1299287 九、發明說明： 【發明所屬之技術領域】 本發明係關於-種賴裝置，侧涉及-種奈米級篩網及其製造方法。 【先前技術】 目前，奈米技術之生產與細齡越肤，而在衫奈米粉體的應用上， 往往要求粉體雑之-雌。相奈練體之製造方法有化學還原法、氣相沈 積法、溶膠凝膠法等，由於反應條件影響及反應過程難以控制，使這些方法並 不能獲得粒徑單-之奈米粉體，因而需借助於其他方法，如通過轉由上述方 法所製備之奈米粉體產物，只要使篩網之網孔直徑一致即可篩選粒徑一致之奈 米粉體。 凊參閱第-圖’為習知篩網結構示意圖。該筛賴包括_底盤2以及由底盤 周緣向上延伸之侧壁3。底盤2包括-位於中央之網格狀篩盤4以及與該筛盤4 周緣相接合之周盤5。此傳統筛網1採用網格狀_盤4，僅能對宏觀粉末微粒進 行篩選，而對於奈米級粉體，該習知篩網不適用，必須採用一些具有奈米 級多孔結構材料之筛網。 2〇〇2年2月28日公開之中國大陸第〇211〇938.9號專利揭露一種以錳結核、 富鈷結殼為原料合成鋇鈣猛礦型分子篩之方法。利用新鮮錳結核或富鈷結殼與 氧化劑反應，以提高原料中錳元素之氧化態；然後將鎂離子植入錳礦物晶格， 使其發揮模板劑作用；經過高溫水熱反應，原料中各種鐵錳氧化物、氫氧化物 均轉變成鋇鈣鐘礦型分子篩。該方法所得分子篩具有3χ3型隧道孔結構，篩孔 直徑約0·69奈米，該奈米篩膜孔徑小，可廣泛應用於化工催化、環境工程、高 性能電池等領域。惟其孔徑太小且過於單一，不能滿足不同孔徑需求之奈米級 1299287 篩網。 2001年2月28日公開之中國大陸第〇麵_號專利申請揭露一種奈米筛 膜’其包括陶莞材料支撐體及在該支撑體上燒結而得之卜Mn〇2奈米筛膜。陶 竟支撐體具有微綠航，篩解職徑為2〜3脑，卜Mn⑽始粒徑為 2㈣臟’聚集粒徑為·韻^，膜層厚度為1〇〜15微米。反應器用陶究支 撐體將7擺02奈米篩賴隔為兩個空間，塗覆卜奈米篩膜—面係催化 反應區’另-面侧放式負壓區。該奈米篩膜孔徑較小，有利於負載催化劑粒 子’提高催化性能。惟其孔_由分子之_形成，因而細面積相對於整個 奈米篩膜之面積較小，即·輪小，不能充分_其有效面積，造成該奈米 篩膜篩選速率降低，過渡效率低下。 有鑑於此，提供-種有效利用面積冑、篩選效率高之奈米筛網及其製造方 法實為必要。 【内容】 為克服先前技術中奈米篩網有效利用面積低下、篩選效率低等不足，本發 明之目的在於提供-種有效彻面躺、_鱗高之奈米筛網。 本發明之另一目的在於提供上述奈米篩網之製造方法。 為實現上述第-目的，本發明提供-種奈料網，其包括_薄膜及用於固 持該薄膜之底盤，該底盤周緣形成有側壁；其中，該薄膜包括具有方向性規則 排列之奈米滤孔結構之氧化紹膜。 而且，其中所述薄膜採用陽極氧化銘膜，所述奈米濾孔之間相互平行且基 本垂直於所述薄絲面’所述奈錢孔按六邊形分佈侧，所述奈米濾孔之孔 1299287 .徑範圍為5奈米〜爾米，所述奈米纽之開孔率在舻娜咖2以上，所述 薄膜厚度範圍1〇奈米〜1〇〇奈米。 為實現上述第二目的，本發明提供上述奈米_之觀方法，其包括以下 步驟： 提供一具有平滑表面之鋁基材； 於所述平滑表面形成具有方向性規則排列之奈米濾孔結構之氧化銘薄膜，· 去除鋁基材，獲得自支撐氧化鋁薄膜，· 使氧化銘薄膜固持於-具周緣侧壁之底盤中央位置，構成奈米筛網。 其中’所述薄膜形成方法採用陽極氧化法，所述陽極氧化法之電解液採用 硫酸、草酸、顧、職雜驗，所雜紐細贼齡金，所述銘基 材採用侧法去除，所義刻法所採祕刻液各组份及其質量分數對應為：鱗 酸：乙酸··硝酸：水=72%: 15%: 8%: 5%，所述奈米滤孔之間相互平行且 基本垂直於所_膜表面，所述奈米濾孔按六邊形分佈排列，所述奈米濾孔之 孔徑乾圍為5奈米〜4GG奈米’所述奈米濾孔之開孔率在1()11個/咖2以上，所 述薄膜形碰it-步對其蹄表面處理、祕理或航處理。 丨 &與先前之奈米篩網相比’本發明提供之奈米篩罐用具有奈米滤孔結構之 氧她薄膜，該義可通過碰電絲_其孔關距，以餅_分佈且按 疋方向I·生規則排列奈米濾孔之薄膜，使薄膜有效糊面積高並加快奈米筛 網之篩選速率，提高其篩選效率。 【實施方式】 下面結合附圖對本發明作進一步詳細說明。 請參閱第二圖，本發明提供之奈米篩網1〇包括一薄膜u、用於固持該薄 1299287 膜之底盤12以及形成於底盤12周緣之側壁13。其中，底盤12係中央為空之 底座，從而可使薄膜11固持於底盤12中央部位。側壁13具有一定高度，以 盛裝-定量待_之粉末(®未示）。_ U係—種多紐氧她薄膜，在其 厚度方向形成有按一定方向規則排列之奈米濾孔14。 請參閱第三圖’為奈米篩網10中薄膜u之表面結構放大示意圖。薄膜 11由許多具有六面柱體狀之晶胞15組成(如目中虛線所示)，每個晶胞Η中央 包含-個_孔狀奈械孔14，每個晶胞15關按六邊形排佈有六個與其相 同之晶胞’即各晶胞所含濾孔之中心連線為一六邊形(如圖中實線所示）。其馨 中，奈米渡孔14為-貫穿義U且垂直於其表面之圓柱通孔奈米遽孔μ 之間相互平行、尺寸_，且按六邊形分佈制'上述奈錢孔Μ之結構可 採用陽極氧化法製得，並通過控制陽極氧化的製備條件，如調節氧化電壓、時 間等製備條件，即可獲得各種尺寸之奈米攄孔14，通常在5奈米〜·奈米範 圍内’深度約為1〇奈米〜100奈米，等同於薄膜u之厚度，奈米濾孔Μ之開 孔率至少為1011個/cm2。 、本發明提供之奈料網1()可根據需要贱選擇與待雜粉末顆粒相同尺_ 寸之奈米濾孔W，從而可篩選出粒徑均勻一致之奈米顆粒。篩選時可配合其 ;、震動裝置如超聲波震綠等—起制，必要時還可採贈水猶之方法筛選 ;刀末由於奈米濾孔w密集分佈且按_定方向性規則排列，使薄膜11有效利 用面2高’並加快奈米篩網10之筛選速率，最終提高奈米篩網10之筛選效率。 叫參，第四圖’為奈米_1G之製造過程示意圖，其包括以下步驟： (1)提供-織材16，其具有_平滑表面17 :選取-舰度較高之平整 1299287 ^㈣(也働鄉並物峨理，如蝴、表峨脂處理及電 千峨料，贿預蝴膜之表蝴—平整光滑之平滑表面17，以 利於進行對其陽極氧化處理。 (2)於_ 16表面形成竭她14結構之氧化罐u ••在硫 酸、卓酸、魏、絡酸或其混合酸等酸性電解液帽織材μ進行陽極氧化， 使其平滑表面17_錄倾_1。域射_自-致，分佈均句之 奈米渡孔14’可去除薄助之複上觸極氧化綠進行二次陽極氧化， 最終可獲__狀奈趣L14結構之_u，^且綱孔μ相 互平行’由薄膜-表面延伸至另一表面。陸梅等人在《蘭州大學學報》（自然 科學版)，2〇〇2,38(4)，47_54，“多孔氧化銘膜的製備及其表徵，，一文中指出， 多孔氧化賴之關距及雜均隨所加氧化電壓的增加而增加。因而，可曰利用 電壓與孔隙間隔大小之正比關係，調整電縣控制孔隙間距，以調節奈米據孔 14之分佈狀況，因而，可獲得密集分佈奈米據孔14之薄膜n，使薄膜^ 有較高有效·面積。_通過控觸極氧化條件，如電解液種類、氧化電壓 溫度、時_及·贿等赚，可獲料·歡奈錢孔14，通常在$ 奈米〜400奈米之間。如當以硫酸為電解液時，所得奈米遽孔14之孔徑較小， 通常在20奈米左右;而以草酸為電解液時，所得奈米觀14之孔控較大，通 常在40奈米以上。 ⑶去除銘基材，獲得自支樓氧化銘薄膜u :去除銘基材ΐό之方法可 採用蝕刻法，以混合酸為蝕刻液’該混合酸中各種酸組份及其所含質量分數對 應為：魏：乙酸：補酸：水=72% : 15% : 8% : 5%。