TWI411571B - A method of dispersing carbon nanotubes with silica particles and a dispersion thereof - Google Patents
A method of dispersing carbon nanotubes with silica particles and a dispersion thereof Download PDFInfo
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本發明係關於一種以二氧化矽粒子分散奈米碳管之方法及所得之分散液，可應用於複合材料、儲氫材料、電子、光電、原子力顯微鏡、生物感測器等領域。The invention relates to a method for dispersing a carbon nanotube by using cerium oxide particles and the obtained dispersion, which can be applied to the fields of composite materials, hydrogen storage materials, electrons, photoelectrics, atomic force microscopes, biosensors and the like.
由於奈米碳管(carbon nanotube)擁有非常優異的性質，因此以奈米碳管為基礎相關應用在近年來有不少人探討，但到目前為止奈米碳管的實際產品仍然不多，主要原因如美國喬治亞理工學院物理系教授de Heer所述「奈米碳管發現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，更重要的是應用時之分散性，製程限制及自我組裝能力」。而影響奈米碳管分散性之關鍵在於奈米碳管間具有很強的凡得瓦爾引力，易造成碳管相互聚集在一起且不易溶於水溶液或有機溶劑中。Due to the excellent properties of carbon nanotubes, many applications have been discussed in recent years. However, the actual products of carbon nanotubes are still few, so far. The reason is as described by De Heer, professor of physics at the Georgia Institute of Technology in the United States. "The carbon nanotubes have not been effectively used after 10 years of discovery. The obstacles are not only the production cost of the carbon nanotubes, but also the dispersion of the application. Limitation and self-assembly capabilities." The key to affecting the dispersibility of carbon nanotubes is that there is a strong van der Waals attraction between the carbon nanotubes, which tends to cause the carbon tubes to gather together and is not easily soluble in aqueous solutions or organic solvents.
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(covalent modification)這種方法主要是利用強酸做為強氧化劑，因奈米碳管結構上的缺陷(如五元環或七元環)，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或頭尾末端會因此反應成含氧的官能基，其中包括羧基、羰基及醇基等，亦有其它文獻研究，將氟或鏈烷等官能基接在奈米碳管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。The traditional methods of dispersing carbon nanotubes can be roughly divided into two categories: a. covalent modification. This method mainly uses strong acid as a strong oxidant, due to defects in the structure of the carbon nanotubes (such as A five-membered ring or a seven-membered ring) can cut a long carbon tube into a short carbon nanotube of several hundred nanometers. During the reaction, the wall or the end of the carbon nanotube will react accordingly. Oxygen-containing functional groups, including carboxyl groups, carbonyl groups, and alcohol groups, etc., and other literature studies, in which a functional group such as fluorine or an alkane is attached to the side wall of the carbon nanotube without cutting the carbon nanotube. Reduce damage to the structure of the carbon nanotubes. The above-mentioned functionalized carbon nanotubes can be effectively dispersed in an aqueous solution or a different organic solvent, and the types and procedures of the functionalization of the carbon nanotubes are considerably recorded in the literature, and should be considered in the field of application. Select the type of functional group that is desired to be attached to the surface of the carbon nanotube.
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。Although the covalent bond modification method can effectively disperse the carbon nanotubes, it changes the structure of the carbon nanotubes during the functionalization process, and changes the unique properties of some carbon nanotubes. Subsequent applications were not as expected, so research into non-covalent bond modification methods was developed to disperse the carbon nanotubes.
b.非共價鍵修飾(noncovalent modification)非共價鍵修飾主要分為二種，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盪，破壞奈米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，微胞的疏水端在內部包覆奈米碳管，親水端則在外部與溶液接觸，形成穩定的分散。b. Noncovalent modification Non-covalent bond modification is mainly divided into two kinds, one is based on surfactant as a dispersing agent, the most common is sodium dodecyl sufate (sodium dodecyl sufate, SDS), the carbon nanotubes are first oscillated by ultrasonic waves to destroy the van der Waals attraction between the carbon nanotubes, and the carbon tubes are respectively coated in the micelles formed by the surfactant, and the microcapsules are hydrophobic. The end is internally coated with a carbon nanotube, and the hydrophilic end is externally contacted with the solution to form a stable dispersion.
