200922865 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種以_ 可應用於複合材料、儲氫；粒子分散奈米碳管之方法及所得之分散液， 域。 4、電子、光電、原子力顯微鏡、生物感測器等領 【先前技術】 ::奈W (carbQn n贈㈣擁有非常優異 ==:::r人探討，但到_止奈',_二 …、不夕主要原因如闕喬治亞理工學院物理系紐de h啦所述石山其 發現10年後仍未有效應用，其障礙不僅在於奈米碳管的生產成本，更重要= 糊及自雜鶴」° _奈靖錄性之關ί 在於間具有很_凡得關引力1造成碳管相互雜在-起且不易 溶於水溶液或有機溶劑中。 傳統分散奈米碳管的方法，大致上可分為二大類： a.共價鍵修飾（covaient m〇dificaii〇n) 這種方法主要是彻舰做為錄化劑，因奈米碳管結構上的缺陷（如五 π環或七元環），可將長的碳管切短成達數百奈米的短奈米碳管，而在反應過 程中奈米碳管的管壁麵尾末端會因此反顧含氧的官能基，其中包括竣^、 羰基及醇鮮，«其它讀研究，賴或舰料録接在奈料f的側管 壁而不將奈米碳管切斷，減低對奈米碳管結構的破壞。上述這些官能基化的奈 米碳管，可有效的分散於水溶液或不同的有機溶劑中，奈米碳管的官能基化種 類與程序在文獻上記載的相當多，應視其應用的領域來選擇所欲接至奈米碳管 表面的官能基種類。 共價鍵修飾的方法雖然能有效的分散奈米碳管，但因為在官能基化的過程 200922865 中’會對奈米碳管的結構造成破壞’而改變了一些奈米碳管特有的性質，使得 之後的應用不如預期’因此便研究發展出非共價鍵修飾的方法來分散奈米碳管。 b.非共價鍵修飾（noncovalent modification) 非共價鍵修飾主要分為一種’一種是以界面活性劑做為分散劑，最常見的 是以十二烷基磺酸鈉（sodium dodecyl sufate，SDS)，先將奈米碳管以超音 波振盈’破壞奈来碳管間的凡得瓦爾引力，將碳管分別包覆在界面活性劑所形 成的微胞（micelles)裡，微胞的疏水端在内部包覆奈米碳管，親水端則在外 部與溶液接觸，形成穩定的分散。 另-類則是以具有極性侧鏈的高分子為主，常用的如聚乙稀辦細 (polyvinylpyrolidone，PVP)、磺酸化聚苯乙烯（polystyrenesulf〇nate， pss)等，分散的方法也是先利用超音波振盪破壞奈米碳管間的凡得瓦爾引力， 再利用高分子的主鏈纏繞在奈米碳管四周，形成分散的奈米碳管超分子 (supramolecular)錯合物’而極性的側鏈則與溶液介質接觸，達到分散效果， 形成錯合物的熱力學驅動力是排除在奈米碳f雜溶齡_疏水性界面，這 種方式也是-種可逆系統，可將溶液置換成極性較小的_ (如四氮咬味， THF) ’因為溶液系統㈣可造成纏繞效果失效。這種方式所形成的 為是-魏合㈣，對奈米碳管本狀高分子·f齡撕提升。 上述這二種非共價鍵修飾方式因為不會破壞奈米碳管結構，故對奈米碳管 本身的性質影響較小’但是就界祕來說，因為在生化❹⑻貞測中，界 面活性劑的存在胃造成電極鈍化、制訊舒擾料著極大的缺點，而高分子200922865 IX. Description of the Invention: [Technical Field] The present invention relates to a method for applying a composite material, hydrogen storage, particle-dispersed carbon nanotubes, and a dispersion liquid obtained. 4, electronics, optoelectronics, atomic force microscopy, biosensors, etc. [prior art] :: Nai W (carbQn n gift (four) has very good ==:::r people to explore, but to _ stop nai, _ two... The main reason for the eve of the eve is that the stone mountain of the Georgia Institute of Technology has not been effectively applied after 10 years of discovery. The obstacle is not only the production cost of the carbon nanotubes, but also the importance of the paste and the crane. ° _Nei Jing recorded the relationship between ί lies in a very close to the gravitational force 1 caused by carbon nanotubes mixed with each other and is not easily soluble in aqueous solutions or organic solvents. Traditional methods of dispersing carbon nanotubes can be roughly divided into Two categories: a. covalent bond modification (covaient m〇dificaii〇n) This method is mainly used as a recording agent, due to defects in the structure of the carbon nanotubes (such as five π rings or seven-membered rings), The long carbon tube can be cut into short nano carbon tubes of several hundred nanometers, and during the reaction, the end of the tube wall of the carbon nanotubes will be backed up with oxygen-containing functional groups, including 