餘刻去除紹基材Μ之 12992871299287 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a seeding device, and a side relates to a nanometer-sized screen and a method of manufacturing the same. [Prior Art] At present, the production of nanotechnology is the skin of the skin, and in the application of the nanofiber, the powder is often required to be female. The manufacturing methods of the lysine are chemical reduction method, vapor deposition method, sol-gel method, etc. Due to the influence of reaction conditions and the difficulty in controlling the reaction process, these methods cannot obtain the particle size of the single-nano powder, and thus By means of other methods, such as by transferring the nano-powder product prepared by the above method, the nano-sized powder having the same particle diameter can be screened by making the mesh diameter of the sieve uniform.凊 Refer to the figure-' is a schematic diagram of the conventional screen structure. The screen includes a chassis 2 and a side wall 3 extending upward from the periphery of the chassis. The chassis 2 includes a centrally located grid-like sieve tray 4 and a peripheral disk 5 joined to the periphery of the sieve tray 4. The conventional screen 1 adopts a grid-like disc 4, which can only screen macroscopic powder particles, while for nano-scale powders, the conventional screen is not suitable, and some sieves having a nano-scale porous structural material must be used. network. The Chinese Patent No. 211〇938.9 published on February 28, 2002 discloses a method for synthesizing strontium-calcium ore-type molecular sieves from manganese nodules and cobalt-rich crusts. The fresh manganese tuberculosis or the cobalt-rich crust is reacted with the oxidant to increase the oxidation state of the manganese element in the raw material; then the magnesium ion is implanted into the manganese mineral crystal lattice to act as a template; after high temperature hydrothermal reaction, various materials in the raw material Iron and manganese oxides and hydroxides are all converted into strontium calcium bell-type molecular sieves. The molecular sieve obtained by the method has a 3χ3 type tunnel pore structure, and the mesh diameter is about 0·69 nm. The nano sieve membrane has a small pore size and can be widely used in chemical catalysis, environmental engineering, high performance batteries and the like. However, the pore size is too small and too single to meet the nanometer 1299287 screen with different pore size requirements. The Chinese Patent Application No. PCT application published on Feb. 28, 2001 discloses a nano sieving film which comprises a ceramic material support and a Mn 〇 2 nano sieving film which is sintered on the support. The ceramic support has a micro green flight, the sieving service is 2~3 brain, the Mn(10) particle size is 2 (four) dirty, the aggregate particle size is rhyme, and the film thickness is 1〇15μm. The reactor was partitioned into two spaces by a sifting sifter with a sifting sifter, and the nucleus was coated with a nucleus-catalyzed reaction zone as a side-by-side negative pressure zone. The nanosiolite membrane has a smaller pore size and is advantageous for supporting the catalyst particles to improve catalytic performance. However, the pore_ is formed by the numerator, so the area of the fine area is small relative to the entire nano-sieve membrane, that is, the wheel is small and cannot be sufficient _ its effective area, resulting in a decrease in the screening rate of the nano-sieve membrane and a low transition efficiency. In view of this, it is necessary to provide a nano screen which is effective in utilizing area 胄 and has high screening efficiency and a manufacturing method thereof. [Contents] In