201022451 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種用以連續製作奈米銀線之方法，並 且特別地，本發明係關於一種以可大量生產高品質之奈米 銀線之方法。 σ 、 不〆、 【先前技藝】 -維的奈米結構，如奈米線、奈米•、奈米棒、夺 米柱以及奈米纖維等，具有低維度的物理與電子傳輸性 質’其特性與-般巨觀材料不同。近年來許多企業以及團 隊不斷地針對-維奈米結構之應用進行研究並獲得重要的 成果，這些應用包含超薄全彩LED、科設備、場發射 、低能消耗性奈米線LED以及吨_ &的感測器 等。 算，屬材料、:例如奈米金、錫、銀、鉑奈米線 有良好的導電特性而經常應用於導線材料。 二下表面效應、量子效應或穿遂效應等微觀效 f曰更加因此—維奈米金屬材料適胁各種應用上 ίϊί之奈米電子元件，並且可進—步翻於電極、低溫 中超導厚膜電路、微波及電磁波吸收材料等。其 視為重點研究。_故奈祕_應用被各界 碳管=未二，品化的—維奈米結構僅有奈米 /、有回導電效果之-維金屬奈米材料的相闕 201022451 維奈米金屬線已有數種製作方法，然而，這些方 、：刀別具有其缺點而不利於商 。 術中數種製作-維奈米金屬線之方法之優先别技 於先前技術中，-維奈米金屬 電化=動模板成長法、電子束照射纺絲法 ;板成=解法以及殼核生成法等。其中，電化=201022451 VI. Description of the Invention: [Technical Field] The present invention relates to a method for continuously producing a nano silver wire, and in particular, the present invention relates to a mass production of high quality nano silver wire method. σ, 不〆, [previous skill] - dimensional nanostructures, such as nanowires, nanometers, nanorods, rice columns, and nanofibers, have low-dimensional physical and electronic transport properties. Different from the general material. In recent years, many companies and teams have been researching and achieving important results for the application of the Venezia structure, including ultra-thin full-color LEDs, equipment, field emission, low-energy consumption nano-line LEDs and tons of _ & Sensors, etc. Counting materials, such as nano gold, tin, silver, and platinum nanowires, have good electrical conductivity and are often used in wire materials. The second surface effect, quantum effect or piercing effect is even more so. The Venin metal material is suitable for various applications of nanoelectronic components, and can be turned into the electrode, superconducting thickness in low temperature. Membrane circuits, microwaves and electromagnetic wave absorbing materials. It is considered a key study. _ 故奈秘_Applications are carbon nanotubes of all circles = not two, the quality of the - Venai structure only nano /, there is a return to the conductive effect - the dimension of the metal nanomaterials 201022451 Venai wire has been number The production method, however, these parties, the knife has its shortcomings and is not conducive to business. In the prior art, several methods of making the Venai wire are preferred in the prior art, - Vennell metal electrochemistry = dynamic template growth method, electron beam irradiation spinning method; plate formation = solution method and shell core generation method, etc. . Among them, electrification =
❹ 伽柄生狀奈米線麵小並且均勻度佳， 製程複雜而不適合大量生產，因此不利於商品 子束騎_法以及觸媒成長法可控制奈米金屬線 =生長位置’ ^同樣地，其設備成本高並且製程複雜， 2不適σ大里生產。化學純解法 用 =金=程r而可量產化，然™合成^ j金屬線直錄大並同時產生微量之奈米顆粒，亦即， ^ =率不如其他方法。殼核生成法係以奈米碳管為核，經 =而形成多功能的複合材料，然而，舰後的材料直徑 fi並且鍍膜的均勻度不易控制，其製程複雜同時成本也 相當高。 &上所述’化學熱裂解法較其他方法更細於量產奈 =銀線^而，此方法問題在於凝聚效應會形成較大的顆 二’並且其反應需在高溫下反應而適用減合成方式，以 產能而言仍嫌不足。 【發明内容】 因此’本發日狀—料在於提供-種能大量製作高品 貝之奈米銀線方法，以解決上述問題。 201022451 根據一具體實施例，本發明之方法可用以製作奈米銀 線，其步驟如下所述。首先，於反應槽以及老化槽中加入 乙二醇溶液並進行預熱。接著，以連續進料之方式加入銀 鹽溶液以及保護溶液至反應槽中混合，接著，混合液可於 適當的反應溫度範圍下在反應槽中進行反應。混合液於反 應槽中經過第一滯留時間並析出固體後，可流入老化槽以 進行老化過程。混合液於老化槽經過第二滯留時間後，可 取出並純化以獲得奈米銀線材料。伽 The stalk-like nanowire has a small surface and good uniformity, and the process is complicated and not suitable for mass production. Therefore, it is not conducive to the commercial beam riding method and the catalyst growth method can control the nano metal wire=growth position'. Similarly, The equipment cost is high and the process is complicated, 2 is not suitable for Sigma production. The chemical pure solution method can be mass-produced with = gold = process r, but the TM synthesis metal wire is directly recorded and produces a small amount of nano particles