竣^ , carbonyl and mellow, «Other studies, Lai or ship materials are recorded in the side wall of the material f without the carbon nanotubes Breaking and reducing the damage to the structure of the carbon nanotubes. These functionalized carbon nanotubes can be effectively dispersed in aqueous solution or different organic solvents. The functionalization types and procedures of the carbon nanotubes are in the literature. There are quite a few records, and the type of functional groups to be attached to the surface of the carbon nanotubes should be selected according to the field of application. The method of covalent bond modification can effectively disperse the carbon nanotubes, but because of the functionalization Process 200922865 'damages the structure of the carbon nanotubes' and changes some of the unique properties of the carbon nanotubes, making the subsequent applications less than expected'. Therefore, research has developed a non-covalent bond modification method to disperse the nanoparticles. Carbon nanotubes b. noncovalent modification Non-covalent modification is mainly divided into one kind of surfactant is used as a dispersing agent, the most common is sodium dodecyl sulfonate (sodium dodecyl) Sufate, SDS), firstly use the ultrasonic vibration of the carbon nanotubes to destroy the van der Waals attraction between the carbon nanotubes, and coat the carbon tubes in the micelles formed by the surfactants. The hydrophobic end is coated with a carbon nanotube inside, and the hydrophilic end is externally contacted with the solution to form a stable dispersion. The other type is mainly a polymer having a polar side chain, and is commonly used as a polyethylene. (polyvinylpyrolidone, PVP), polystyrene polystyrene (PSS), etc., the dispersion method is also to use the ultrasonic oscillation to destroy the van der Waals attraction between the carbon nanotubes, and then use the main chain of the polymer to wrap around Around the carbon nanotubes, a dispersed nanocarbon tube supramolecular complex is formed, and the polar side chain is in contact with the solution medium to achieve a dispersion effect, and the thermodynamic driving force for forming the complex is excluded from the nanometer. Carbon f miscellaneous age _ hydrophobic interface, this way is also a kind of reversible system, the solution can be replaced by a less polar _ (such as four nitrogen bite, THF) 'because the solution system (four) can cause the winding effect to fail. In this way, it is - Weihe (4), which is a toughening of the carbon nanotubes. These two non-covalent bond modification methods have little effect on the properties of the carbon nanotubes themselves because they do not destroy the structure of the carbon nanotubes, but in terms of boundaries, because of the interfacial activity in biochemical ❹(8) speculation The presence of the agent causes the electrode to be passivated, and the stimuli of the signal are extremely disadvantageous, while the polymer