另一類則是以具有極性側鏈的高分子為主，常用的如聚乙烯吡喀烷酮(polyvinylpyrolidone，PVP)、磺酸化聚苯乙烯(polystyrenesulfonate，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管壁與溶液介質的疏水性界面，這種方式也是一種可逆系統，可將溶液置換成極性較小的溶劑(如四氫呋喃，THF)，因為溶液系統改變可造成纏繞效果失效。這種方式所形成的分散也可視為是一種複合材料，對奈米碳管本身及高分子的性質都會有所提升。The other type is mainly a polymer with polar side chains. Commonly used, such as polyvinylpyrolidone (PVP), polystyrene sulfonate (PSS), etc., the dispersion method is also the first to use ultrasonic waves. Oscillation destroys the van der Waals attraction between the carbon nanotubes, and then the main chain of the polymer is wrapped around the carbon nanotubes to form a dispersed nanocarbon tube supramolecular complex, while the polar side chains are Contact with the solution medium to achieve the dispersion effect, the thermodynamic driving force for forming the complex is to exclude the hydrophobic interface between the carbon nanotube wall and the solution medium. This method is also a reversible system, which can replace the solution with a less polar one. Solvents (such as tetrahydrofuran, THF) can cause the winding effect to fail due to changes in the solution system. The dispersion formed by this method can also be regarded as a composite material, which will improve the properties of the carbon nanotube itself and the polymer.
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，但是就界面活性劑來說，因為在生化感測器偵測中，界面活性劑的存在易造成電極鈍化、偵測訊號干擾等有著極大的缺點，而高分子則可以拿來做為阻擋這些界面活性劑的隔絕層，但是也會稍微降低偵測的電流訊號。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 the case of surfactants, because they are detected in biochemical sensors. The presence of surfactants has the potential to cause electrode passivation, detection of signal interference, etc., and polymers can be used as an insulating layer to block these surfactants, but will also slightly reduce the detected current signal.
本發明之目的在於提供一種以二氧化矽粒子分散奈米碳管之方法，可有效減少操作步驟，並且保留奈米碳管原有的結構。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for dispersing a carbon nanotube with cerium oxide particles, which can effectively reduce the number of steps and preserve the original structure of the carbon nanotube.
本發明之另一目的在於提供一種奈米碳管之分散液，可保留奈米碳管原有的結構及性質，並提升其應用性。Another object of the present invention is to provide a dispersion of a carbon nanotube that retains the original structure and properties of the carbon nanotube and enhances its applicability.
本發明以二氧化矽粒子分散奈米碳管之方法係將帶正電荷之二氧化矽粒子與奈米碳管於一無機溶劑中混合，使奈米碳管被二氧化矽粒子環繞，以達到分散之效果，並據此得到一奈米碳管之分散液。The method for dispersing a carbon nanotube by using cerium oxide particles is to mix positively charged cerium oxide particles with a carbon nanotube in an inorganic solvent, so that the carbon nanotubes are surrounded by cerium oxide particles to achieve The effect of dispersion is obtained, and a dispersion of a carbon nanotube is obtained accordingly.
上述帶正電荷之二氧化矽粒子與奈米碳管較佳為超音波震盪之方式混合。本發明之奈米碳管可為多層壁奈米碳管或其他型式之奈米碳管；奈米碳管之含量通常小於40 mg/mL，較佳為小於20 mg/mL。The positively charged cerium oxide particles are preferably mixed with the carbon nanotubes in a manner that is ultrasonically oscillated. The carbon nanotube of the present invention may be a multi-walled carbon nanotube or other type of carbon nanotube; the content of the carbon nanotube is usually less than 40 mg/mL, preferably less than 20 mg/mL.
而二氧化矽之直徑為1~50 nm，較佳為10~15 nm；二氧化矽粒子水溶液之pH值通常為小於3，較佳為約2；二氧化矽粒子水溶液之濃度通常小於15 wt%，較佳為1~10 wt%。The diameter of the cerium oxide is 1 to 50 nm, preferably 10 to 15 nm; the pH of the aqueous cerium oxide particle solution is usually less than 3, preferably about 2; the concentration of the aqueous cerium oxide particle solution is usually less than 15 wt. %, preferably 1 to 10 wt%.