at the same time, that is, the ^ = rate is not as good as other methods. The shell-nuclear formation method uses a carbon nanotube as the core to form a multifunctional composite material. However, the material diameter of the ship is fi and the uniformity of the coating is difficult to control, and the process is complicated and the cost is also high. & described above, 'Chemical thermal cracking method is more fine than other methods to produce nai = silver wire ^, the problem of this method is that the coagulation effect will form a larger particle II' and its reaction needs to be reacted at high temperature and applied to reduce The synthesis method is still insufficient in terms of production capacity. SUMMARY OF THE INVENTION Therefore, the present invention is intended to provide a method for producing a high-quality nano-silver wire in a large amount to solve the above problems. 201022451 According to a specific embodiment, the method of the present invention can be used to make nano silver wires, the steps of which are as follows. First, an ethylene glycol solution is added to the reaction tank and the aging tank and preheated. Next, the silver salt solution and the protective solution are added to the reaction tank for continuous feeding, and then the mixture is allowed to react in the reaction tank at an appropriate reaction temperature range. After the mixed solution passes through the first residence time in the reaction tank and precipitates solids, it can flow into the aging tank to carry out the aging process. After the mixed solution is passed through the aging tank for a second residence time, it can be taken out and purified to obtain a nano silver wire material.
於本具體實施例中’銀鹽溶液係使用硝酸銀溶於乙二 醇溶液中而形成，保護溶液則以聚乙烯吡咯酮(p〇lyvinyl pyrrolidone，PVP)溶於乙二醇溶液中而形成。 、進一步地，純化混合液以獲得奈米銀線材料之方法可 進步包含下列步驟：將丙酮加入混合液中以大體上移除 乙二醇而得到沈澱物；將沈澱物溶於熱水中並進行離子交 換；於加熱鮮狀態下進行固液分離數次而獲得含有高品 ^之不米，線之錢。此外’上述含有奈米銀線之溶液可 一步以喷霧絲之枝去除水分喊得奈練線粉末。 關於本土明之優點與精神可以藉由以下的發明詳述及 斤附圖式得到進—步的瞭解。 【實施方式】 > ]圖 圖一係搶示根據本發明之一且體實施例 製作奈米銀線之方法的示意圖。如[I ’實例之方法包含下列步驟：於步驟S10中，加入 201022451 第一溶液至反應槽以及老化槽巾並預熱第—溶液至第一溫 度範圍；於步驟S12中，加人銀餘液以及倾溶液至= ，槽中，使銀鹽溶液以及保護溶液於第二溫度範圍下進行 混合並於反應槽中停留第一滯留時間以形成第二溶液；於 步驟S14中’將第二溶液加入老化槽並使第二溶液於老化 槽停留第一滯留時間以形成第三溶液；於步驟S16中，純 化第三溶液以獲得奈米銀線。 於本具體實施例中，第一溶液為乙二醇溶液，但於實 務中並不限定於乙二醇。此外，銀鹽溶液可以硝酸銀溶於 乙一醇中而开>成，但於實務中，亦可以水溶性銀鹽原料溶 於其他溶劑中而形成，並不限定於硝酸銀以及乙二醇。舉 例而言，可使用醋酸銀或是亞硝酸銀溶於有機溶劑中而二 成銀鹽溶液。同樣地，保護溶液可以，但不受限於，聚乙 烯°比咯酮溶於乙二醇溶液而形成。 上述之步驟S12中，加入銀鹽溶液以及保護溶液至反 應槽之步驟可依照一比例同時加入，於本具體實施例中係 以等比例加入。請注意，由於銀鹽溶液以及保護溶液於反 應槽中才會接觸，故可避免其提早接觸而於非設定條件下 進行反應導致奈米銀顆粒或是其他非預期的效應產生。 另一方面，銀鹽溶液以及保護溶液可以連續進料方式 進入反應槽中，因此，反應可以連續進行而能大量生產奈 米銀線。舉例而言’反應槽於實務中可包含兩個不同的入 料口’銀鹽溶液以及保護溶液則可利用幫浦分別自兩入料 口以等比例連續打入反應槽中。請注意，由於連續進料的 201022451 過程會降低混合液的溫度，因此步驟S10中之預熱動作必 須確實以確保銀鹽溶液以及保護溶液可直接於反應溫度下 進行反應。若無上述預熱過程，當銀鹽溶液以及保護溶液 進料後會於較低溫度條件下反應而形成較多的奈米銀顆 粒0In the present embodiment, the silver salt solution is formed by dissolving silver nitrate in an ethylene glycol solution, and the protective solution is formed by dissolving p〇lyvinyl pyrrolidone (PVP) in an ethylene glycol solution. Further, the method of purifying the mixture to obtain a nanosilver material can be further carried out by adding acetone to the mixture to substantially remove the ethylene glycol to obtain a precipitate; dissolving the precipitate in hot water and Ion exchange is carried out; solid-liquid separation is carried out several times in a heated state to obtain a high-quality product containing no rice and no wires. Further, the above solution containing the nano silver wire can be removed in one step by removing the water from the branches of the spray wire. The advantages and spirit of the local Ming can be further understood by the following