1242540 案號 93100727 年 月 曰 修正 五 性 符 9m 米 法 法 件 反 晶 例 並 放 方 晶 成 氧 此 過 .發明說明（1) 發明所屬之 本發明係 種氧化鋅奈 先前技術】 奈米科技 產業到尖端 號係為n in ’ )，且奈米 線之製造方 、水熱合成 、化學氣相 ，其中以化 該化學氣 應來合成薄 片作為基板 如：鐵、鋁 取2塊耐火 有碳粉氧化 向位置，通 片避免氧化 長，且當反 化鋅奈米線 但，其習 在使用實施 f呈較為複雜1242540 Case No. 93100727 Amends the inversion example of pentagram 9m meter method and puts the crystals into oxygen. Explanation of the invention (1) The prior art of the invention belongs to the type of zinc oxide nanotechnology] Nanotechnology industry to the cutting edge The number is n in '), and the manufacture of nanowires, hydrothermal synthesis, and chemical vapor phase, in which the chemical gas should be used to synthesize a thin sheet as the substrate, such as: iron and aluminum. Position, the through piece avoids oxidative growth, and when the zinc nanowire is reversed, its practice is more complicated in use.
第4頁 技術領域】 有關一種製造奈米級金屬之技術領域，尤指 米線之製造方法。 係為目前最要的產業之一，其含蓋民生消費 的高科技領域，且奈米（nanometer )數學 其中一奈米即為十億分之一公尺（lnm=lx 、、、。構係為1〜1 〇 〇奈米，而對於一般氧化鋅奈 法，目前大都藉由化學製造法、氧化還原 法、喷霧法、溶膠凝膠法、微乳液法、電解 沉積法（C V D )，且受限於各方面的條 學氣相沉積法使用最為廣泛。 相沉積法（C V D )係以氣體原料經由化學 膜或微小粒子等固態材料的方法，其需以石夕 且使用離子錢鍛法在基板上錢一層觸媒， 、鎳粉末，再將試片放置水平式加溫爐管， 碑，分別擺放碳粉氧化鋅粉及矽晶片，再把 ，^之耐火磚，放置相對於該矽晶片順氣流 月性氣體例如：氬氣（A r )，以保護石夕 ’再將爐管加溫至9〇o°c，而供氧化鋅奈米 應進行完成後’待試片降至室溫後，即完成 之化學氣相沉積法製造方法。 =氧化鋅奈米線製造方法上仍有其缺失，因 ’由於需要準備有基板及觸媒，造 及麻煩，且製造的效果不佳 ^ ____ 夂大幅增加製造 1242540 案號 93100727 年 月 曰 修正 五、發明說明（2) 的成本。 【發明内容】 本發明之主要目的，在於解決上述的問題而提供一種 氧化鋅奈米線之製造方法，其係藉由直接氧化法製造出氧 化鋅奈米線，而能簡化製造過程，且製造效果佳，並能大 幅降低製造成本。 為達前述之目的，本發明係包括將直徑為1 0 // m -6 (10 m )以下之鋅粉（Ζ η )加入於一反應槽内，且使 該反應槽能均勻攪拌該鋅粉，並同時注入鈍氣，以保護鋅 粉避免氧化，再持續加熱至4 0 0 °C時，且該反應槽持續攪 拌的狀態之下，停止供應鈍氣，並注入水蒸氣，以持續加 熱至5 0 0 °C，且該鋅粉的熔解溫度為4 2 0 °C，而使該鋅粉加 熱至熔融溫度後，該鋅粉表面的原子會解離出來，並在表 面長出線球狀的氧化辞奈米線體，而水蒸氣與鋅分表面解 離出來的原子產生還原反應，其化學式為： Z n + Η 2 Ο ~> Ζ η 0 + Η 2 且維持溫度於一反應溫度，該反應溫度係為4 0 0 °C〜 5 0 0 °C，並持續通入水蒸氣，以成長氧化鋅奈米線體至反 應完成，再冷卻至室溫，而能於該鋅粉表面長成有多數氧 化鋅奈米線體。 本發明之上述及其他目的與優點，不難從下述所選用 實施例之詳細說明與附圖中，獲得深入了解。 當然，本發明在某些另件上，或另件之安排上容許有 所不同，但所選用之實施例，則於本說明書中，予以詳細 說明，並於附圖中展示其構造。Page 4 Technical Field] The technical field related to the manufacture of nano-grade metals, especially the method of manufacturing noodles. It is one of the most important industries at present. It covers the high-tech field of people's livelihood, and one nanometer in nanometer mathematics is one billionth of a meter (lnm = lx ,,,.). It is 1 to 100 nanometers, and for the general zinc oxide nanometer method, most of them are currently manufactured by chemical manufacturing method, redox method, spray method, sol-gel method, microemulsion method, electrolytic deposition method (CVD), and Limited by all aspects, the stripe vapor deposition method is most widely used. Phase deposition (CVD) is a method that uses gaseous materials to pass through solid films such as chemical films or fine particles. A layer of catalyst, nickel powder is placed on the substrate, and then the test piece is placed in a horizontal heating furnace tube, a tablet, a carbon zinc oxide powder and a silicon wafer, respectively, and the refractory brick is placed relative to the silicon. The wafer is flowed with a monthly gas such as argon (Ar) to protect Shi Xi ', and then the furnace tube is heated to 90o ° C, and the zinc oxide nanometer should be