本發明之無機溶劑可為水或其他適當之無機溶劑。The inorganic solvent of the present invention may be water or other suitable inorganic solvent.
本發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方式分散奈米碳管於水溶液中。它利用帶有正電荷的奈米粒子水溶液加入奈米碳管後，帶有高電荷的奈米粒子會環繞在奈米碳管上，最後利用奈米粒子帶同電荷的緣故，以斥力將奈米碳管均勻的分散在水溶液中。The method for dispersing a carbon nanotube of the present invention is to disperse a carbon nanotube in an aqueous solution by means of a non-covalent bond and a non-organic solvent modification. After it is added to the carbon nanotube by using a positively charged aqueous solution of nanoparticle, the nanoparticle with high charge will surround the carbon nanotube, and finally the nanoparticle will be charged with the same charge. The carbon nanotubes are uniformly dispersed in the aqueous solution.
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 nanotubes，純度約99%，東元奈米應材製造。The medicines used in the preferred embodiments of the present invention include: 1. Multi-walled carbon nanotubes, having a purity of about 99%, manufactured by TECO.
2.二氧化矽懸浮液：colloidal silica，為三氧化二鋁包覆二氧化矽粒子之懸浮水溶液，帶有正電荷，30 wt%，DuPont製造，商標名LUDOX CL。2. Ceria suspension: colloidal silica, a suspension aqueous solution of cerium oxide coated with cerium oxide particles, with a positive charge, 30 wt%, manufactured by DuPont under the trade name LUDOX CL.
3.氯化氫：純度約96%，SHOWA製造。3. Hydrogen chloride: purity of about 96%, manufactured by SHOWA.
4.氫氧化納：純度約35%，OSAKA製造。4. Sodium Hydroxide: Purity is about 35%, manufactured by OSAKA.
a.配製二氧化矽粒子水溶液(1 wt%)，並以氯化氫(0.1M)調整其pH值為2；b.將多層壁奈米碳管加入二氧化矽粒子水溶液中，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，並靜置數天，觀察多層壁奈米碳管在二氧化矽粒子水溶液中的分散情形。a. preparing an aqueous solution of cerium oxide particles (1 wt%) and adjusting its pH value to 2 with hydrogen chloride (0.1 M); b. adding a multi-layered wall carbon nanotube to an aqueous solution of cerium oxide particles to form a carbon nanotube a mixture of 5 mg/mL; c. Fully disperse the multi-walled carbon nanotubes in an aqueous solution of cerium oxide particles using an ultrasonic oscillator, and let stand for several days to observe the oxidation of the multi-walled carbon nanotubes The dispersion in the aqueous solution of cerium particles.
重複實施例1之操作步驟，但其中二氧化矽粒子水溶液的pH值分別以氯化氫(0.1M)及氫氧化鈉(0.1M)調整為3、4、5、6、7，如表1所示。The procedure of Example 1 was repeated except that the pH of the aqueous solution of cerium oxide particles was adjusted to 3, 4, 5, 6, and 7 with hydrogen chloride (0.1 M) and sodium hydroxide (0.1 M), respectively, as shown in Table 1. .
重複實施例1之操作步驟，但其中多層壁奈米碳管之含量分別改變為10 mg/mL、20 mg/mL、40 mg/mL，如表1所示。The procedure of Example 1 was repeated except that the content of the multilayered wall carbon nanotubes was changed to 10 mg/mL, 20 mg/mL, and 40 mg/mL, respectively, as shown in Table 1.
重複實施例2之操作步驟，但步驟a使用不含二氧化矽粒子之去離子水，且步驟b之多層壁奈米碳管含量為5 mg/mL，如表1所示。The procedure of Example 2 was repeated, except that step a used deionized water containing no cerium oxide particles, and the multi-walled nanotubes of step b were 5 mg/mL, as shown in Table 1.