detailed description of the invention and the figure. [Embodiment] FIG. 1 is a schematic view showing a method of fabricating a nano silver wire according to one embodiment of the present invention. The method of the [I' example includes the following steps: in step S10, adding the first solution of 201022451 to the reaction tank and aging the sump and preheating the first solution to the first temperature range; in step S12, adding the silver residual liquid And pouring the solution into the tank, mixing the silver salt solution and the protective solution at the second temperature range and staying in the reaction tank for a first residence time to form a second solution; and adding the second solution in step S14 The aging tank is allowed to leave the second solution in the aging tank for a first residence time to form a third solution; in step S16, the third solution is purified to obtain a nano silver wire. In the present embodiment, the first solution is an ethylene glycol solution, but is not limited to ethylene glycol in practice. Further, the silver salt solution may be formed by dissolving silver nitrate in ethyl alcohol, but in practice, the water-soluble silver salt raw material may be dissolved in another solvent, and is not limited to silver nitrate and ethylene glycol. For example, silver acetate or silver nitrite may be dissolved in an organic solvent to form a silver salt solution. Similarly, the protective solution can be, but is not limited to, formed by dissolving the polyethylene ketone in an ethylene glycol solution. In the above step S12, the step of adding the silver salt solution and the protective solution to the reaction tank may be simultaneously added in accordance with a ratio, and is added in an equal proportion in the present embodiment. Please note that since the silver salt solution and the protective solution are contacted in the reaction tank, it is possible to avoid the early contact and the reaction under non-set conditions, resulting in nano silver particles or other unintended effects. On the other hand, the silver salt solution and the protective solution can be continuously fed into the reaction tank, so that the reaction can be continuously carried out to mass-produce the nano silver wire. For example, the reaction vessel may contain two different inlets in the practice. The silver salt solution and the protective solution can be continuously pumped into the reaction tank from the two inlets in equal proportions. Please note that since the continuous feed 201022451 process will reduce the temperature of the mixture, the preheating action in step S10 must be performed to ensure that the silver salt solution and the protective solution react directly at the reaction temperature. If there is no such preheating process, when the silver salt solution and the protective solution are fed, the reaction will be carried out at a lower temperature to form more nano silver particles.
於本具體實施例中，保護劑係以聚乙烯吡咯酮溶於乙 二醇溶液中而形成。聚乙烯吡咯酮為水溶性的高分子化合 物，因此其可溶於乙二醇巾。#㈣溶液與傾溶液之混合 液於反應溫度τ析綠顆㈣，聚乙烯对酮分子可以提供 立體空間屏障以抑制銀雜之絲，以達到奈米尺寸之要 求°另-方面’於反應射，聚乙烯轉_之長鏈上的氧官 ，基可引導銀微粒於-維方向±接合並開始安定地成長，接 著在老化槽的老化過程中形成一維奈米銀線。 為;了能_勻混合銀鹽频以及保護溶液，因此反應 ^可f置均質機、磁攪拌機或馬達獅财幫助兩溶液 t二意’若使㈣械式機，賴所用的第 1液(於本具财施财紅二_液)力认反 可達到勝葉片能·到之最小量為原則。 於本具體實施例中，銀鹽溶液中包含之確酸銀 可大於0.5Wt%。另外’保護溶 ： 酮的分子量範圍可為漏〜36_ 1絲乙婦比洛 保護溶液加人反㈣時之聚㈣ θ。“㈣溶液與該 05~6 ^ ^ ^烯吡咯酮與硝酸銀的重量比 二Vi二：槽中維持之第二溫度範圍可為 140 WC，並且預熱的第—溫度範圍可為 201022451 180°C。請注意，於實務中，可藉由微波加熱方式進行預 熱或維持反應槽及老化槽内之溫度範圍，但不以此為限。 由於上述反應時的溫度會影響混合液析出奈米銀線之 速率，因此，第二溶液於反應槽中所停留之第一滯留時間 可為，但不受限於10〜30分鐘之間。接著第二溶液進入 老化槽後所停留之第二滯留時間可為，但不受限於30分 鐘。於實務中，若配合可進行反應的溫度以及濃度之下， 第一滯留時間可合理的設定為10〜45分鐘之間。