completed after the completion of the test piece. After the temperature, the chemical vapor deposition method is completed. = Zinc oxide There are still some defects in the method of wire manufacturing, because 'the substrate and catalyst need to be prepared, which is troublesome and the manufacturing effect is not good ^ _ 夂 夂 A substantial increase in manufacturing 1242540 Case No. 93100727 Amendment 5. Invention Description (2 [Abstract] The main object of the present invention is to provide a method for manufacturing zinc oxide nanowires by solving the above-mentioned problems. The method is to produce zinc oxide nanowires by a direct oxidation method, thereby simplifying the manufacturing. Process, and the manufacturing effect is good, and the manufacturing cost can be greatly reduced. In order to achieve the aforementioned purpose, the present invention includes adding a zinc powder (Z η) having a diameter of less than 10 // m -6 (10 m) to a reaction In the tank, the reaction tank can evenly stir the zinc powder, and at the same time, inert gas is injected to protect the zinc powder from oxidation. When the zinc powder is continuously heated to 400 ° C, and the reaction tank is continuously stirred, Stop supplying inert gas and inject water vapor to continue heating to 500 ° C, and the melting temperature of the zinc powder is 4 2 0 ° C. After the zinc powder is heated to the melting temperature, the Atom will dissociate , And a linear spherical oxidized nanowire body grows on the surface, and the reduction reaction of water vapor and the atoms dissociated from the zinc surface has a chemical formula: Z n + Η 2 Ο ~ > Zn η 0 + Η 2 and maintain the temperature at a reaction temperature, the reaction temperature is from 400 ° C ~ 500 ° C, and continuous water vapor to grow zinc oxide nanowires until the reaction is completed, and then cooled to room temperature, Many zinc oxide nanowires can be grown on the surface of the zinc powder. The above and other objects and advantages of the present invention can be easily understood from the detailed description and accompanying drawings of selected embodiments below. Of course The present invention allows some differences in the arrangement or arrangement of other parts, but the selected embodiment is described in detail in this specification and its structure is shown in the drawings.
第5頁 1242540 _案號93100727_年月日_Ifi_ 五、發明說明（3) 【實施方式】 請參閱第1圖至第3圖，圖中所示者為本發明所選用 之實施例結構，此僅供說明之用，在專利申請上並不受此 種結構之限制。 本實施例之氧化鋅奈米線之製造方法，如第1圖至第 3圖所示，其製造步驟係包含： 第一階段：將直徑為1 0 // m ( 1 0 -6m )以下之鋅粉 (Ζ η ) 10加入於一反應槽20内，且使該反應槽20 持續旋轉，均勻攪拌該鋅粉（Ζ η ) 1 〇 ，並注入鈍氣， 且加熱該反應槽2 0 ，該鈍氣可為氬氣，以保護鋅粉（Ζ η ) 1 0避免氧化。 第二階段：持續加熱至4 0 0 °C時，在該反應槽2 0持 續旋轉的狀態之下，停止供應氬氣，並注入水蒸氣，以持 續加熱至5 0 0 °C，且該鋅粉（Ζ η ) 1 〇的熔解溫度為 4 2 0 °C，而使該鋅粉（Ζ η ) 1 〇加熱至熔融溫度後，該 鋅粉（Ζη) 10表面的原子會解離出來，並在表面長出 線球狀的氧化鋅奈米線體1 1 ，而水蒸氣與鋅粉（Ζ η ) 1 0表氣面解離出來的原子產生還原反應，其化學式為： Ζη+Η20— Ζη0+Η2 且維持溫度於5 0 0 °C，並持續通入水蒸氣，以成長氧 化鋅奈米線體1 1至反應完成，再冷卻至室溫2 5 °C，而能 .於該鋅粉（Ζ η ) 1 0表面長成有多數氧化鋅奈米線體 1 1 ，如附件所示。 