TWI421210B - Method to separate the carbon nanotubes by jelly fig pectin - Google Patents
Method to separate the carbon nanotubes by jelly fig pectin Download PDFInfo
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本發明係有關於一種以天然愛玉果膠分散奈米碳管之方法，尤指一種採用台灣特有天然愛玉果膠(jelly fig pectin)為材料，係具有低表面張力及高黏性可有效應用於奈米碳管之分散。The invention relates to a method for dispersing a carbon nanotube by natural jade pectin, in particular to using a unique jadely pectin of Taiwan, which has low surface tension and high viscosity. Used in the dispersion of carbon nanotubes.
由於奈米碳管具有獨特的結構，極佳的機械、熱傳導、物性、化性與其高長寬比之特性，使其應用極為廣泛。但因為奈米碳管之間具有微弱的凡得瓦力，所以彼此易聚集在一起且不溶於水或有機溶劑中，造成奈米碳管在使用上無法發揮最佳的功用，因此分散奈米碳管將是奈米碳管應用上的一大關鍵技術。按傳統分散奈米碳管的技術，一般都是以化學性的界面活性劑、有機溶劑為主，然而，過程中所使用的化學原料皆有毒性，不僅容易造成人員傷害，而且更會造成嚴重的環境污染。例如目前習知專利前案技術，有中華民國公開第20071194號專利申請案，其主要係利用具有共價結合的親水物質之官能化奈米碳管，將該等奈米碳管添加至極性溶劑之水溶液中，使該等奈米碳管分散於該水溶液中，但分散過程中所使用的極性溶劑皆有毒性且會造成環境污染。再者，中華民國專利第I258789號專利案，其技術係利用水為基礎溶劑，加入分散劑、穩定劑、成膜劑與增黏劑等溶質，以及奈米碳管，其中基礎溶劑與溶質形成低黏度水溶液，奈米碳管則懸浮於其中，形成奈米碳管懸浮液，分散過程中所使用的溶劑皆為有機溶劑，也會會造成環境污染。此外，目前習知中華民國專利前案技術，公告第I258789號與第I284116號，及公開第200700312號與第200710029號等專利前案，其專利技術範疇無針對使用天然愛玉果膠當分散劑，及規範分散單壁奈米碳管方法。顯然，本發明為最新的分散奈米碳管技術，而且不會對人員造成傷害及環境的污染。Because of its unique structure, the carbon nanotubes have excellent mechanical, thermal, physical, chemical and high aspect ratio characteristics, making them extremely versatile. However, because of the weak van der Waals force between the carbon nanotubes, they are easy to gather together and are insoluble in water or organic solvents, which causes the carbon nanotubes to not perform optimally in use, thus dispersing the nanoparticles. Carbon tubes will be a key technology in the application of carbon nanotubes. According to the traditional technology of dispersing carbon nanotubes, chemical surfactants and organic solvents are generally used. However, the chemical materials used in the process are toxic, which not only causes personal injury, but also causes serious damage. Environmental pollution. For example, the prior art patent application technology has the patent application No. 20071194 of the Republic of China, which mainly utilizes a functionalized carbon nanotube having a hydrophilic substance bonded in a covalent manner, and the carbon nanotubes are added to the polar solvent. In the aqueous solution, the carbon nanotubes are dispersed in the aqueous solution, but the polar solvents used in the dispersion process are both toxic and cause environmental pollution. Furthermore, the Patent No. I258789 of the Republic of China patent uses a water-based solvent to add a solute such as a dispersant, a stabilizer, a film former and a tackifier, and a carbon nanotube in which a base solvent and a solute are formed. The low-viscosity aqueous solution, the carbon nanotubes are suspended therein to form a carbon nanotube suspension, and the solvent used in the dispersion process is an organic solvent, which may also cause environmental pollution. In addition, at present, the patents of the Republic of China patents, the publications No. I258789 and No. I284116, and the publications of the patents No. 200700312 and No. 200710029, etc., have no patents for the use of natural jade pectin as a dispersant. And standard methods for dispersing single-walled carbon nanotubes. Obviously, the present invention is the latest dispersing carbon nanotube technology, and does not cause harm to personnel and environmental pollution.