此外， 當銀鹽溶液以及保護溶液加入反應槽後30分鐘即可達到 穩態’然而，兩溶液仍連續進料，故反應槽中銀離子轉化 為奈米銀之轉化率大體上為一穩定值，於實務中，大約為 90% °另一方面’當反應液進入老化槽後30分鐘，可將 轉化率提升至1〇〇〇/。，因此若在反應液於反應槽滯留30分 鐘後進入老化槽’可合理地設定其於老化槽的滯留時間為 3 0分鐘。 請參閱圖二，圖二係繪示根據另一具體實施例之純化 反應液以獲得奈米銀線之步驟流程圖。如圖二所示，於本 具體實施例中，上一具體實施例之步驟S16可進一步包含 下列步驟：於步驟S160，加入過量丙醇至第三溶液中與 乙二醇互溶，致使第三溶液形成澄清液部分以及沈澱部 分’於步驟S162，將澄清液部分移除而得到沈澱部分， 並將沈殿部分溶於熱水中而形成第四溶液；於步驟 S164 ’以離子交換法處理第四溶液以形成第五溶液；於步 驟S166 ’重複加熱攪拌並固液分離處理第五溶液數次， 進而獲得第六溶液；於步驟S168，以噴霧乾燥方式去除 201022451 第六溶液之水分以獲得奈米銀線之粉末。 ❹In this embodiment, the protective agent is formed by dissolving polyvinylpyrrolidone in an ethylene glycol solution. Polyvinylpyrrolidone is a water-soluble polymer compound, so it is soluble in glycol towels. #(四) The mixture of the solution and the decanted solution is liquefied at the reaction temperature τ (4), and the polyethylene-to-ketone molecule can provide a three-dimensional space barrier to suppress the silver wire to meet the nanometer size requirement. The oxygen on the long chain of the polyethylene can guide the silver particles to join in the -dimensional direction and begin to grow stably, and then form a one-dimensional nano silver wire during the aging process of the aging tank. For the _ even mixed silver salt frequency and protection solution, so the reaction can be set to homogenizer, magnetic mixer or motor lion to help two solutions t two meanings if the (four) machine, the first liquid used In this case, the wealth of the money is red and the second is the principle that the minimum amount of the blade can be reached. In this embodiment, the silver salt solution may comprise more than 0.5 wt% of silver. In addition, the protective solution: the molecular weight of the ketone can be in the range of ~36_1 乙 妇 比 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 保护 。 。 "(4) The weight ratio of the solution to the 05~6 ^ ^ enepyrrolone to silver nitrate. The second temperature range maintained by the tank is 140 WC, and the temperature range of the preheating may be 201022451 180 ° C. Please note that in practice, the temperature range of the reaction tank and the aging tank can be preheated or maintained by microwave heating, but not limited thereto. The temperature during the above reaction will affect the precipitation of nano silver in the mixed liquid. The rate of the line, therefore, the first residence time of the second solution in the reaction tank may be, but is not limited to, between 10 and 30 minutes. Then the second residence time after the second solution enters the aging tank It can be, but is not limited to, 30 minutes. In practice, the first residence time can be reasonably set between 10 and 45 minutes if it is combined with the temperature at which the reaction can be carried out and the concentration. In addition, when the silver salt solution and The steady state is reached 30 minutes after the protection solution is added to the reaction tank. However, the two solutions are continuously fed, so the conversion rate of silver ions converted to nano silver in the reaction tank is substantially a stable value. In practice, it is about 90. % ° the other party When the reaction liquid enters the aging tank for 30 minutes, the conversion rate can be increased to 1 〇〇〇 /. Therefore, if the reaction liquid enters the aging tank after being retained in the reaction tank for 30 minutes, it can be reasonably set in the aging tank. The retention time is 30 minutes. Please refer to FIG. 2 , which is a flow chart showing the steps of purifying the reaction liquid to obtain a nano silver wire according to another embodiment. As shown in FIG. 2 , in the specific embodiment, Step S16 of the previous embodiment may further include the following steps: in step S160, adding excess propanol to the third solution to be miscible with ethylene glycol, so that the third solution forms a clear liquid portion and a precipitate portion 'in step S162, The clarified liquid is partially removed to obtain a precipitated portion, and the sump portion is dissolved in hot water to form a fourth solution; the fourth solution is treated by ion exchange to form a fifth solution in step S164; and the heating is repeated at step S166 Stirring and solid-liquid separation processing the fifth solution several times to obtain a sixth solution; in step S168, removing the moisture of the sixth solution of 201022451 by spray drying to obtain the powder of nano silver wire End. ❹
丙酮具有可與乙二醇互溶卻不溶解聚乙烯吡咯酮之特 性，因此，於本具體實施例中，步驟S160所加入之過量 丙酮可與第三溶液之乙二醇互溶，因此奈米銀線與包覆^ 米銀線之聚乙稀咕嘻酮會向下沈殿導致第三溶液中双、、主 液部分以及沈澱部分，其中，澄清液部分係丙酮與乙二 溶而成之溶液。待沈澱一段時間後，抽掉上層之澄清液邙 分，如步驟S162所述。接著，步驟Sl62中係以熱水溶解沈 澱部^而形成第四溶液。熱水除了可以溶解聚乙烯吡咯酮之 外’還可加速沈澱部分中之殘留丙嗣揮發。. 於本具體實施例中，上述第四溶液可利用離子交換法處 理第四溶液(如步驟S164所述），以清除殘留於溶液中之 陰、陽離子’進-步形成呈中性之第五溶液。請注音，於 進行步驟随之前，可先冷卻第四溶㈣進行離子交 ，。進行步驟後所獲得之第五溶液具有分散良好、 咼純度並且外部包覆聚乙烯吡咯酿I的奈米銀線。 於實際應用時’可先去除包覆奈米銀線之聚乙婦咖各 =直接應用奈米銀線本體。因此，可重複對第五溶液進行 加…、授拌以使聚乙烯轉輯水的溶解度提高，同時進行固 糖次，如步驟S166所述。軸上述步驟可去除包 二二、、:V、銀線外之聚乙烯如各_獲得第六溶液，因此， S168^H具有無外部包覆之奈米銀線。最後，利用步驟 = 射之水分絲而獲得高純度之奈米銀線的 201022451 進一步地，本發明之用以連續製作奈米銀線之方法， 其保護溶液中之高分子化合物的分子量、高分子化合物對 銀鹽的重量比例、反應溫度以及銀鹽溶液與保護溶液的進 料濃度均對所生成之奈米銀線的產量以及品質有影響。 明參閱表一，表一標示應用不同分子量之聚乙稀〇比洛 酮之各具體實施例所生成之奈米銀線的外觀。請注意，表一 之實施例1係以20克硝酸銀溶於1200克之乙二醇溶液形成 銀鹽溶液(銀之濃度為l.66wt%)，並以8〇克聚乙烯吡咯酮溶 於1200克之乙二醇溶液以形成保護溶液。反應槽以及老化槽 分別加入乙二醇l〇〇g並以17〇〇c進行預熱，並且兩者於於反 應時維持150 C之反應溫度。此外，反應液於反應槽内之滯 留時間係30分鐘’並且於老化槽内之滯留時間係3〇分鐘。 最後，自老化槽中取出反應液並萃取出奈米銀線。表一中之 實施例2以及3之反應條件均與實施例1相同，但各實施例 所使用之聚乙烯吡咯酮的分子量具有差異。 同分f量之聚乙烯吡咯酮對奈米銀線之影響 實施例 聚乙烯吡咯酮分子量 奈米銀線型態 1 58000 直徑80〜100 nm 長度6〜10 μιη 2 8000 直徑60〜80 nm 長度2〜5 μιη 3 360000 直徑90〜120 mn 長度8〜12 μιη 11 201022451 如表一所示，所使用之聚乙烯吡咯酮之分子量越高， 所生成之奈米銀線越長並且越粗。 •=參閱表二，表二標示具有不同的聚乙烯吡咯酮對銀鹽 之重里比例之各具體實施例所生成之奈米銀線的外觀。其 中’實施例丨，與表—巾之實麵1相同。表二t之實施例 4 5，及6係使用不同重量之聚乙烯^摘溶於丨謂克的 乙二醇溶液以形成保護溶液，其餘條件則與實施例i相同。 對奈米銀線之影響 聚乙烯《比咯酮重量(g) 奈米銀線型態 實施例 - Γ 80 直控80〜100 nm 長度6〜10 μιη 5 Ο 6 20 30 160 直徑〜2301 長度15〜25 μιη 直桂90〜120 nm 長度5〜15 μηι 多為顆粒狀 僅少量奈米銀線 如表二所示，聚乙烯吡咯酮與銀鹽之比例太高將會產 ^奈米銀顆粒而不利於奈米銀線生成。此外，比例越低則生 成之奈米銀線直徑越粗並且長度越長。 ^月，閱表表二係標示應用不同反應溫度之各具體 把例所生成之奈米銀線的外觀。其中，實施例1與表一中 12 201022451 之實施例1相同。表三中之實施例7、8以及9所設定之反應 溫度均不相同，其餘條件則與實施例1相同。 g、不同反應溫度對奈米銀線之影^ 實施例 --~~--- 反應溫度(°C) 奈米銀線型態 1 ------- 150 直徑80〜100 nm 長度6〜10 μιη 7 ------- 140 顆粒狀固體 無奈米銀線 8 160 直徑100〜110 nm 長度7〜10 μιη 9 170 直徑130〜150 nm 長度7〜11 μιη 如表三所示，反應溫度低於15〇〇C時將會產生奈米銀 顆粒而無奈米銀線生成。此外，隨著反應溫度上升，所生成 之奈米銀線之直徑越粗並且長度越長。 …凊參閱圖二，圖三係繪示表三之各具體實施例之轉化 率y對反應時間τ之分佈圖。如圖三所示，曲線2〇、 22 24、26分別代表實施例j、7、8、9之轉化率對反應 時間的*佈曲線。反應溫度若低於丨資。，由於其反應速 率低，因此僅能析出銀微粒而無法析出奈米銀線。此和若 ^應溫度高於15〇。〇：以上，則3G分鐘内即大量析出奈米銀 、’：:因此反舰於反應狀可合理地奴為如分鐘 13 201022451 請參閱表四，表四係標示進料濃度斜奈米銀線直徑之 影響。其中，實施例1與表一中之實施例i相同。表四中之 實施例1G、η、12、13以及14係使用不同重量之硝酸銀溶 於1200克的乙二醇中以形成銀鹽溶液，並且使用不同重量之 聚乙烯吡咯酮溶於1200克的乙二醇溶液以形成保護溶液， 其餘條件則與具體實施例1相同。 表四、3 ;同進料濃度對奈米銀線之影響 實施例 硝酸銀重量(g) 聚乙烯《比°各酮重量(g) 奈米銀線型態 1 20 80 直徑80〜100 nm 長度6〜10 μηι 10 10 160 顆粒狀固體 無奈米銀線 11 40 160 直徑〜160 nm 長度5〜8 μιη 12 60 240 直徑〜210 nm 長度〜5 μτη 13 100 400 直徑〜290 nm 長度〜5 μπι 14 265 400 直徑〜540 nm 長度〜5 μιηAcetone has the property of being miscible with ethylene glycol but not dissolving polyvinylpyrrolidone. Therefore, in this embodiment, the excess acetone added in step S160 can be miscible with the ethylene glycol of the third solution, so the nano silver wire The polyethylene ketone with the coated silver wire will swell down to the double solution, the main liquid portion and the precipitate portion in the third solution, wherein the clear liquid portion is a solution in which acetone and ethylene are dissolved. After a period