en) * | 1993-11-12 | 1995-06-01 | Cornelis Johannes Maria Van Ri | Membrane for microfiltration, ultrafiltration, gas separation and catalysis, method for manufacturing such a membrane, mold for manufacturing such a membrane, as well as various separation systems comprising such a membrane. |
| US6547858B1 (en) | 1999-03-22 | 2003-04-15 | Idatech, Llc | Hydrogen-permeable metal membrane and hydrogen purification assemblies containing the same |
| US6152995A (en) | 1999-03-22 | 2000-11-28 | Idatech Llc | Hydrogen-permeable metal membrane and method for producing the same |
| US6319306B1 (en) | 2000-03-23 | 2001-11-20 | Idatech, Llc | Hydrogen-selective metal membrane modules and method of forming the same |
| US6183542B1 (en) * | 1998-11-09 | 2001-02-06 | Peter R. Bossard | Method and apparatus for purifying hydrogen |
| DE19983751B4 (en) * | 1998-11-10 | 2008-04-17 | ATI Properties, Inc., Gardena | Hydrogen Segregation membrane |
| US6602325B1 (en) | 1999-10-21 | 2003-08-05 | Ati Properties, Inc. | Fluid separation assembly |
| US6419726B1 (en) | 1999-10-21 | 2002-07-16 | Ati Properties, Inc. | Fluid separation assembly and fluid separation module |
| US6475268B2 (en) * | 2000-12-22 | 2002-11-05 | Ford Global Technologies, Inc. | Supported membrane for hydrogen separation |
| US7247210B2 (en) | 2004-02-23 | 2007-07-24 | Ecolab Inc. | Methods for treating CIP equipment and equipment for treating CIP equipment |
| US7220358B2 (en) | 2004-02-23 | 2007-05-22 | Ecolab Inc. | Methods for treating membranes and separation facilities and membrane treatment composition |
| US7392811B2 (en) | 2004-02-23 | 2008-07-01 | Ecolab Inc. | Delivery head for multiple phase treatment composition, vessel including a delivery head, and method for treating a vessel interior surface |
| JP2010058076A (en) * | 2008-09-05 | 2010-03-18 | Panasonic Corp | Metallic filter and electric cleaner employing the same |
| US10476093B2 (en) | 2016-04-15 | 2019-11-12 | Chung-Hsin Electric & Machinery Mfg. Corp. | Membrane modules for hydrogen separation and fuel processors and fuel cell systems including the same |
| US11712655B2 (en) | 2020-11-30 | 2023-08-01 | H2 Powertech, Llc | Membrane-based hydrogen purifiers |
-
1988
- 1988-04-13 JP JP9049788A patent/JPH07112532B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01262903A (en) | 1989-10-19 |
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