有鑑於目前現有奈米碳管分散技術仍存在缺點，本發明人基於豐富的學識與經驗，乃積極努力投入研究，經潛心研發，終於發展出確具進步性及產業利用性之本發明。本發明所使用之無毒性的天然植物愛玉果膠，為台灣現特有農產品，愛玉凍在台灣是一種廣受歡迎之夏日飲品，其主要成分是由愛玉瘦果(achenes)之外果皮(pericarp)所溶離之高酯化度果膠受到果膠溶出之內生性(endogenous)果膠酯(pectinesterase,PE)作用而生成低酯化度果膠，再與水中之二價陽離子如：鈣、鎂等離子形成架橋連結成網狀結構而成膠。由於本發明人觀察到愛玉果膠具有低表面張力與高黏性等特性，果膠溶解後，經過超音波震盪，有助於愛玉果膠能進入單壁奈米碳管的管壁末端及表面，並吸附於單壁奈米碳管表面，造成單壁奈米碳管間的凡得瓦爾力下降，有效的分散單壁奈米碳管，以避免團聚現象再現。In view of the shortcomings of the existing carbon nanotube dispersion technology, the present inventors have actively invested in research based on rich knowledge and experience, and have developed the present invention which is progressive and industrially usable. The non-toxic natural plant love jade pectin used in the present invention is a unique agricultural product in Taiwan, and the jade jelly is a popular summer drink in Taiwan, and its main component is the peel of the achene achenes. (pericarp) high esterification degree pectin dissolved by pectin ester endogenous pectin esterase (PE) to produce low esterification degree pectin, and then with divalent cations in water such as: calcium The magnesium plasma forms a bridge and is connected into a mesh structure to form a glue. Since the inventors have observed that the jade pectin has low surface tension and high viscosity, after the pectin is dissolved, after ultrasonic vibration, it can help the jade pectin enter the end of the wall of the single-walled carbon nanotube. And the surface, and adsorbed on the surface of the single-walled carbon nanotubes, resulting in a decrease in the van der Waals force between the single-walled carbon nanotubes, effectively dispersing the single-walled carbon nanotubes to avoid the agglomeration phenomenon.
本發明之主要目的，在於提供一種製造簡便、無污染性，可有效分散奈米碳管於水溶液中，充份發揮奈米碳管之效能的製造方法。其技術內容，尤指一種採用台灣特有天然愛玉果膠(jelly fig pectin)為材料，係具有低表面張力及高黏性可有效應用於奈米碳管之分散，並利用超音波震盪進行分散處理，進一步的降低碳管間的凡得瓦爾力。具體的技術手段流程包括有準備原料、分散化處理、過濾處理及烘乾處理。準備原料包括備妥一預定量的單壁奈米碳管及一預定量的純化愛玉果膠。備妥一預定量的單壁奈米碳管，係包括純化改質：將該單壁奈米碳管置於硫酸/硝酸溶液中進行一預定時間的超音波震盪；過濾分離：將震洗完畢之溶液以過濾方式將該單壁奈米碳管與該硫酸/硝酸溶液分離；中性化處理：以去離子水洗掉殘留在該單壁奈米碳管上的該硫酸/硝酸溶液，直至單壁奈米碳管的pH值維持在中性；及烘乾處理：將經中性化處理過的該單壁奈米碳管以一預定溫度及一預定時間烘烤，以去除其上的水氣。備妥一預定量的純化愛玉果膠，係包括稀釋處理：取一預定量之純化後的愛玉果膠，以去離子水稀釋；及攪拌：進行一預定時間的攪拌使該愛玉果膠均勻溶於該去離子水中，形成愛玉果膠水溶液。分散化處理：將備妥之該單壁奈米碳管加入備妥之愛玉果膠水溶液中，利用超音波震盪一預定時間，使單壁奈米碳管均勻分散於愛玉果膠水溶液中。過濾處理：利用抽氣過濾裝置濾去該愛玉果膠水溶液中的多餘愛玉果膠與去離子水。烘乾處理：將剩餘的單壁奈米碳管以一預定溫度烘烤一預定時間，以去除多餘水氣，獲得分散處理後的該單壁奈米碳管。The main object of the present invention is to provide a manufacturing method which is easy to manufacture and non-polluting, and can effectively disperse a carbon nanotube in an aqueous solution to fully exert the performance of the carbon nanotube. Its technical content, especially the use of Taiwan's unique jadely pectin as a material, has low surface tension and high viscosity, can be effectively applied to the dispersion of carbon nanotubes, and is dispersed by ultrasonic vibration. Treatment, further reducing the Van der Waals force between the carbon tubes. The specific technical means includes preparation of raw materials, dispersion treatment, filtration treatment and drying treatment. Preparing the raw materials includes preparing a predetermined amount of single-walled carbon nanotubes and a predetermined amount of purified jade pectin. Preparing a predetermined amount of single-walled carbon nanotubes, including purification and modification: placing the single-walled carbon nanotubes in a sulfuric acid/nitric acid solution for a predetermined period of ultrasonic oscillation; filtering separation: shaking up The solution is separated from the sulfuric acid/nitric acid solution by filtration; neutralization treatment: the sulfuric acid/nitric acid solution remaining on the single-walled carbon nanotube is washed away with deionized water until The pH of the single-walled carbon nanotube is maintained at neutral; and the drying treatment: the neutralized single-walled carbon nanotube is baked at a predetermined temperature and for a predetermined time to remove the steam. Preparing a predetermined amount of purified Aiguo pectin, including dilution treatment: taking a predetermined amount of purified Aiyu pectin diluted with deionized water; and stirring: stirring for a predetermined time to make the love jade fruit The gum is uniformly dissolved in the deionized water to form an aqueous solution of jade pectin. Dispersion treatment: the prepared single-walled carbon nanotubes are added to the prepared aqueous solution of Ai Jade Pectin, and ultrasonic waves are shaken for a predetermined time to uniformly disperse the single-walled carbon nanotubes in the aqueous solution of Aiyu Pectin. . Filtration treatment: the excess jade pectin and deionized water in the aqueous solution of the jade pectin are filtered by a suction filter device. Drying treatment: the remaining single-walled carbon nanotubes are baked at a predetermined temperature for a predetermined time to remove excess moisture, and the single-walled carbon nanotubes after dispersion treatment are obtained.