則可以拿來做為阻擋這些界祕性細隔絕層，但是也錢微降低細彳的電流 訊號。 ；IL 200922865 【發明說明】 本發明之目的在於提供一種以二氧化石夕粒子分散奈 減少操作步驟，並且保留奈米碳管原有的結構。 〃 e 、’可有效 本發明之另—目的在於提供_種奈米碳管之分散液，可保留 的結構及性質，並提升其應用性。 ’、不/、厌&原有 本發_二氧化雜子分散奈轉管之方法係It can be used as a barrier to these secret layers, but it also reduces the fine current signal. IL 200922865 [Description of the Invention] It is an object of the present invention to provide a process for reducing the dispersion of carbon dioxide particles by the oxidized particles and retaining the original structure of the carbon nanotubes. 〃 e , ' can be effective Another aspect of the present invention is to provide a dispersion of the carbon nanotubes, retaining the structure and properties, and improving the applicability thereof. ‘,不/, 厌& original method _ dioxide dimerization dispersion nebula method
政之效果，並據此得到一奈米碳管之分散液。 達L 上述帶正電狀二氧化雜子與奈米碳管較 =伽管可為多層壁奈米碳管或其他型式之奈米== 罝通常小於40 mg/mL，較佳為小於2〇 mg/mL。 s之3 而一乳化石夕之直控為1〜50 nm，較佳為彳ς . _ PH值通常為小於3，較佳為約2 ;二氧化雜液之 較佳為H〇 wt%。 f于“液之辰度通常小於15Wt%， 本發明之無機溶劑可為水或其他適#之無機溶劑。 【實施方法】 =明分散奈米碳管之方法，是利用一種非共價鍵且非有機溶劑修飾的 式为U碳官於水溶液中。它帶有正電荷的奈綠子水溶液加 =後，帶有高電荷的奈米粒子會環繞在奈㈣管上，最後利用奈米粒子帶同 電何的緣故，以斥力將奈米碳管均勻的分散在水溶液中。 本發明較佳實施例所使用之藥品包括： 1·多層壁奈米碳管：multi-walled carbon職otubes，純度約99 米應材製造。 丁、 2.二氧化賴浮液：c〇llc)idal siUca，為三氧化二銘包覆二氧切粒子之懸 200922865 浮水溶液，帶有正電荷，3〇 wt%，DuPont製造，商標名lud〇x CL。 3. 氯化氫：純度約96 %，SH0WA製造。 4. 氫氧化納：純度約35 %，OSAKA製造。 實施例1 a. 配製二氧化石夕粒子水溶液（lwt%) ’並以氣化氫（〇 im)調整其邱值 為2 ; b. 將多層壁奈来碳管加入二氧化石夕粒子水溶液中，形成奈米碳管含量為5 mg/mL之混合液； c. 利用超音波震盪器使多層壁奈米碳管完全分散於二氧化矽粒子水溶液 中，並靜錄天’觀❹層壁奈米碳管在二氧化雜子水溶液巾的分散情形。 比較例1〜5 重複實施例1之操作步驟，但其中二氧化♦粒子水溶液的pH值分別以氣化 氫（0.1M)及氫氧化納（0· 1M)調整為3、4、5、6、7，如表1所示。 實施例2〜3及比較例6 Μ實關1之操作麵，但其巾多層壁奈米碳管之含量分觀變為 mg/mL、20 mg/mL、40 mg/mL，如表 1 所示。 比較例7 重複實施例2之操作步驟，但步驟a個待二氧化雜仅去離子水， 且步驟b之多層壁奈米碳管含量為5呢/乱，如表1所示。 8 200922865 實施例4〜6及比較例§〜9 重複實施例4之操作步驟，但步驟b之多層壁奈米碳管之含息 且二氧化矽粒子之重量百分比分別改變為2wt%、5 wt%、l〇 wt%、里為如呢/虬， 如表1所示。 則^、3〇对％， 表1The effect of politics, and according to this, a dispersion of carbon nanotubes is obtained. Up to L The positively charged dioxins are compared with the carbon nanotubes = the gamma can be a multi-walled carbon nanotube or other type of nanometer == 罝 is usually less than 40 mg/mL, preferably less than 2 〇 Mg/mL. The s 3 and the emulsified stone are directly controlled to be 1 to 50 nm, preferably 彳ς. The _PH value is usually less than 3, preferably about 2; and the dioxic liquid is preferably H 〇 wt%. f is "the liquid is usually less than 15% by weight, and the inorganic solvent of the present invention may be water or other inorganic solvent. [Methods] = The method of dispersing the carbon nanotubes is to use a non-covalent bond