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量為20 mg/mL，且二氧化矽粒子之重量百分比分別改變為2 wt%、5 wt%、10 wt%、15 wt%、30 wt%，如表1所示。The procedure of Example 4 was repeated, but the content of the multi-walled carbon nanotubes of step b was 20 mg/mL, and the weight percentage of the cerium oxide particles was changed to 2 wt%, 5 wt%, 10 wt%, 15 respectively. Wt%, 30 wt%, as shown in 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。The dispersion effects of the above examples and comparative examples are illustrated by photographs and microscopic analysis, and are summarized in Table 1.
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1~5，多層壁奈米碳管(5 mg/mL)在不同pH值之二氧化矽粒子水溶液(1 wt%)中的分散情形如第1及2圖所示。A. Effect of pH value of aqueous solution of cerium oxide particles on dispersion effect From Example 1 and Comparative Examples 1 to 5, multi-layered wall carbon nanotubes (5 mg/mL) at different pH values of cerium oxide particle aqueous solution (1 wt The dispersion in %) is shown in Figures 1 and 2.
其中，第1圖為超音波震盪1小時後的分散情形：(a)pH＝2；(b)pH＝3；(c)pH＝4；(d)pH＝5；(e)pH＝6；(f)pH＝7；經超音波震盪1小時後，可以發現多層壁奈米碳管均勻分散在各水溶液中，無任何沉澱產生。1 is the dispersion after ultrasonic oscillation for 1 hour: (a) pH = 2; (b) pH = 3; (c) pH = 4; (d) pH = 5; (e) pH = 6 (f) pH=7; after ultrasonic vibration for 1 hour, it was found that the multilayered-walled carbon nanotubes were uniformly dispersed in each aqueous solution without any precipitation.
第2圖為靜置24小時後的分散情形：(a)pH＝2；(b)pH＝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的二氧化矽粒子水溶液中(a瓶)仍然均勻的分散在溶液中；而在pH＝3~7的二氧化矽粒子水溶液中(b~f瓶)皆可發現有分層或是沉澱的現象發生，表示多層壁奈米碳管有聚集在一起的現象發生。可知二氧化矽粒子水溶液(1 wt%)分散多層壁奈米碳管(5 mg/mL)的pH值應小於3，較佳為約2。Figure 2 shows the dispersion after standing for 24 hours: (a) pH = 2; (b) pH = 3; (c) pH = 4; (d) pH = 5; (e) pH = 6; ) pH = 7. After standing for 24 hours, it can be clearly seen that the multi-walled carbon nanotubes are still uniformly dispersed in the solution in the aqueous solution of cerium oxide particles (a bottle) of pH=2; and the oxidation at pH=3~7 In the aqueous solution of cerium particles (b~f bottle), delamination or precipitation may occur, indicating that the multi-walled carbon nanotubes are clustered together. It is understood that the pH of the aqueous solution of the cerium oxide particles (1 wt%) dispersed multi-walled carbon nanotubes (5 mg/mL) should be less than 3, preferably about 2.
B.多層壁奈米碳管添加量之影響由實施例1~3及比較例6~7，不同量的多層壁奈米碳管在二氧化矽粒子水溶液(pH＝2，1 wt%)中的分散情形如第3及4圖所示。B. Effect of the amount of multi-layered wall carbon nanotubes added From Examples 1 to 3 and Comparative Examples 6 to 7, different amounts of multi-layered wall carbon nanotubes were used in an aqueous solution of cerium oxide particles (pH = 2, 1 wt%). The dispersion is shown in Figures 3 and 4.
第3圖為超音波震盪1小時後的分散情形：(a)5 mg/mL多層壁奈米碳管分散於pH＝2的去離子水；(b)5 mg/mL；(c)10 mg/mL；(d)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；經超音波震盪1小時後，可以發現多層壁奈米碳管均勻分散在各水溶液中，無任何沉澱產生。Figure 3 shows the dispersion after 1 hour of ultrasonic oscillation: (a) 5 mg/mL multi-walled nanotubes dispersed in deionized water at pH=2; (b) 5 mg/mL; (c) 10 mg (d) 20 mg/mL; (e) 40 mg/mL multi-walled nanotubes dispersed in an aqueous solution of cerium oxide particles; after ultrasonic vibration for 1 hour, it was found that the multi-walled carbon nanotubes were uniformly dispersed. In each aqueous solution, no precipitation occurred.