第三階段：將多數的氧化鋅奈米線體1 1由各鋅粉 (Ζ η ) 1 0分離，再將氧化鋅奈米線體1 1與剩餘之鋅Page 5 of 1242540 _Case No. 93100727_year month_Ifi_ V. Description of the invention (3) [Embodiment] Please refer to Fig. 1 to Fig. 3, which shows the structure of the embodiment of the present invention, This is for illustration purposes only and is not restricted by this structure in patent applications. As shown in Figures 1 to 3, the manufacturing method of the zinc oxide nanowires in this embodiment includes the following steps: The first stage: the diameter is less than 1 0 // m (1 0 -6m) Zinc powder (Z η) 10 is added to a reaction tank 20, and the reaction tank 20 is continuously rotated, the zinc powder (Z η) 1 0 is uniformly stirred, inert gas is injected, and the reaction tank 20 is heated. The inert gas may be argon to protect zinc powder (Z η) 1 0 from oxidation. The second stage: when the heating is continued to 400 ° C, under the state that the reaction tank 20 is continuously rotating, the supply of argon gas is stopped, and water vapor is injected to continuously heat to 500 ° C, and the zinc The melting temperature of powder (Z η) 1 〇 is 4 2 0 ° C, and after the zinc powder (Z η) 1 〇 is heated to the melting temperature, the atoms on the surface of the zinc powder (Zη) 10 will be dissociated, and A linear spherical zinc oxide nanowire body 1 1 grows on the surface, and water vapor and zinc powder (Z η) 1 0 dissociate from the surface surface of the atom to produce a reduction reaction. Its chemical formula is: Znη + Η20— Znη0 + Η2 And maintain the temperature at 500 ° C, and continue to pass water vapor to grow zinc oxide nanowires 11 until the reaction is complete, and then cooled to room temperature 2 5 ° C, so that the zinc powder (Z η ) 1 0 The surface grows into most zinc oxide nanowires 1 1, as shown in the attachment. The third stage: Most zinc oxide nanowires 1 1 are separated from each zinc powder (Z η) 1 0, and then zinc oxide nanowires 1 1 and the remaining zinc
1242540 案號 93100727 曰 修正 五、發明說明（4) 粉（Ζ η ) 1 完成氧化鋅奈 其中，第 餘之鋅粉（Ζ 1 ·超音 2 ·離心 藉由離心 奈米線體1 1 3 ·比重 猎由該乳 鋅粉（Ζ η ) 同，將該氧化 離。 4 •熔點 藉由該氧 (Ζ η ) 10 該氧化鋅奈米 另外，第 間，且依不同 直徑大小也不 〇分離，收集製造完成之氧化鋅奈米線，即 米線之製造。 三階段有許多將該氧化鋅奈米線體1 1與剩 η ) 1 0分離之方法，且說明如下： 波分離法 式分離法 滾筒高速旋轉，而產生離心力，將該氧化鋅 與該鋅粉（Ζ η ) 1 〇分離。 不同方式 化鋅奈米線體1 1之比重為5. 642g/cm3 ，該 1 0之比重為7.133g/cm3，以利用比重之不 鋅奈米線體1 1與該鋅粉（Ζ η ) 1 〇分 不同方式 化鋅奈米線體1 1之熔點為1 9 7 7 °C，該鋅粉 之熔點約為4 2 0 °C ，而利用熔點之不同，將 線體1 1與該鋅粉（Ζ η ) 1 〇分離。 二階段之反應溫度於控制在4 0 0 °C〜5 0 0 °C 之反應溫度，所產生氧化鋅奈米線體1 1之 同，如下所示： 反應溫度5 0 0 °C (1 0 0 nm ) 〇 氧化鋅奈米線體 2 ·反應溫度4 5 0 C - ----氧化辞奈米線體1242540 Case No. 93100727 Amendment V. Description of the Invention (4) Powder (Z η) 1 Among which zinc oxide is completed, and the remaining zinc powder (Z 1 · Ultrasonic 2 · Centrifugation by centrifuging the nanowire 1 1 3 · The specific gravity hunting is the same as the milk zinc powder (Z η), and the oxidation is separated. 4 • The melting point is by the oxygen (Z η) 10 The zinc oxide nano is also separated by different diameters and sizes. Collect the finished zinc oxide nanowires, that is, the production of rice noodles. There are many methods to separate the zinc oxide nanowires 11 from the remaining η) 10 in the three stages, and they are explained as follows: Wave separation method separation method drum Rotate at high speed to generate centrifugal force, and separate the zinc oxide from the zinc powder (Z η) 10. The specific gravity