如圖1所示，本發明以天然愛玉果膠分散奈米碳管之方法，係包括：As shown in FIG. 1 , the method for dispersing a carbon nanotube in natural jade pectin of the present invention comprises:
(a)準備原料，其包括：(a) Preparing raw materials, including:
(a1)備妥一預定量的單壁奈米碳管；及(a1) preparing a predetermined amount of single-walled carbon nanotubes; and
(a2)備妥一預定量的純化愛玉果膠，其包括：(a2) Preparing a predetermined amount of purified Ai Pectin comprising:
(b)分散化處理：隨後秤取適量純化改質過之單壁奈米碳管加入愛玉果膠水溶液中，使單壁奈米碳管均勻分散於愛玉果膠水溶液中；(b) Dispersing treatment: then adding an appropriate amount of purified and modified single-walled carbon nanotubes to the aqueous solution of Ai Jade Pectin, so that the single-walled carbon nanotubes are uniformly dispersed in the aqueous solution of Aiyu Pectin;
(c)過濾處理：利用抽氣過濾裝置濾去多餘的愛玉果膠；及(c) Filtration treatment: filtering out excess jade pectin by using a suction filter device;
(d)烘乾處理：最後將剩餘的單壁奈米碳管置於真空烘箱內烘烤，進而得到分散處理後的單壁奈米碳管。(d) Drying treatment: Finally, the remaining single-walled carbon nanotubes are baked in a vacuum oven to obtain a single-walled carbon nanotube after dispersion treatment.
如圖1所示，本發明以天然愛玉果膠分散奈米碳管之方法，係包括：As shown in FIG. 1 , the method for dispersing a carbon nanotube in natural jade pectin of the present invention comprises:
(a)準備原料，其包括：(a) Preparing raw materials, including:
(a1)備妥一預定量的單壁奈米碳管，其包括：(a1) Preparing a predetermined amount of single-walled carbon nanotubes, including:
(a11)純化改質：由於單壁奈米碳管本身具有雜質，必須將單壁奈米碳管進行純化改質處理，即先將單壁奈米碳管置於含有體積比為3：1的硫酸/硝酸溶液(硫酸98%，硝酸70%)中進行超音波震盪(請配合參看附件一所示)，震盪時間為1小時；(a11) Purification and modification: Since the single-walled carbon nanotubes themselves have impurities, the single-walled carbon nanotubes must be purified and modified, that is, the single-walled carbon nanotubes are first placed in a volume ratio of 3:1. Ultrasonic vibration in a sulfuric acid/nitric acid solution (98% sulfuric acid, 70% nitric acid) (please refer to Appendix 1), the oscillation time is 1 hour;
(a12)過濾分離：再將震洗完畢之溶液以過濾方式將單壁奈米碳管與硫酸/硝酸溶液分離；(a12) Filtration separation: separating the shock-washed solution into a single-walled carbon nanotube and a sulfuric acid/nitric acid solution by filtration;
(a13)中性化處理：接著再以去離子水洗掉殘留在單壁奈米碳管上的硫酸/硝酸溶液，直至單壁奈米碳管的pH值維持在中性(pH值約為7)；(a13) Neutralization treatment: then the sulfuric acid/nitric acid solution remaining on the single-walled carbon nanotubes is washed away with deionized water until the pH of the single-walled carbon nanotubes is maintained at neutral (pH is about 7);
(a14)烘乾處理：再將經中性化處理的單壁奈米碳管置於約100℃的真空烘箱烘烤約24小時，以去除其上的水氣；及(a14) drying treatment: the neutralized single-walled carbon nanotubes are then baked in a vacuum oven at about 100 ° C for about 24 hours to remove moisture from them;
(a2)備妥一預定量的純化愛玉果膠，其包括：(a2) Preparing a predetermined amount of purified Ai Pectin comprising:
(a21)稀釋處理：秤取一預定量之純化後的愛玉果膠，以去離子水稀釋；及(a21) Dilution treatment: weighing a predetermined amount of purified Aiyu pectin diluted with deionized water;
(a22)攪拌：即利用磁石攪拌機攪拌約1小時，以便愛玉果膠能均勻溶於去離子水中；(a22) stirring: stirring with a magnet mixer for about 1 hour, so that the jade pectin can be uniformly dissolved in deionized water;