第4圖為靜置72小時後的分散情形：(a)5 mg/mL多層壁奈米碳管分散於去離子水；(b)5 mg/mL；(c)10 mg/mL；(d)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。Figure 4 shows the dispersion after 72 hours of standing: (a) 5 mg/mL multi-walled nanotubes dispersed in deionized water; (b) 5 mg/mL; (c) 10 mg/mL; 20 mg/mL; (e) 40 mg/mL multi-walled nanotubes were dispersed in an aqueous solution of cerium oxide particles.
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)，多層壁奈米碳管很快就聚集產生沉澱，證明多層壁奈米碳管之所以能分散於二氧化矽粒子水溶液中，的確是因為二氧化矽粒子所造成的影響，並不會因為溶液的酸鹼值改變就能有效的分散多層壁奈米碳管。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-walled carbon nanotubes quickly aggregated to form a precipitate, which proved that the multilayered-walled carbon nanotubes were Dispersion in the aqueous solution of cerium oxide particles is indeed due to the influence of cerium oxide particles, and does not effectively disperse the multi-walled carbon nanotubes due to the change in the pH value of the solution.
在實施例1~3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。In Examples 1 to 3, 5~20 mg/mL multi-walled carbon nanotubes were added to the cerium oxide particle aqueous solution (b~d bottle), which remained well dispersed after 72 hours, without precipitation. Occurrence and uniform dispersion can last for about two weeks.
然而，在比較例6中，加入了40 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碳管，其原因是多層壁奈米碳管所加入的量(40 mg/mL)已經超過二氧化矽粒子水溶液(pH＝2，1wt%)所能負載的含量，多層壁奈米碳管會聚集無法再維持均勻分散的情況。However, in Comparative Example 6, 40 mg/mL multi-walled carbon nanotubes were added to the aqueous solution of cerium oxide particles (e-bottle), and stratification was apparent after 72 hours, and the multi-layered nano-crystals could not be effectively dispersed. Carbon tube, the reason is that the amount of multi-walled carbon nanotubes (40 mg / mL) has exceeded the content of the aqueous solution of cerium oxide particles (pH = 2, 1wt%), multi-walled carbon nanotubes Aggregation can no longer maintain a uniform dispersion.
經由上述結果，二氧化矽粒子水溶液(pH＝2，1 wt%)可分散含量低於40 mg/mL之多層壁奈米碳管；較佳為低於20 mg/mL。Through the above results, an aqueous solution of cerium oxide particles (pH = 2, 1 wt%) can disperse a multi-walled carbon nanotube having a content of less than 40 mg/mL; preferably less than 20 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8~9，在不同重量百分比的二氧化矽粒子水溶液中，多層壁奈米碳管(20 mg/mL)的分散情形如第5及6圖所示。C. Effect of weight percentage of cerium oxide particles From Examples 3 to 6 and Comparative Examples 8 to 9, dispersion of multi-walled nanotubes (20 mg/mL) in aqueous solutions of different weight percentages of cerium oxide particles The situation is shown in Figures 5 and 6.
第5圖為超音波震盪1小時後的分散情形二氧化矽粒子的重量百分比：(a)1；(b)2；(c)5；(d)10；(e)15；(f)30 wt%。經超音波震盪1小時後，可以發現多層壁奈米碳管均勻分散在各水溶液中，無任何沉澱產生。Figure 5 is the weight percentage of cerium oxide particles in the dispersion after 1 hour of ultrasonic oscillation: (a) 1; (b) 2; (c) 5; (d) 10; (e) 15; (f) 30 Wt%. After 1 hour of ultrasonic vibration, it was found that the multi-walled carbon nanotubes were uniformly dispersed in each aqueous solution without any precipitation.
第6圖為靜置72小時後的分散情形，二氧化矽粒子的重量百分比：(a)1；(b)2；(c)5；(d)10；(e)15；(f)30 wt%。在靜置72小時後，可以發現1~10 wt%的二氧化矽粒子水溶液(a~d瓶)，對於分散多層壁奈米碳管(20 mg/mL)的效果很好。Figure 6 is the dispersion after 72 hours of standing, the weight percentage of cerium oxide particles: (a) 1; (b) 2; (c) 5; (d) 10; (e) 15; (f) 30 Wt%. After standing for 72 hours, 1 to 10 wt% of cerium oxide particle aqueous solution (a~d bottle) can be found to work well for dispersing multi-walled carbon nanotubes (20 mg/mL).