order to overcome the deficiencies in the prior art, such as the low effective utilization area of the nano screen and the low screening efficiency, the object of the present invention is to provide a nano screen which is effective for lying on the surface and having a high scale. Another object of the present invention is to provide a method for producing the above nano screen. In order to achieve the above-mentioned first object, the present invention provides a seed net comprising a film and a chassis for holding the film, the chassis having a sidewall formed thereon; wherein the film comprises a nano filter having a directional regular arrangement Oxidation of the pore structure. Moreover, wherein the film is anodized, the nanofiltration holes are parallel to each other and substantially perpendicular to the thin wire surface, and the nanopore is distributed on the side of the hexagon, the nanofiltration hole The hole is 1299287. The diameter ranges from 5 nm to ermi, and the opening ratio of the nanonews is above 2, and the thickness of the film ranges from 1 nanometer to 1 nanometer. In order to achieve the above second object, the present invention provides the above-described nanometer method, comprising the steps of: providing an aluminum substrate having a smooth surface; forming a nanofiltration structure having a directional regular arrangement on the smooth surface; The oxidized film, · removes the aluminum substrate, and obtains a self-supporting alumina film. · The oxidized film is held at the center of the chassis with the peripheral side wall to form a nano-screen. Wherein the film forming method adopts an anodizing method, and the electrolyte of the anodizing method adopts sulfuric acid, oxalic acid, Gu, and miscellaneous tests, and the mixed substrate is replaced by gold, and the substrate is removed by side method. The components of the secret engraving liquid and the mass fraction of the engraving method correspond to: squaric acid: acetic acid · nitric acid: water = 72%: 15%: 8%: 5%, the nanofiltration pores are parallel to each other And substantially perpendicular to the surface of the membrane, the nanofiltration pores are arranged in a hexagonal shape, and the pore diameter of the nanofiltration pores is 5 nm to 4 GG nanometers. The rate is 1 () 11 / coffee 2 or more, and the film is in contact with its hoof surface treatment, secret treatment or aerial treatment.丨& compared with the previous nano-screens, the nano-screened tank provided by the present invention uses an oxygen-sheathing membrane having a nanopore structure, which can be distributed by the wire _ The film of the nanofiltration pores is arranged according to the direction of the crucible I. The effective paste area of the film is high and the screening rate of the nano-screen is accelerated, and the screening efficiency is improved. [Embodiment] The present invention will be further described in detail below with reference to the accompanying drawings. Referring to the second drawing, the nanowire screen 1 of the present invention comprises a film u, a chassis 12 for holding the thin 1299287 film, and a side wall 13 formed on the periphery of the chassis 12. Among them, the chassis 12 is a base in which the center is empty, so that the film 11 can be held at the center of the chassis 12. The side wall 13 has a height to accommodate the powder to be dosed (® not shown). _ U-type-multi-oxygen