of time to be precipitated, the supernatant liquid of the upper layer is removed, as described in step S162. Next, in step S62, the precipitation solution is dissolved in hot water to form a fourth solution. In addition to the fact that the hot water can dissolve the polyvinylpyrrolidone, the residual propidium volatilization in the precipitated portion can be accelerated. In the specific embodiment, the fourth solution may be treated by the ion exchange method to treat the fourth solution (as described in step S164) to remove the negative ions and cations remaining in the solution to form a neutral fifth. Solution. Please note that the fourth solution (four) can be cooled before the step is performed. The fifth solution obtained after the step was carried out with a silver nanowire which was well dispersed, ruthenium purity and externally coated with polyvinylpyrrolidone. In practical applications, the polyester silver-coated coffee beans can be removed first. The nano silver wire body is directly applied. Therefore, the fifth solution can be repeatedly added, and mixed to increase the solubility of the polyethylene-transferred water while performing the fixing, as described in step S166. The above steps of the shaft can remove the polyethylene of the package 22, V, and the silver wire, such as each to obtain the sixth solution. Therefore, the S168^H has a nano silver wire without external coating. Finally, 201022451 for obtaining a high-purity nano silver wire by using the step = shot moisture yarn. Further, the method for continuously producing a nano silver wire of the present invention protects the molecular weight of the polymer compound in the solution and the polymer The weight ratio of the compound to the silver salt, the reaction temperature, and the feed concentration of the silver salt solution and the protective solution all have an effect on the yield and quality of the produced nano silver wire. Referring to Table 1, Table 1 shows the appearance of the nanosilver lines produced by the specific examples of the different molecular weights of polyethylene bisulpirone. Please note that Example 1 of Table 1 is prepared by dissolving 20 g of silver nitrate in 1200 g of ethylene glycol solution to form a silver salt solution (concentration of silver is 1.66 wt%), and dissolving 8 g of polyvinylpyrrolidone in 1200 g. The ethylene glycol solution is used to form a protective solution. The reaction tank and the aging tank were separately charged with ethylene glycol l〇〇g and preheated at 17 ° C, and both maintained a reaction temperature of 150 C in the reaction. Further, the residence time of the reaction liquid in the reaction tank was 30 minutes' and the residence time in the aging tank was 3 minutes. Finally, the reaction solution was taken out from the aging tank and the nano silver wire was extracted. The reaction conditions of Examples 2 and 3 in Table 1 were the same as those in Example 1, but the molecular weights of the polyvinylpyrrolidone used in each Example were different. Effect of the same amount of p-polypyrrolidone on the nano-silver wire Example Polyvinylpyrrolidone molecular weight nano silver wire type 1 58000 Diameter 80~100 nm Length 6~10 μιη 2 8000 Diameter 60~80 nm Length 2 ~5 μιη 3 360000 Diameter 90~120 mn Length 8~12 μιη 11 201022451 As shown in Table 1, the higher the molecular weight of the polyvinylpyrrolidone used, the longer and thicker the resulting nanowire. • = Refer to Table 2, which shows the appearance of nanowires produced by various embodiments having different ratios of polyvinylpyrrolidone to silver salt. The embodiment 相同 is the same as the solid