而15 wt%的二氧化矽粒子水溶液(e瓶)明顯有分層的現象發生，代表過多的二氧化矽粒子不利於多層壁奈米碳管的分散。亦即，二氧化矽粒子水溶液的濃度上限應小於15 wt%；較佳為1~10 wt%。The 15 wt% aqueous solution of cerium oxide particles (e bottle) obviously has delamination, which means that excessive cerium oxide particles are not conducive to the dispersion of multi-walled carbon nanotubes. That is, the upper limit of the concentration of the aqueous cerium oxide particle solution should be less than 15% by weight; preferably from 1 to 10% by weight.
至於30 wt%的二氧化矽粒子水溶液(f瓶)則凝固了，這是因為二氧化矽粒子的重量百分比過高了，導致在加入多層壁奈米碳管後，水溶液變成了凝膠的狀態。As for the 30 wt% aqueous solution of ceria particles (f bottle), it is solidified because the weight percentage of the ceria particles is too high, resulting in the gelation of the aqueous solution after the addition of the multi-walled carbon nanotubes. .
D.穿透式電子顯微鏡分析使用穿透式電子顯微鏡(Transmission electron microscope，TEM)(JEM－200CX from，JEOL)，觀察奈米碳管分散前後之表面形貌，並確認二氧化矽粒子是否環繞於奈米碳管表面。第7圖為多層壁奈米碳管(a)分散前；(b)分散後之TEM圖形。D. Transmission electron microscopy analysis Using a transmission electron microscope (TEM) (JEM-200CX from, JEOL), the surface morphology of the carbon nanotubes before and after dispersion was observed, and it was confirmed whether the cerium oxide particles were surrounded. On the surface of the carbon nanotubes. Figure 7 is a multi-layered wall carbon nanotube (a) before dispersion; (b) TEM pattern after dispersion.
由圖(a)可以發現多層壁奈米碳管聚集在一起，形成一束束的樣子。而從圖(b)可以看到多層壁奈米碳管是一根一根分散開來，證明了二氧化矽粒子的確可以分散多層壁奈米碳管，而且多層壁奈米碳管的表面也看到有奈米粒子的存在，表示二氧化矽粒子確實環繞在多層壁奈米碳管的周圍。從圖(b)的局部放大圖中，可以看出二氧化矽粒子，其粒子直徑約10~14nm，而多層壁奈米碳管直徑約為40 nm，很清楚的顯示出二氧化矽粒子圍繞住多層壁奈米碳管周圍的情形。It can be seen from Fig. (a) that the multi-walled carbon nanotubes are gathered together to form a bundle. From the figure (b), it can be seen that the multi-walled carbon nanotubes are dispersed one by one, which proves that the cerium oxide particles can indeed disperse the multi-walled carbon nanotubes, and the surface of the multi-walled carbon nanotubes is also The presence of nanoparticles is observed, indicating that the cerium oxide particles do surround the multi-layered wall carbon nanotubes. From the partial enlarged view of Fig. (b), it can be seen that the cerium oxide particles have a particle diameter of about 10 to 14 nm, and the multilayered wall carbon nanotubes have a diameter of about 40 nm, which clearly shows that the cerium oxide particles surround Living around a multi-walled carbon nanotube.
E.原子力顯微鏡分析使用原子力顯微鏡(atomic force microscope，AFM)(SPA－400 multiple function units together with SPI－3800N，Seiko)輕拍式掃描模式，觀察奈米碳管分散前後之表面形貌和確認二氧化矽粒子是否環繞於奈米碳管表面。第8圖為多層壁奈米碳管(a)分散前；(b)分散後之AFM之2－D圖形。E. Atomic force microscopy analysis using atomic force microscope (AFM) (SPA-400 multiple function units together with SPI-3800N, Seiko) tapping scanning mode to observe the surface morphology and confirmation of carbon nanotubes before and after dispersion Whether the cerium oxide particles surround the surface of the carbon nanotubes. Figure 8 is a multi-layered wall carbon nanotube (a) before dispersion; (b) 2-D pattern of AFM after dispersion.