of the zinc nanowire 11 is 5.642g / cm3 in different ways, and the specific gravity of the 10 is 7.133g / cm3, so as to utilize the specific gravity of the non-zinc nanowire 11 and the zinc powder (Z η). The melting point of zinc nanowire 1 1 in different ways of 10 minutes is 197 7 ° C, and the melting point of the zinc powder is about 4 2 0 ° C. The difference in melting point is used to compare the wire 11 and the zinc. Powder (Z η) 1 0 was isolated. The reaction temperature in the second stage is controlled at a reaction temperature of 400 ° C ~ 50 0 ° C. The zinc oxide nanowire body 1 1 is the same as shown below: The reaction temperature is 50 0 ° C (1 0 0 nm) 〇 Zinc oxide nanowires 2 · Reaction temperature 4 5 0 C----- Oxide nanowires
界於90nm〜50nm之間。 3 ·反應溫度4 3 0 °C 氧化鋅奈米線體 直徑約 直徑約 直徑小The boundary is between 90nm and 50nm. 3 Reaction temperature 4 3 0 ° C Zinc oxide nanowires Approx. Diameter Approx. Diameter Approx. Small diameter
1242540 _案號 93100727_年月日__ 五、發明說明（5) 於 5 0 nm 〇 由此可知，越接近鋅粉（Z η ) 1 0的熔點4 2 0 °C， 所產生的氧化鋅奈米線體1 1直徑越小。 本發明利用上述之技術手段，而能方便實施，且不用 如習用需要準備有基板及觸媒，因此，能大幅簡化製造過 程較，以及降低製造成本。1242540 _Case No. 93100727_ 年月 日 __ V. Description of the invention (5) at 50 nm 〇 It can be seen that the closer to the melting point of zinc powder (Z η) 1 0 4 2 0 ° C, the produced zinc oxide The smaller the diameter of the nanowire body 1 1. The present invention utilizes the above-mentioned technical means, which can be conveniently implemented, and does not need to prepare a substrate and a catalyst as in practice. Therefore, the manufacturing process can be greatly simplified, and the manufacturing cost can be reduced.
以上所述實施例之揭示係用以說明本發明，並非用以 限制本發明，故舉凡數值之變更或等效元件之置換仍應隸 屬本發明之範疇。 由以上詳細說明，可使熟知本項技藝者明瞭本發明的 確可達成前述目的，實已符合專利法之規定，爰提出專利 申請。The disclosure of the embodiments described above is used to illustrate the present invention, and is not intended to limit the present invention. Therefore, any change in the value or replacement of equivalent components should still belong to the scope of the present invention. From the above detailed description, those skilled in the art can understand that the present invention can indeed achieve the aforementioned purpose, and it has indeed complied with the provisions of the Patent Law, and filed a patent application.
第8頁 1242540 _案號93100727_年月曰 修正_ 圖式簡單說明 【圖式簡皁說明】 第1圖係本發明反應槽之組合剖視示意圖。 第2圖係本發明製造過程之時間與溫度變化示意圖。 第3圖係本發明氧化鋅奈米線形成之之流程圖。 附件：本發明成長為氧化鋅奈米線之照片。 【圖號說明】 (本發明部分） 鋅粉（Z η ) 1 0 氧化鋅奈米線體1 1Page 8 1242540 _Case No. 93100727_ Year Month Amendment _ Brief Description of Drawings [Simplified Description of Drawings] Figure 1 is a schematic sectional view of the combination of the reaction tank of the present invention. Figure 2 is a schematic diagram of the time and temperature changes during the manufacturing process of the present invention. Figure 3 is a flow chart of the formation of zinc oxide nanowires according to the present invention. Attachment: Photograph of the invention growing into a zinc oxide nanowire. [Illustration of drawing number] (Part of the present invention) Zinc powder (Z η) 1 0 Zinc oxide nanowire body 1 1
反應槽2 0Reaction tank 2 0
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