JPH0568553B2 - - Google Patents
Info
- Publication number
- JPH0568553B2 JPH0568553B2 JP61249543A JP24954386A JPH0568553B2 JP H0568553 B2 JPH0568553 B2 JP H0568553B2 JP 61249543 A JP61249543 A JP 61249543A JP 24954386 A JP24954386 A JP 24954386A JP H0568553 B2 JPH0568553 B2 JP H0568553B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- substrate
- film
- glass
- filler
- 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
- 239000010409 thin film Substances 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 23
- 239000011148 porous material Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 16
- 239000005373 porous glass Substances 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229940057995 liquid paraffin Drugs 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001298 alcohols Chemical group 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000005295 porous vycor glass Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006268 silicone film Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0069—Inorganic membrane manufacture by deposition from the liquid phase, e.g. electrochemical deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/0213—Silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
- B01D2323/081—Heating
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Surface Treatment Of Glass (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】
［発明の目的］
（産業上の利用分野）
本発明は多孔質体表面開孔部を覆つて薄膜を形
成させる方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a method of forming a thin film to cover the openings on the surface of a porous body.
（従来の技術）
Pd膜、Ni膜、シリコーンゴム膜、ポリイミド
膜等の薄膜は水素分離、酸素富化等の各種用途に
使用される。従来法にあつては、予め所定厚みの
薄膜を製造し、この薄膜を支持枠等で支持して使
用する。薄膜には、このような枠体への取付方
法、支持方法に耐えるだけの機械的強度を附与す
る必要があり、あまり薄い膜を使用すると枠体へ
の取付工程或は使用中に破損し易い。又薄膜の厚
みには製造工程上の制約もあり、あまり厚みの小
さいものは実用化されていない。(Prior Art) Thin membranes such as Pd membranes, Ni membranes, silicone rubber membranes, and polyimide membranes are used for various purposes such as hydrogen separation and oxygen enrichment. In the conventional method, a thin film of a predetermined thickness is manufactured in advance, and this thin film is supported by a support frame or the like for use. It is necessary to give the thin film enough mechanical strength to withstand such attachment and support methods to the frame; if the membrane is too thin, it may be damaged during the process of attaching it to the frame or during use. easy. Furthermore, there are restrictions on the thickness of the thin film due to the manufacturing process, and thin films have not been put into practical use.
薄膜を支持枠で支持して使用する場合、支持枠
開孔部のデイメンシヨンが小さい程、厚みの小さ
い膜を使用することが可能となる筈である。又支
持枠開孔部を覆つて直接薄膜を形成させることが
できれば、薄膜を枠体に取付ける際の破損も生ず
ることがなく、薄い膜を使用することが可能とな
る理である。しかし乍ら、このような技術的命題
を解決する方法は知られておらず、膜厚が大きく
なると性能が低下する場合でも、止むを得ず、厚
い膜を使用せざるを得なかつた。 When using a thin film supported by a support frame, the smaller the dimension of the opening of the support frame, the smaller the thickness of the film can be used. Furthermore, if a thin film can be directly formed to cover the support frame opening, there will be no damage when attaching the thin film to the frame, making it possible to use a thin film. However, there is no known method to solve such a technical problem, and even if the performance deteriorates as the film thickness increases, thick films have been unavoidably used.
（発明が解決しようとする問題点）
本発明は従来技術が有していた前述の問題点を
解決し、従来知られていなかつた枠体の開孔部を
覆つて直接薄膜を形成する方法を新規に提供する
ことを目的とするものである。(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems that the prior art had, and provides a method of directly forming a thin film to cover the opening of the frame, which has not been known in the past. The purpose is to provide new information.