surface 1 of the watch-towel. Example 2 of Table 2 t 4, and 6 series use different weights of polyethylene to extract a solution of bismuth in ethylene glycol to form a protective solution, and the rest of the conditions are the same as in the embodiment i. Effect on Nano Silver Wire Polyethylene "Byrothone Weight (g) Nano Silver Line Type Example - Γ 80 Direct Control 80~100 nm Length 6~10 μιη 5 Ο 6 20 30 160 Diameter ~ 2301 Length 15 ~25 μιη 直桂90~120 nm Length 5~15 μηι Mostly granular, only a small amount of nano silver wire is shown in Table 2. If the ratio of polyvinylpyrrolidone to silver salt is too high, it will produce nano silver particles. Not conducive to the formation of nano silver wire. In addition, the lower the ratio, the thicker the diameter of the nanowire produced and the longer the length. ^ month, the second table of the table shows the appearance of the nano silver wire generated by the specific examples of different reaction temperatures. Embodiment 1 is the same as Embodiment 1 of Table 12 201022451 in Table 1. The reaction temperatures set in Examples 7, 8, and 9 in Table 3 were all the same, and the remaining conditions were the same as in Example 1. g, different reaction temperature on the nano silver wire ^ Example --~~--- Reaction temperature (°C) Nano silver wire type 1 ------- 150 diameter 80~100 nm length 6 ~10 μιη 7 ------- 140 Granular solid nanowires 8 160 Diameter 100~110 nm Length 7~10 μιη 9 170 Diameter 130~150 nm Length 7~11 μιη As shown in Table 3, reaction When the temperature is lower than 15 °C, nano silver particles will be produced and the nano silver wire will be formed. Further, as the reaction temperature rises, the diameter of the generated nano silver wire is thicker and the length is longer. ... 凊 Referring to Figure 2, Figure 3 is a graph showing the distribution of the conversion rate y versus the reaction time τ for each of the specific examples of Table 3. As shown in Fig. 3, curves 2〇, 22 24, and 26 represent the * cloth curves of the conversion rates of the examples j, 7, 8, and 9 for the reaction time, respectively. The reaction temperature is lower than that of the capital. Since the reaction rate is low, only silver fine particles can be precipitated and the nano silver wire cannot be precipitated. This and if ^ should be higher than 15 温度. 〇: Above, a large amount of nano silver is precipitated within 3G minutes, ':: Therefore, the anti-ship can be reasonably slaved as a minute. 13 201022451 Please refer to Table 4, Table 4 indicates the feed concentration oblique nano silver wire The effect of the diameter. Among them, Embodiment 1 is the same as Embodiment i in Table 1. Examples 1G, η, 12, 13 and 14 in Table 4 were prepared by dissolving different weights of silver nitrate in 1200 g of ethylene glycol to form a silver salt solution, and using different weights of polyvinylpyrrolidone in 1200 g. The ethylene glycol solution was used to form a protective solution, and the other conditions were the same as in the specific example 1. Table 4, 3; Effect of the same feed concentration on the nano silver wire Example Silver nitrate weight (g) Polyethylene "ratio ketone weight (g) nano silver wire type 1 20 80 diameter 80~100 nm length 6 ~10 μηι 10 10 160 Granular solid nanowires 11 40 160 diameter ~160 nm length 5~8 μηη 12 60 240 diameter ~210 nm length ~5 μτη 13 100 400 diameter ~290 nm length ~5 μπι 14 265 400 Diameter ~ 540 nm length ~ 5 μιη