and The non-organic solvent modified formula is U carbon in aqueous solution. After it has a positively charged aqueous solution of nepheline, the nanoparticle with high charge will surround the nanotube, and finally the nanoparticle will be used. For the sake of electricity, the carbon nanotubes are uniformly dispersed in the aqueous solution by repulsive force. The medicines used in the preferred embodiments of the present invention include: 1. Multi-walled carbon nanotubes: multi-walled carbon otubes, purity 99 m should be made of material. Ding, 2. Dioxide floating liquid: c〇llc) idal siUca, for the coating of dioxate particles of 200922865 floating aqueous solution, with positive charge, 3〇wt%, Made by DuPont under the trade name lud〇x CL. 3. Hydrogen chloride: purity about 96%, manufactured by SHOWA 4. Nanoparticles: purity about 35%, manufactured by OSAKA. Example 1 a. Preparation of aqueous solution of cerium oxide particles (lwt %) 'and adjust its Qi value to 2 with gasification hydrogen (〇im); b. The wall-necked carbon nanotubes are added to the aqueous solution of the cerium oxide particles to form a mixed liquid having a carbon nanotube content of 5 mg/mL; c. the multi-walled carbon nanotubes are completely dispersed in the cerium oxide by using an ultrasonic oscillator In the aqueous solution of the particles, the dispersion of the surface carbon nanotubes in the aqueous solution of the dioxins was observed. Comparative Examples 1 to 5 The procedure of Example 1 was repeated, but the pH of the aqueous solution of the oxidized particles was repeated. The values were adjusted to 3, 4, 5, 6, and 7 with hydrogenated hydrogen (0.1 M) and sodium hydroxide (0.1 M), respectively, as shown in Table 1. Examples 2 to 3 and Comparative Example 6 The operation surface, but the content of the multi-walled carbon nanotubes of the towel was changed to mg/mL, 20 mg/mL, and 40 mg/mL, as shown in Table 1. Comparative Example 7 The procedure of Example 2 was repeated. However, in step a, the deionized water is only deionized water, and the multi-walled carbon nanotube content of step b is 5/disorder, as shown in Table 1. 8 200922865 Examples 4 to 6 and Comparative Examples § ~ 9 The operation procedure of Example 4, but the content of the multi-walled carbon nanotubes of step b and the weight percentage of the cerium oxide particles are changed to 2 wt%, 5 wt%, l, respectively. 〇 wt%, inside is like /虬, as shown in Table 1. Then ^, 3〇 to %, Table 1