［発明の構成］
（問題点を解決するための手段）
本発明は前述の問題点を解決すべくなされたも
のであり、表面に開孔する多数の小孔を有する基
体の該小孔開孔部に充填材を充填し、次いで基体
表面に薄膜を被着せしめた後充填材を除去するこ
とを特徴とする多孔質体表面開孔部を覆つて薄膜
を形成させる方法を提供するものである。[Structure of the Invention] (Means for Solving the Problems) The present invention has been made to solve the above-mentioned problems. The present invention provides a method for forming a thin film covering the openings on the surface of a porous body, which method comprises filling the openings on the surface of a porous body with a filler, then depositing the thin film on the surface of the substrate, and then removing the filler. .
本発明においては、表面に開孔する多数の小孔
を有する多孔質体を使用する。このような多孔質
体としてはAl2O3等のセラミツクス微粒の焼結
体、金属微粒の焼結体、多孔質硝子が例示される
が、多孔質硝子を使用するのが好ましい。 In the present invention, a porous body having a large number of small pores on its surface is used. Examples of such a porous body include a sintered body of fine ceramic particles such as Al 2 O 3 , a sintered body of fine metal particles, and porous glass, but it is preferable to use porous glass.
多孔質硝子としてはバイコール硝子、或は
SiO245〜70wt％、B2O38〜30wt％、CaO8〜25wt
％、Al2O35〜15wt％、Na2O3〜８％、K2O1〜５
％、Na2O＋K2O4〜13wt％、MgO0〜8wt％なる
組成を有する硝子（以下硝子Ａという）又は
SiO245〜70wt％、B2O38〜30wt％、CaO8〜25wt
％、Al2O35〜15％なる組成を有する硝子（以下
硝子Ｂという）を熱処理してB2O3、CaOを主体
とする相を分相せしめ、この相を溶解除去するこ
とによつて得られる多孔質硝子（以下、多孔質硝
子Ａ又はＢと呼ぶ）が特に適当である。 As the porous glass, Vycor glass or
SiO2 45~70wt%, B2O3 8 ~30wt%, CaO8~25wt
%, Al2O3 5 ~15wt%, Na2O3 ~8%, K2O1 ~ 5
%, Na2O + K2O4 ~13wt%, MgO0~8wt% (hereinafter referred to as glass A) or
SiO2 45~70wt%, B2O3 8 ~30wt%, CaO8~25wt
%, Al 2 O 3 5-15% (hereinafter referred to as glass B) is heat-treated to separate a phase mainly composed of B 2 O 3 and CaO, and this phase is dissolved and removed. The porous glass obtained in this manner (hereinafter referred to as porous glass A or B) is particularly suitable.
上述した組成を有する硝子Ａ又はＢの上記成分
のうちSiO2は分相、除去工程によつて得られる
多孔硝子の骨格を形成するための記幹成分であ
り、Al2O3は補助成分として得られた多孔硝子の
脆さを減少させる作用を有する。B2O3は一方に
おいて多孔硝子の骨格を形成する補助成分として
機能するが、他方CaOと協同して、熱処理によつ
て微少な分相を生成する作用を有する。そしてこ
のようにして生成したCaO、B2O3を主成分とす
る分相を溶解除去することによつて多孔質硝子が
形成される。 Among the above-mentioned components of glass A or B having the above-mentioned composition, SiO 2 is the key component for forming the skeleton of the porous glass obtained by the phase separation and removal process, and Al 2 O 3 is used as an auxiliary component. It has the effect of reducing the brittleness of the obtained porous glass. On the one hand, B 2 O 3 functions as an auxiliary component that forms the framework of the porous glass, but on the other hand, in cooperation with CaO, it has the effect of producing minute phase separation through heat treatment. Then, porous glass is formed by dissolving and removing the thus generated separated phase mainly composed of CaO and B 2 O 3 .