film, formed in the thickness direction of the nanofiltration holes 14 arranged in a certain direction. Please refer to the third figure' for an enlarged view of the surface structure of the film u in the nano screen 10. The film 11 is composed of a plurality of unit cells 15 having a hexagonal column shape (as indicated by a broken line in the figure), and each cell has a hole-shaped hole 14 in the center thereof, and each cell 15 is closed by six sides. The shape of the cell is the same as the cell cell of the same cell, that is, the center line of the filter cell contained in each cell is a hexagon (shown by the solid line in the figure). In the scent, the nano-pores 14 are parallel to the surface U and perpendicular to the surface of the cylindrical through-hole nano-pores μ, which are parallel to each other, and have a size _, and are distributed in a hexagonal shape. The structure can be prepared by anodizing, and by preparing conditions for controlling anodization, such as adjusting oxidation voltage, time, etc., various sizes of nanopores 14 can be obtained, usually in the range of 5 nm to nanometer. 'The depth is about 1 nanometer to 100 nanometers, which is equivalent to the thickness of the film u. The opening ratio of the nanofiltration hole is at least 1011/cm2. The ingot mesh 1 () provided by the present invention can select the nanometer filter pores W of the same size as the powder particles to be mixed as needed, thereby screening the nano particles having uniform particle diameters. It can be matched with it when it is screened; it can be used for vibration equipment such as ultrasonic vibration green, etc., if necessary, it can also be filtered by water. The end of the knife is densely distributed due to the nanofiltration pores and arranged according to the directional principle. The film 11 is effectively utilized to increase the surface 2' and accelerate the screening rate of the nanowire 10, ultimately improving the screening efficiency of the nanowire 10. The fourth figure 'is a schematic diagram of the manufacturing process of nano-1G, which includes the following steps: (1) Provide - woven material 16, which has _ smooth surface 17: select - the higher degree of flatness 1299287 ^ (four) ( Also, the township is arbitrarily treated, such as butterfly, table rouge treatment and electric millennium, bribe pre-film film - flat smooth smooth surface 17, in order to facilitate its anodizing treatment. (2) in _ The surface of the 16 is formed into a oxidizing tank for the structure of her 14 u. • Anodizing is carried out in an acidic electrolyte cap woven material such as sulfuric acid, acid, sulphur, sulphuric acid or a mixed acid thereof, so that the surface thereof is smoothed. The domain shot _ self-induced, the distribution of the sentence of the nano-peripheral 14' can be removed from the thin-assisted upper touch oxidized green for secondary anodization, and finally can get __ shape of the L14 structure _u, ^ and The pores μ are parallel to each other' from the film-surface to the other surface. Lu Mei et al., Journal of Lanzhou University (Natural Science Edition), 2〇〇2, 38(4), 47_54, “Porous Oxidized Membrane Preparation and characterization, it is pointed out in the article that the pore distance and the heterogeneity of the porous oxide increase with the increase of the applied oxidation voltage. By using the proportional relationship between the voltage