上述實施例及比較例之分散效果以照片及顯微鏡分析說明於下，並摘要列 於表1中。 9 200922865 A.二氧化矽粒子水溶液pH值對分散效果的影響 由實施例1及比較例卜5，多層壁奈米碳管（5mg/mL)在不同邱值之二氧 化矽粒子水溶液（1 wt%)中的分散情形如第丨及2圖所示。 其中’第1圖為超音波震蓋！小時後的分散情形：（a) pH=2;⑸pH=3; (c) pH-4’（d) pH=5，（e) pH=6 ;⑴PH=7 ;經超音波震盡丨小時後，可以發 現多層壁奈米碳料自分散在各水溶齡，無任何沉殿產生。 第2圖為靜置24小時後的分散情形：（a) pH=2 ;⑹pH=3 ; (c) pH=4 ; (d) pH 5 ’（e) pH-6 ’（f) PH=7。當靜置24小時後，可以清楚看到多層壁奈米碳管 在pH=2的二氧化石夕粒子水溶液中（&瓶）仍然均句的分散在溶液中；而在㈣巧 的二氧化雜子水溶液中（b〜fw皆可發現有分層或是纖的現紐生，表示 多層壁奈来碳管有糕在—起的現象發生。可知二氧化雜子水溶液（1㈣） 分散多層》米碳管（5 mg/mL)的邱值應小於3，較佳為約2。 B·多層壁奈米碳管添加量之影響 由實知例1〜3及比較則〜7，不同量㈣層壁奈米碳管在二氧化雜子水溶 液（pH=2，1 wt%)中的分散情形如第3及4圖所示。The dispersion effects of the above examples and comparative examples are illustrated by photographs and microscopic analysis, and are summarized in Table 1. 9 200922865 A. Effect of pH value of aqueous solution of cerium oxide particles on dispersion effect From Example 1 and Comparative Example 5, multi-walled nanotubes (5 mg/mL) in different values of cerium oxide particles (1 wt The dispersion in %) is shown in Figures 2 and 2. Among them, the first picture is the ultrasonic shock cover! Dispersion after hours: (a) pH=2; (5) pH=3; (c) pH-4'(d) pH=5, (e) pH=6; (1)PH=7; after ultrasonic shock It can be found that the multi-walled nano carbon material is self-dispersed in each water-soluble age and is produced without any sinking. Figure 2 shows the dispersion after standing for 24 hours: (a) pH = 2; (6) pH = 3; (c) pH = 4; (d) pH 5 '(e) pH-6 '(f) PH=7 . After standing for 24 hours, it can be clearly seen that the multi-layered wall carbon nanotubes are still dispersed in the solution in the aqueous solution of the dioxide dioxide particles of pH=2 (&bottle); In the aqueous solution of miscellaneous (b~fw can be found to have delamination or fiber, it is a phenomenon that the multi-layered wall has a cake-like phenomenon. It is known that the aqueous solution of dioxins (1(4)) is dispersed in multiple layers. The carbon value of the carbon nanotubes (5 mg/mL) should be less than 3, preferably about 2. The influence of the amount of B. multi-walled carbon nanotubes added by the practical examples 1 to 3 and the comparison of ~7, the different amounts (four) The dispersion of the wall-walled carbon nanotubes in the aqueous dioxate solution (pH = 2, 1 wt%) is shown in Figures 3 and 4.
第3圖為超音波震盪丄小時後的分散情形：⑷5 mg/mL多層壁奈米碳管分 » pH=2 ； (b) 5 mg/mL ； (c) 10 mg/mL ; (d) 20 mg/mL ； (e) 40 mg/mL 多層壁奈米碳管分餘二氧化雜子水溶液；經超音波紐丨小時後，可以發 現多層壁奈米碳管均勻分散在各水溶财，無任何沉澱產生。 ' 第4圖為靜置72小時後的分散情形：⑷5 多層壁奈米碳管分散於 離子 X (b) 5 mg/mL ’（c) 10 mg/mL ;⑷ 20 mg/mL ; (e) 40 mg/mL 多層壁 奈米碳管分散於二氧化矽粒子水溶液。 靜置72小時後，在比較例7中，可以發現在pH=2去離子水水溶液中（a瓶）， 多層壁奈祕餘快就料產生峨，證明多層絲米碳f之所雜分散於二 氧化雜子水溶液巾’的確是因為二氧化雜子所造細卿，料會因為溶 200922865 液的酸鹼值改變就能有效的分散多層壁奈米碳管。 在實施例卜3中，加入了 5〜20 mg/mL多層壁奈米碳管於二氧化矽粒子水溶 液（b〜d瓶），在經過72小時後仍能保持良好的分散，沒有沉澱現象發生，且 均勻分散的情況可持續兩星期左右。 然而，在比較例6中，加入了 4〇 mg/mL多層壁奈米碳管於二氧化矽粒子水 溶液（e瓶），在經過72小時後已明顯產生分層，無法有效的分散多層壁奈米 反& /、原因疋夕層壁奈米碳管所加入的量（40 mg/mL)已經超過二氧化石夕粒 子水溶液（pH=2，lwt%)所能負載的含量，多層壁奈米碳管會料無法再維持 均勻分散的情況。 經由上述結果，二氧化石夕粒子水溶液(pH=2，i wt%)可分散含量低於4〇呢航 之多層壁奈米碳管；較佳為低於2〇 mg/mL。 C.二氧化矽粒子之重量百分比之影響 由實施例3〜6及比較例㈣，在不同重量百分比的二氧化義子水溶液中， 多層壁奈米碳管（2G mg/mL)的分散情形如第5及6圖所示。 .第5圖為超音波震盪i小時後的分散情形二氧化石夕粒子的重量百分比：⑷ 1 (b) 2 ’（c) 5 ’⑷1〇 ’（e) 15 ;⑴30 wt%。經超音波震盪j小時後，可 以發現多層壁料碳管均勻分散在各水溶財，無任何職產生。 第6圖為靜置72小時後的分散情形，二氧化石夕粒子的重量百分比：⑷工； ()2 (c) 5’（d) 1G ’（e) 15 ’⑴3G wt%。在靜置72小時後，可以發現卜1〇 ’二氧化雜子水溶液（a~d瓶）’對於分散多層壁奈米碳管⑽呢M) 的效果很好。 夕而15 wt%的二氧化石夕粒子水溶液（e瓶）明顯有分層的現象發生 5代表過 夕=二氧化雜子邱於多層壁奈米碳管的分散。亦即，二氧化雜子水溶液 的濃度上限應小於15 wt% ;較佳為1〜1〇 wt〇%。 至於30 Λ的二氧化石夕粒子水溶液（f瓶）顺固了，這是因為二氧化石夕 11 200922865 粒子的重1百分比過高了，導致在加人绍縣米碳管後，水溶液變成了凝膠 的狀態。 D.穿透式電子顯微鏡分析 使用穿透式電子顯微鏡（Transmissi〇n eleetrOn mi_eQpe， (JEM-200CX from，舰），觀察奈米碳管分散之表面形貌，並確認二氧 化石夕粒子是否環繞於奈米碳管表面。第7圖為多層壁奈米碳管⑷分散前；⑹ 分散後之TEM圖形。 由圖(a)可以發現多層壁奈米碳管聚集在—起，形成—束束的樣子。而從圖 (b)可以看到夕層壁奈米碳;I»是—根—根分散開來，翻了二氧化雜子的確可 以分散多層壁奈米碳管’而衫層壁奈米碳f的表面也看财奈米粒子的存 在’表不一乳化石夕粒子確實環繞在多層壁奈米碳管的周圍。從圖⑹的局部放大 圖中，可以看出二氧化錄子，其粒子直徑約1(H4nm，而多層壁奈米碳管直徑 約為40 nm ’很賴_*出二氧化雜子圍齡錢壁奈米碳管顺的情形。 E.原子力顯微鏡分析 (atomic force microscope > AFM) (SPA-400 multiple together with SPI_3800N 5 Seiko) 同4刖後之表面形貌和確認二氧化雜子是否環繞於奈米碳管表面。第8 為夕層壁奈米碳管(a)分散前；⑹分散後之AFM之2-D圖形。 圓⑷為單根多層壁奈米碳管表_細，可以清制知❹㈣奈 <，、徑40 nm的直圓管，其形貌符合利用電弧放電法所合成，且目 描得:的單根多層壁綱管同樣簡子力顯微鏡進行掃 月顯發現在多層壁奈米碳管周圍環繞著二氧化石夕粒子，其粒 12 200922865 子直徑也在10〜 m石m左右’與穿透式電子顯微鏡之社果;^ 被-氧化錄子雜的單根多層壁奈米碳管其 。_⑻上得知 過多層壁奈米碳管的直徑增加了不少loo nm，比之毫無修飾 米碳管周圍。 月—氧化矽粒子環繞在多層壁奈 藉由原子力顯微鏡與穿透式電子顯微鏡分析， 粒子的確圍繞於多層壁奈米碳管周圍。且因二氧化雜子:有 非Γ層壁奈米碳管可均勻的分散於二氧化雜子水溶液中: _非4鍵且非有機溶劑的方式，可有效減少操作步驟，並且保留住奈米石山 管原有的優異性質，可進而利用在許多產業上。 Ί 13 200922865 【圖式簡單說明】 第3及4圖為不^奈米碳官在不同邱值之二氧化雜子水溶液中的分散情形。 第5及6 衫層壁料碳#在二氧化雜子水溶液巾的分散情形。Figure 3 shows the dispersion after ultrasonic oscillation for a few hours: (4) 5 mg/mL multi-walled carbon nanotubes » pH=2; (b) 5 mg/mL; (c) 10 mg/mL; (d) 20 Mg/mL; (e) 40 mg/mL multi-walled carbon nanotubes with a residual aqueous solution of dioxins; after ultrasonication for a few hours, it can be found that the multi-walled carbon nanotubes are evenly dispersed in each water, without any Precipitation occurs. Figure 4 shows the dispersion after 72 hours of standing: (4) 5 multi-walled nanotubes dispersed in ion X (b) 5 mg/mL '(c) 10 mg/mL; (4) 20 mg/mL; (e) The 40 mg/mL multi-walled carbon nanotubes were dispersed in an aqueous solution of cerium oxide particles. After standing for 72 hours, in Comparative Example 7, it was found that in the aqueous solution of pH=2 deionized water (a bottle), the multi-layer wall was quickly produced to produce ruthenium, which proved that the multi-layered silk rice carbon f was dispersed in The aqueous solution of the dioxins is indeed because of the fineness of the dioxins, which is expected to effectively disperse the multi-walled carbon nanotubes due to the change in the pH of the solution 200922865. In the embodiment 3, 5~20 mg/mL multi-walled carbon nanotubes were added to the cerium oxide particle aqueous solution (b~d bottle), and the dispersion was maintained after 72 hours, and no precipitation occurred. And evenly dispersed for