B2O3は上述の説明からも首肯しうるように小
孔の大きさを決定する重要な因子であり、分相中
に移行して除去されるB2O3量、或は逆に多孔硝
子中に残存するB2O3量は、小孔の径の均一性と
密接な関係を有することが判明した。 As can be agreed from the above explanation, B 2 O 3 is an important factor that determines the size of small pores, and the amount of B 2 O 3 transferred and removed during phase separation, or conversely, the size of pores It was found that the amount of B 2 O 3 remaining in the glass has a close relationship with the uniformity of the pore diameter.
上記成分を前述の範囲内に保つことにより好適
な多孔質体をうることができる。 A suitable porous body can be obtained by keeping the above components within the above ranges.
硝子Ａ、Ｂを所定形状に成型した後熱処理して
CaO、B2O3を主体とする相（以下CaO、B2O3相
という）を分相せしめる。加熱処理温度が高い
程、又熱処理時間が長い程CaO、B2O3相は大き
くなり、従つて得られる多孔硝子の小孔の径は大
きくなる傾向を有し、熱処理条件を選択すること
によつて小孔の径を40〜100000Åの範囲所望の値
とすることができる。このようにして得られた多
孔質硝子は、小孔の径は均一であり、本発明の目
的を達成するのに極めて好適なものである。 Glasses A and B are formed into a predetermined shape and then heat treated.
A phase mainly composed of CaO and B 2 O 3 (hereinafter referred to as CaO and B 2 O 3 phase) is phase-separated. The higher the heat treatment temperature and the longer the heat treatment time, the larger the three phases of CaO and B 2 O, and therefore the diameter of the small pores in the resulting porous glass tends to become larger. Therefore, the diameter of the small pores can be set to a desired value in the range of 40 to 100,000 Å. The porous glass thus obtained has small pores of uniform diameter and is extremely suitable for achieving the object of the present invention.
加熱処理を行つた硝子をHCl、H2SO4、HNO3
等の酸中に浸漬してCaO、B2O3相を溶解除去す
る。なお酸処理を行なうに先立ち、HF溶液で短
時間その表面をエツチング処理するのが望まし
い。 Heat-treated glass is treated with HCl, H 2 SO 4 , HNO 3
etc. to dissolve and remove the three phases of CaO and B 2 O. Note that prior to acid treatment, it is desirable to etching the surface for a short time with an HF solution.
前述したように熱処理の条件によつて、得られ
る多孔硝子の小孔の径を制御することができる
が、小孔の径は多孔質硝子中に残存するB2O3の
量に応じて変化すること及びこのB2O3の量は熱
処理、酸処理の条件によつて左右されることが判
明した。そしてB2O3が望ましく0.5wt％以上残存
するようこれらの条件を定めることにより特に好
適な結果の得られることが判明した。 As mentioned above, the diameter of the small pores in the resulting porous glass can be controlled by the heat treatment conditions, but the diameter of the small pores changes depending on the amount of B 2 O 3 remaining in the porous glass. It has been found that the amount of B 2 O 3 depends on the conditions of heat treatment and acid treatment. It has been found that particularly favorable results can be obtained by setting these conditions so that B 2 O 3 desirably remains in an amount of 0.5 wt % or more.
望ましい処理条件は次の通りである。 Desirable processing conditions are as follows.
加熱温度 600〜850℃
加熱時間 ２〜48hr、望ましくは12〜24hr
酸の種類 Hcl、H2SO4、HNO3
酸の濃度0.01〜2.0N、望ましくは0.1〜1.0N
処理時間 ２〜20hr、望ましくは４〜16hr
温 度 50〜95℃、望ましくは80〜90℃
本発明においては、所定形状に形成した多孔質
体を基体として使用する。このような基体は例え
ば所定形状に成型した原料硝子に分相処理、溶解
処理を施こすことによつて得ることができる。Heating temperature 600-850℃ Heating time 2-48hr, preferably 12-24hr Type of acid Hcl, H 2 SO 4 , HNO Concentration of 3 acids 0.01-2.0N, preferably 0.1-1.0N Treatment time 2-20hr, preferably 4 to 16 hours Temperature 50 to 95°C, preferably 80 to 90°C In the present invention, a porous body formed into a predetermined shape is used as the substrate. Such a substrate can be obtained, for example, by subjecting raw material glass molded into a predetermined shape to phase separation treatment and dissolution treatment.