如表四所示，進料濃度對奈米銀線之直徑呈現非線性 的正比關係，亦即，進料濃度越高所產生之奈米銀線直徑 越粗，然而其長度並無明顯變化。請注意，於實施例仞 14 201022451 中，由於銀離子濃度不足導致其碰撞機率低，因此僅能形 成奈米銀微粒而無法形成奈米銀線。 睛參閱圖四’圖四係緣示根據表四之各實施例之奈米 銀線直徑D對銀鹽進料濃度c❺分佈圖。如圖四所示， 銀鹽進料濃度C (wt%)與奈米銀線直徑D (nm)之間具有非 線性的正比關係。 此外’請參閱圖五，圖五係繪示上述之實施例】所生 春 叙奈米銀線的SEM圖。如圖五所示，實施例】所生成 之奈米銀線直徑其直徑大約在8〇〜1〇〇奈米之間。 、相較於先W技術，本發明之㈣連續製作奈米銀線之 • ^相水雜銀鹽絲在適當溫度下析岭米織粒， 啊加人倾㈣提供立體空間屏障* _奈祕微粒成 長為奈米銀顆粒’另一方面，藉由保護劑上之官能基可導 引銀微粒於、維方向上成長為奈米銀線。本發明之用以連 續製作奈求銀線之方法可以連續進料之方式生長高品質的 ® 奈米銀線，其有利於奈米銀線的大量生產。 藉由以上較佳具體實施例之詳述’係希望能更加清楚 描述本發明之特徵與精神，而並非以上述所揭露的較佳具 體實，例，對本發明之範嘴加以限制。相反地，其目的是 希望旎涵蓋各種改變及具相等性的安排於本發明所欲申 之專利範圍的範疇内。 15 201022451 【圖式簡單說明】 圖一係繪示根據本發明之一具體實施例之用以連續製 作奈米銀線之方法的示意圖。 圖二係繪示根據另一具體實施例之純化反應液以獲得 奈米銀線之步驟流程圖。 圖三係纟會示表三之各具體實施例之轉化率對反應時間 0 之分佈圖。 圖四係繪示根據表四之各實施例之奈米銀線直徑對銀 鹽進料濃度的分佈圖。 χ 圖五鱗轉侧1所生成之奈米銀_應圖。 【主要元件符號說明】 S10〜S16 :流程步驟 ❿ S160〜S168 :流程步驟 Τ反應時間 Υ :轉化率 20、22、24、26 :曲線 C:銀鹽進料濃度 D:奈米銀線直徑 16As shown in Table 4, the feed concentration has a non-linear proportional relationship with the diameter of the nano-silver wire, that is, the higher the feed concentration, the coarser the diameter of the nano-silver wire, but the length does not change significantly. Note that in Example 2010 14 201022451, since the collision probability is low due to insufficient silver ion concentration, only nano silver particles can be formed and the nano silver wire cannot be formed. Referring to Figure 4, the relationship between the diameter of the nanowire and the concentration of the silver salt feed c❺ according to the examples of Table 4 is shown. As shown in Figure 4, there is a non-linear proportional relationship between the silver salt feed concentration C (wt%) and the nano-silver wire diameter D (nm). In addition, please refer to Fig. 5, which shows the SEM image of the spring Sinami silver wire produced in the above embodiment. As shown in Fig. 5, in the embodiment, the diameter of the generated nano silver wire is about 8 〇 to 1 〇〇 nanometer. Compared with the prior W technology, the present invention (4) continuously produces nano silver wire • ^ phase water miscellaneous silver salt wire at a suitable temperature to analyze the ridge rice woven grain, ah plus people tilt (four) to provide a three-dimensional space barrier * _ nai secret The microparticles grow into nano-silver particles. On the other hand, the functional groups on the protective agent can guide the silver microparticles to grow into nano-silver lines in the dimension direction. The method for continuously producing the silver wire of the present invention can continuously grow a high quality ® nano silver wire, which is advantageous for mass production of the nano silver wire. The features and spirits of the present invention are more apparent from the detailed description of the preferred embodiments of the present invention, and are not intended to limit the scope of the invention. On the contrary, the intention is to cover various modifications and equivalent arrangements within the scope of the invention as claimed. 15 201022451 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing a method for continuously producing a nano silver wire according to an embodiment of the present invention. Figure 2 is a flow chart showing the steps of purifying the reaction liquid to obtain a nano silver wire according to another embodiment. Figure 3 shows the distribution of conversion rate versus reaction time 0 for each of the specific examples in Table 3. Figure 4 is a graph showing the distribution of the diameter of the nanosilver wire to the concentration of the silver salt feed according to the examples of Table 4. χ Figure 5 shows the nano silver generated by the side of the scale. [Main component symbol description] S10~S16: Flow procedure ❿ S160~S168: Process step Τ Reaction time Υ : Conversion rate 20, 22, 24, 26: Curve C: Silver salt feed concentration D: Nano silver wire diameter 16