about two weeks. However, in Comparative Example 6, 4 〇mg/mL multi-walled nanotubes were added to the cerium oxide particle aqueous solution (e-bottle), and stratification was apparent after 72 hours, and the multi-layered wall was not effectively dispersed. The amount of rice (</, the reason) added to the layer of carbon nanotubes (40 mg/mL) has exceeded the content of the aqueous solution of the dioxide (pH=2, lwt%), The carbon nanotubes are no longer able to maintain uniform dispersion. Through the above results, the aqueous solution of the cerium oxide particles (pH = 2, i wt%) can be dispersed in a multi-walled carbon nanotube having a content of less than 4 Å; preferably less than 2 〇 mg/mL. C. Effect of weight percentage of cerium oxide particles From Examples 3 to 6 and Comparative Example (4), in different weight percentages of aqueous dioxide solution, the dispersion of multi-walled nanotubes (2G mg/mL) is as follows. Figures 5 and 6 show. Fig. 5 is a graph showing the weight percentage of the dispersed particles of the cerium oxide after i-hour of ultrasonic oscillation: (4) 1 (b) 2 '(c) 5 '(4) 1 〇 '(e) 15 ; (1) 30 wt%. After ultrasonic shock for j hours, it can be found that the multi-layer wall carbon tube is evenly dispersed in each water, and no job is produced. Fig. 6 is a dispersion after 72 hours of standing, the weight percentage of the cerium oxide particles: (4) work; () 2 (c) 5' (d) 1G '(e) 15 '(1) 3G wt%. After standing for 72 hours, it was found that the aqueous solution of the dioxins (a~d bottle) had a good effect on dispersing the multi-walled carbon nanotubes (10). On the other hand, 15 wt% of the aqueous solution of the dioxide dioxide (e bottle) is obviously stratified. 5 represents the dispersion of the multi-layered carbon nanotubes. That is, the upper limit of the concentration of the aqueous dioxide solution should be less than 15 wt%; preferably 1 to 1 〇 wt 〇 %. As for the 30 Λ 二 夕 夕 粒子 粒子 粒子 粒子 f f f f , , , , 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 2009 The state of the gel. D. Penetrating electron microscopy analysis using a transmission electron microscope (Transmissi〇n eleetrOn mi_eQpe, (JEM-200CX from, ship), observe the surface morphology of the carbon nanotube dispersion, and confirm whether the dioxide particles surround On the surface of the carbon nanotubes, Figure 7 shows the TEM pattern after dispersion of the multi-walled carbon nanotubes (4); (6) The TEM pattern after dispersion. It can be seen from the diagram (a) that the multi-walled carbon nanotubes are clustered together to form bundles. From the figure (b), we can see the nano-carbon of the smectite wall; I» is the root-root disperse, and the oxidized dioxide can indeed disperse the multi-walled carbon nanotubes. The