基体の小孔開孔部に充填材を充填し、小孔を閉
塞し、この状態で基体表面に薄膜を被着せしめる
ことにより、基体開孔部を覆つて薄膜を形成さ
せ、次いで充填材を除去することにより、多孔質
体開孔部を支持枠とした薄膜を形成させることが
できる。多孔質体の開口部の大きさは極めて小さ
く直径40〜10000Å程度とすることができ、薄膜
はこの開孔部を覆つて直接形成されるので、本発
明の方法によるときは、0.5μ程度の薄膜を破損の
恐れなく製造、使用することが可能となつた。 A filler is filled into the small pores of the substrate to close the pores, and in this state a thin film is applied to the surface of the substrate to form a thin film covering the substrate openings, and then the filler is applied. By removing it, a thin film can be formed using the porous body openings as a support frame. The size of the openings in the porous body is extremely small and can be approximately 40 to 10,000 Å in diameter, and the thin film is formed directly covering these openings, so when the method of the present invention is used, It has become possible to manufacture and use thin films without fear of damage.
充填材としてはパラフイン、低融点合金、
CMC（カルボキシメチルセルローズ）、澱粉等を
用いることができる。これらの充填材は溶融或は
溶解して液状として使用し、小孔中に充填した
後、冷却或は溶媒の蒸発等の手段により望ましく
は固化せしめる。 Fillers include paraffin, low melting point alloys,
CMC (carboxymethyl cellulose), starch, etc. can be used. These fillers are melted or dissolved and used in a liquid state, and after being filled into the small holes, they are desirably solidified by means such as cooling or evaporation of the solvent.
小孔に充填する手段に特に限定はないが、基体
の一方の側を減圧状態として、上記のような充填
材を含む液体を基体の他方の側に接触させて吸引
する方法、或は基体を容器中に収納し、容器を真
空源と接続して基体の小孔中に含まれる空気を充
分脱気し、次いで容器中に充填材を含む液体を注
入する等の方法を用いることができる。 There are no particular limitations on the means for filling the small pores, but there may be a method in which one side of the substrate is under reduced pressure and a liquid containing the filler as described above is brought into contact with the other side of the substrate and sucked, or A method can be used, such as storing the substrate in a container, connecting the container to a vacuum source to sufficiently remove air contained in the small pores of the substrate, and then injecting a liquid containing the filler into the container.
小孔を閉塞した基体上に薄膜を形成させる。こ
の際基体の開孔部以外の表面部分に附着している
充填材は、予め充分除去するのが適当である。 A thin film is formed on the substrate with the small pores closed. At this time, it is appropriate to sufficiently remove the filler adhering to the surface portions of the substrate other than the openings in advance.
薄膜の種類及び形成方法には特に限定はなく、
形成方法としては化学メツキ法、気相法、スパツ
タリング法、真空蒸着法、塗布法等の公知の方法
を、又薄膜としては金属膜、セラミツクス膜、プ
ラスチツク膜、ゴム膜、シリコーン膜等を例示す
ることができ、0.5〜50μ程度の薄膜を形成させる
ことができる。なお充填材は、薄膜を形成する
際、薄膜を形成すべき材料が、小孔中に侵入する
のを防止し、該材料を支持する作用を有するもの
であれば足り、必ずしも固体である必要はなく、
流動パラフイン、寒天、水銀、比較的粘稠な澱粉
糊等を用いることも可能である。 There are no particular limitations on the type of thin film or the method of forming it.