and the pore spacing, the control of the pore spacing of the electricity county is adjusted to adjust the distribution of the nanoholes according to the pores 14. Therefore, the thin film n of the densely distributed nano-holes 14 can be obtained, so that the film is more effective. · Area. _ By controlling the extreme oxidation conditions, such as the type of electrolyte, oxidation voltage temperature, time _ and bribes, etc., you can get the material, Huan Nai Qian Kong 14, usually between $ nanometer ~ 400 nm. For example, when sulfuric acid is used as the electrolyte, the pore diameter of the obtained nanopores 14 is small, usually about 20 nm; and when oxalic acid is used as the electrolyte, the pore size of the obtained nano-view 14 is large, usually at 40 nm. (3) Remove the base material and obtain the self-supporting oxidized film u: The method of removing the etched substrate 可采用 can be etched, using mixed acid as the etchant'. The various acid components in the mixed acid and the quality thereof The score corresponds to: Wei: Acetic acid: Acid supplement: Water = 72%: 15%: 8%: 5%. The remaining substrate is removed.
後，剩下自支撐之氧化銘薄膜u，該薄膜u厚度範圍為ι〇奈米〜_奈米。 如欲獲得足夠大孔徑之奈米觀14，還可對該自支㈣mi進行觀H ⑷使氧化紹薄膜η固持於一具周緣側壁13之底盤12中央，構成奈米 相ίο取具周緣侧壁13之底盤12，該底盤12中央為空，薄膜η即可^ 置於底盤12中央，從而構成具奈米篩孔之奈米篩網ι〇。 另’薄膜11使用前還可進一步對其進行表面處理或熱處理，以提高其硬 度、抗跪性等相關性能。 良丁、上所述’本發明符合發明專利之要件，爰依法提出專利申請。惟，以上 所述者僅為本發日㈣嫌實_，自不能灿關本紅冑料娜園。舉凡 …β本案技藝之人士 ’在援依本案發明精神所作之等效修飾或變化，皆應包含 於以下之申請專利範圍内。 【圖式簡單說明】 第一圖係習知篩網結構示意圖。 第二圖係本發明之奈米篩網結構示意圖。 第二圖係本發明之奈米篩網中薄 臈之表面結構放大示意圖。 第四圖係本發明之奈米篩 網之製造過程示意圖。 【主要元件符號說明】 奈米篩網 10 薄膜 11 底盤 12 側壁 13 奈米濾孔 14 晶胞 15 1呂基材 16 平滑表面 17After that, the self-supporting oxidized film u is left, and the thickness of the film u ranges from ι 〇 nanometer to _ nanometer. If a nanometer view 14 having a sufficiently large aperture is obtained, the self-supporting (four) mi may be subjected to H (4) to hold the oxidized film η in the center of the chassis 12 of a peripheral side wall 13 to form a peripheral side wall of the nano phase. The chassis 12 of the chassis 12 is empty in the center of the chassis 12, and the film η can be placed in the center of the chassis 12 to form a nano screen having a nano mesh. Further, the film 11 may be further subjected to surface treatment or heat treatment before use to improve the properties such as hardness, smash resistance and the like. Liang Ding, supra' The invention meets the requirements of the invention patent, and the patent application is filed according to law. However, the above mentioned is only true on the date of this issue (four), and it is impossible to make a copy of the red garden. The equivalent modifications or changes made by the person in the case of the invention in the case of the invention shall be included in the scope of the following patent application. [Simple description of the diagram] The first diagram is a schematic diagram of a conventional screen structure. The second figure is a schematic view of the structure of the nano-screen of the present invention. The second drawing is an enlarged schematic view showing the surface structure of the thin ruthenium in the nanowire of the present invention. The fourth drawing is a schematic view showing the manufacturing process of the nano screen of the present invention. [Main component symbol description] Nano screen 10 Film 11 Chassis 12 Side wall 13 Nano filter hole 14 Unit cell 15 1 Lu substrate 16 Smooth surface 17