surface of the nano-carbon f also looks at the presence of the nano-particles. The emulsified stone particles do surround the multi-walled carbon nanotubes. From the partial enlargement of Figure (6), the oxidized record can be seen. The particle diameter is about 1 (H4nm, and the multi-layered wall carbon nanotubes are about 40 nm in diameter). It is very close to the case where the dioxins are in the wall of the carbon nanotubes. E. Atomic force microscopy analysis (atomic) Force microscope > AFM) (SPA-400 multiple together with SPI_3800N 5 Seiko) with 4 The surface morphology of the crucible and confirm whether the dioxins surround the surface of the carbon nanotubes. The eighth is the layer of carbon nanotubes (a) before dispersion; (6) the 2-D pattern of the dispersed AFM. For a single multi-walled carbon nanotube table _ fine, you can clear the know-how (four) nai <, 40 mm diameter straight round tube, the shape is consistent with the use of arc discharge method, and the appearance of: a single The multi-layered wall tube is also simulated by a simple force microscope. The multi-layered wall carbon nanotubes are surrounded by the cerium dioxide particles, and the particles 12 200922865 are also in the diameter of 10~m stone m' and the transmission electron microscope. The fruit is a single multi-walled nanocarbon tube that is oxidized and recorded. _(8) It is known that the diameter of the multi-walled carbon nanotubes has increased by a lot of loo nm, compared to the unmodified carbon nanotubes. The cerium-cerium oxide particles are surrounded by a multi-layer wall and analyzed by atomic force microscopy and transmission electron microscopy. The particles do surround the multi-walled carbon nanotubes. And because of the dioxins: there are non-tantalum nanocarbons. The tube can be uniformly dispersed in the aqueous dioxide solution: _ non-4 bond and non-organic solvent The method can effectively reduce the operation steps and retain the original excellent properties of the nanostone mountain tube, which can be utilized in many industries. Ί 13 200922865 [Simple diagram of the diagram] Figures 3 and 4 are not carbon nano officials Dispersion in aqueous solutions of dioxins of different values. 5th and 6th wall carbons# Dispersion in aqueous dioxins.
队W形。 ---- 第8二，奈米碳管分散前後之TEM > 碳管分散前後之AFM 散情形。 _百分_二氧化雜子水絲巾1層縣米碳管的分 二，奈米碳管分散前後之TEM圖形。 夕曰壁奈米碳管分散前後之AFM之2-D圖形。Team W shape. ---- No. 8 2, TEM > before and after carbon nanotube dispersion. AFM dispersion before and after carbon tube dispersion. _Percentage _ Dioxon water silk scarf 1 layer of county carbon tube Dimensions Second, the TEM pattern before and after the dispersion of the carbon nanotubes. The 2-D pattern of AFM before and after the dispersion of the Nippon carbon nanotubes.