As the formation method, known methods such as chemical plating method, vapor phase method, sputtering method, vacuum evaporation method, and coating method are used, and as the thin film, metal film, ceramic film, plastic film, rubber film, silicone film, etc. are exemplified. It is possible to form a thin film of about 0.5 to 50μ. Note that the filler does not necessarily have to be solid, as long as it has the function of preventing the material from which the thin film is to be formed from entering the pores and supporting the material when forming the thin film. Without,
It is also possible to use liquid paraffin, agar, mercury, relatively viscous starch paste, and the like.
又或る種の液体も充填材として機能することが
判明した。例えば［Pd（NH3）4］Cl2を用いて化
学メツキ法によつてPd膜を形成させる際、低級
アルコールが有効に機能することが判明した。 It has also been found that certain liquids also function as fillers. For example, it has been found that lower alcohols function effectively when forming a Pd film by chemical plating using [Pd(NH 3 ) 4 ]Cl 2 .
その作用については明らかではないが、［Pd
（NH3）4］Cl2は低級アルコールに溶解性を有しな
いため、低級アルコールを充填した基体に［Pd
（NH3）4］Cl2溶液を接触せしめると、界面におい
て［Pd（NH3）4］Cl2が折出することも一因と考
えられる。 Although its effect is not clear, [Pd
(NH 3 ) 4 ]Cl 2 has no solubility in lower alcohols, so [Pd
One possible reason is that [Pd(NH 3 ) 4 ]Cl 2 is precipitated at the interface when a (NH 3 ) 4 ]Cl 2 solution is brought into contact with the solution.
薄膜を形成させた後、充填材を除去する。除去
手段に特に限定はなく、加熱溶融蒸発、物理的又
は化学的溶解或は化学分解等の手段を例示するこ
とができる。例えばパラフイン、低融点合金は加
熱溶融、或は物理的又は化学的溶解によつて、澱
粉質充填材は酵素を用いて分解することにより除
去することができる。 After forming the thin film, the filler is removed. There is no particular limitation on the removal means, and examples include means such as heating melting and evaporation, physical or chemical dissolution, and chemical decomposition. For example, paraffin and low melting point alloys can be removed by heat melting or physical or chemical dissolution, and starchy fillers can be removed by decomposing them using enzymes.
本発明薄膜は各種用途に使用することができ
る。 The thin film of the present invention can be used for various purposes.
例えば多孔質硝子を基体として用いてPd膜を
形成させ、水素分離用媒体として用いることがで
きる。又Al2O3粒焼結体を基体として用い、極め
て微少な小孔を有するセラミツク薄膜を形成さ
せ、或は金属膜を形成させ、フイルターとして用
いることもできる。 For example, a Pd film can be formed using porous glass as a substrate and used as a hydrogen separation medium. It is also possible to use the Al 2 O 3- grain sintered body as a substrate to form a ceramic thin film having extremely small pores, or to form a metal film and use it as a filter.
（作用）
基体小孔開口部に充填された充填材が、基体表
面に薄膜を形成させる際の支持体として機能し、
小孔開口部を覆つて薄膜が形成され、開口部が薄
膜の支持枠として機能する。(Function) The filler filled in the opening of the small pores of the substrate functions as a support when forming a thin film on the surface of the substrate,
A membrane is formed over the stoma opening, with the opening serving as a support frame for the membrane.
（実施例）
平均5000Åの多数の小孔を有する、Al2O3焼結
体よりなる仮状体（厚み10mm、大きさ10cm×10
cm）を基体として使用した。(Example) A temporary body made of Al 2 O 3 sintered body (thickness 10 mm, size 10 cm x 10
cm) was used as the substrate.
この基体を容器中に収納して脱気し、該容器中
に流動パラフインを注入し、基体の開口部を流動
パラフインで充填した。表面に付着したパラフイ
ンを充分除去し、その一面に銀鏡反応を利用し、
厚さ２〜3μのAg膜を形成させ、次いで基体をで
充分洗滌し、充填されたパラフインを除去するこ
とによりAl2O3焼結体の開口部を覆つて厚さ２〜
3μのAg薄膜を形成させた。 This substrate was placed in a container and degassed, and liquid paraffin was poured into the container to fill the opening of the substrate with liquid paraffin. The paraffin attached to the surface is thoroughly removed, and a silver mirror reaction is applied to the entire surface.