圖(a)為單根多層壁奈米碳管表面形貌圖，可以清楚的知道多層壁奈米碳管為直徑40 nm的直圓管，其形貌符合利用電弧放電法所合成，具有筆直棒狀且結構完整缺陷少之特徵，與低溫製程的化學氣相沉積法所製備出來呈彎曲狀且缺陷較多的多層壁奈米碳管形貌有著相當大的差別。Figure (a) shows the surface topography of a single multi-walled carbon nanotube. It can be clearly seen that the multi-walled carbon nanotube is a straight tube with a diameter of 40 nm. The morphology is consistent with the arc discharge method and has straightness. The characteristics of the rod-shaped and structurally intact defects are quite different from those of the multi-layered wall carbon nanotubes prepared by the chemical vapor deposition method of the low-temperature process and having a curved shape and many defects.
將被二氧化矽粒子環繞的單根多層壁奈米碳管同樣以原子力顯微鏡進行掃描得到圖(b)，可以明顯發現在多層壁奈米碳管周圍環繞著二氧化矽粒子，其粒子直徑也在10~15 nm左右，與穿透式電子顯微鏡之結果相符。由圖(b)上得知被二氧化矽粒子環繞的單根多層壁奈米碳管其直徑約為100 nm，比之毫無修飾過多層壁奈米碳管的直徑增加了不少，再次證明二氧化矽粒子環繞在多層壁奈米碳管周圍。A single multi-walled carbon nanotube surrounded by cerium oxide particles is also scanned by atomic force microscopy to obtain the figure (b). It is obvious that the cerium oxide particles are surrounded by the multilayered carbon nanotubes, and the particle diameter is also At about 10~15 nm, it is consistent with the results of the transmission electron microscope. It is known from Figure (b) that the single-walled nano-carbon nanotubes surrounded by cerium oxide particles have a diameter of about 100 nm, which is much larger than the diameter of the multi-walled carbon nanotubes. It was demonstrated that the cerium oxide particles surround the multi-layered wall carbon nanotubes.
藉由原子力顯微鏡與穿透式電子顯微鏡分析，可證明帶正電荷之二氧化矽粒子的確圍繞於多層壁奈米碳管周圍。且因二氧化矽粒子帶有正電荷的緣故，彼此間產生斥力，故多層壁奈米碳管可均勻的分散於二氧化矽粒子水溶液中。此種非共價鍵且非有機溶劑的方式，可有效減少操作步驟，並且保留住奈米碳管原有的優異性質，可進而利用在許多產業上。By atomic force microscopy and transmission electron microscopy analysis, it can be proved that the positively charged cerium oxide particles do surround the multi-walled carbon nanotubes. Moreover, since the cerium oxide particles have a positive charge, a repulsive force is generated between them, so that the multilayered wall carbon nanotubes can be uniformly dispersed in the aqueous solution of the cerium oxide particles. Such a non-covalent bond and a non-organic solvent can effectively reduce the number of operating steps and retain the original excellent properties of the carbon nanotubes, which can be utilized in many industries.
第1及2圖為多層壁奈米碳管在不同pH值之二氧化矽粒子水溶液中的分散情形。Figures 1 and 2 show the dispersion of multi-walled nanotubes in aqueous solutions of cerium oxide particles at different pH values.
第3及4圖為不同量的多層壁奈米碳管在二氧化矽粒子水溶液中的分散情形。Figures 3 and 4 show the dispersion of different amounts of multi-walled nanotubes in an aqueous solution of cerium oxide particles.
第5及6圖為不同重量百分比的二氧化矽粒子水溶液中，多層壁奈米碳管的分散情形。Figures 5 and 6 show the dispersion of multi-walled nanotubes in aqueous solutions of different weight percentages of cerium oxide particles.
第7圖為多層壁奈米碳管分散前後之TEM圖形。Figure 7 is a TEM image of the multilayered wall carbon nanotubes before and after dispersion.
第8圖為多層壁奈米碳管分散前後之AFM之2－D圖形。Figure 8 is a 2-D pattern of the AFM before and after the dispersion of the multilayered wall carbon nanotubes.
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