An Ag film with a thickness of 2 to 3 μm is formed, and then the substrate is thoroughly washed with water to remove the filled paraffin, thereby covering the opening of the Al 2 O 3 sintered body and forming an Ag film with a thickness of 2 to 3 μm.
A 3 μm Ag thin film was formed.
実施例 ２
平均40Åの多数の小孔を有するバイコール硝子
よりなる実施例１ど同一の大きさの板状体を基体
として使用した。Example 2 A plate-shaped body made of Vycor glass having a large number of pores with an average size of 40 Å and having the same size as in Example 1 was used as a substrate.
実施例１と同様の手段により開口部に低融点合
金を充填し、スパツタリング法により厚み
0.5μAu膜を形成させた。 The opening was filled with a low melting point alloy by the same means as in Example 1, and the thickness was reduced by sputtering.
A 0.5μAu film was formed.
充填された合金を酸処理によつて除去し、バイ
コール硝子の開口部を覆つて厚さ0.5μのAu製薄
膜を形成させた。 The filled alloy was removed by acid treatment, and a thin Au film with a thickness of 0.5 μm was formed to cover the opening of the Vycor glass.
Claims (1)
小孔開孔部に充填材を充填し、次いで基体表面に
薄膜を被着せしめた後充填材を除去することを特
徴とする多孔質体表面開孔部を覆つて薄膜を形成
させる方法。 ２ 多孔質体は多孔質硝子であることを特徴とす
る特許請求の範囲第１項記載の薄膜を形成させる
方法。 ３ 小孔の大きさは40〜100000Åであることを特
徴とする特許請求の範囲第１項又は第２項記載の
薄膜を形成させる方法。[Scope of Claims] 1. Filling the small pores of a substrate having a large number of small holes on the surface with a filler, then depositing a thin film on the surface of the substrate, and then removing the filler. A method for forming a thin film covering the openings on the surface of a porous body, characterized by: 2. The method for forming a thin film according to claim 1, wherein the porous body is porous glass. 3. The method for forming a thin film according to claim 1 or 2, characterized in that the size of the small pores is 40 to 100,000 Å.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61249543A JPS63105977A (en) | 1986-10-22 | 1986-10-22 | Method for forming thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61249543A JPS63105977A (en) | 1986-10-22 | 1986-10-22 | Method for forming thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63105977A JPS63105977A (en) | 1988-05-11 |
| JPH0568553B2 true JPH0568553B2 (en) | 1993-09-29 |
Family
ID=17194552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61249543A Granted JPS63105977A (en) | 1986-10-22 | 1986-10-22 | Method for forming thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63105977A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9073053B2 (en) | 1999-05-28 | 2015-07-07 | Cepheid | Apparatus and method for cell disruption |
| US9789481B2 (en) | 1999-05-28 | 2017-10-17 | Cepheid | Device for extracting nucleic acid from a sample |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327942C (en) | 2004-01-09 | 2007-07-25 | 中国科学院大连化学物理研究所 | Composite metal palladium membrane or alloy palladium membrane and its preparing method |
| JP2008018387A (en) * | 2006-07-14 | 2008-01-31 | Ngk Insulators Ltd | Method for applying seed crystal to porous base material |
-
1986
- 1986-10-22 JP JP61249543A patent/JPS63105977A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9073053B2 (en) | 1999-05-28 | 2015-07-07 | Cepheid | Apparatus and method for cell disruption |
| US9789481B2 (en) | 1999-05-28 | 2017-10-17 | Cepheid | Device for extracting nucleic acid from a sample |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63105977A (en) | 1988-05-11 |
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