(b)分散化處理：隨後秤取適量純化改質過之單壁奈米碳管加入愛玉果膠水溶液中，利用超音波震盪約1小時使單壁奈米碳管均勻分散於愛玉果膠水溶液中；(b) Decentralized treatment: Then, an appropriate amount of purified and modified single-walled carbon nanotubes were added to the aqueous solution of Aiyu Pectin, and the single-walled carbon nanotubes were uniformly dispersed in Aiyuguo by ultrasonic vibration for about 1 hour. In the aqueous solution of glue;
(c)過濾處理：利用抽氣過濾裝置濾去多餘的愛玉果膠與去離子水；及(c) Filtration treatment: filtering excess jade pectin and deionized water by means of a suction filtering device;
(d)烘乾處理：最後將剩餘的單壁奈米碳管置於約100℃真空烘箱內烘烤約24小時以去除多餘的水氣，進而得到分散處理後的單壁奈米碳管。(d) Drying treatment: Finally, the remaining single-walled carbon nanotubes were baked in a vacuum oven at about 100 ° C for about 24 hours to remove excess moisture, thereby obtaining a dispersed single-walled carbon nanotube.
本發明係利用穿透式電子顯微鏡分析，其可作為判斷單壁奈米碳管分佈情形的工具。附件二圖1(a)所示為單壁奈米碳管在未經愛玉果膠處理前之結構情形，整體管徑範圍分佈較廣，可看出單壁奈米碳管分散性不佳，具有糾結團聚之現象，造成奈米碳管在使用上無法發揮最佳的作用。附件二圖1(b)所示為團聚的單壁奈米碳管經超音波震盪分散及愛玉果膠包覆下成單獨型式存在的證據之TEM照片。The present invention utilizes a transmission electron microscope analysis which can be used as a tool for judging the distribution of single-walled carbon nanotubes. Figure 1 (a) of Annex II shows the structure of single-walled carbon nanotubes before they are treated with Aiyu Pectin. The overall diameter range is widely distributed. It can be seen that the single-walled carbon nanotubes have poor dispersion. It has the phenomenon of entanglement and agglomeration, which causes the carbon nanotubes to not play the best role in use. Figure 1 (b) of Annex II shows the TEM photograph of the evidence for the existence of agglomerated single-walled carbon nanotubes in a separate form by ultrasonic vibration dispersion and a mixture of jade pectin.
本發明實驗例中，證明單壁奈米碳管經由超音波震盪及愛玉果膠雙重分散作用下確實能降低奈米碳管間的凡得瓦爾力，改善團聚現象之功效。附件三圖1(a)為單壁奈米碳管於水溶液中僅以超音波震盪1小時，並於室溫下放置2小時後之情形。由照片中可明顯看出下層的單壁奈米碳管因彼此糾結與纏繞，造成團聚沉澱現象而出現分層。而純化後之單壁奈米碳管在相同條件下加入愛玉果膠分散之水溶液經超音波震盪1小時，於室溫下放置超過6個月，如附件三圖1(b)所示，仍然保持穩定均勻分散的黑色懸浮液。In the experimental example of the present invention, it is proved that the single-walled carbon nanotubes can effectively reduce the van der Waals force between the carbon nanotubes and improve the agglomeration phenomenon through the ultrasonic vibration and the double dispersion of the jade pectin. Figure 3 (a) of Annex III shows the case where the single-walled carbon nanotubes are only oscillated by ultrasonic waves for 1 hour in an aqueous solution and left at room temperature for 2 hours. It is apparent from the photograph that the underlying single-walled carbon nanotubes are entangled and entangled with each other, causing agglomeration and precipitation to cause delamination. The purified single-walled carbon nanotubes were added to the aqueous solution of the jade pectin dispersion under the same conditions and subjected to ultrasonic vibration for 1 hour, and left at room temperature for more than 6 months, as shown in Figure 3 (b) of Annex III. A black suspension that remains stable and evenly dispersed remains.
以上所述，僅為本創作之一可行實施例，並非用以限定本創作之專利範圍，凡舉依據下列請求項所述之內容、特徵以及其精神而為之其他變化的等效實施，皆應包含於本創作之專利範圍內。本創作除上述優點外，並深具產業之利用性，可有效改善習用所產生之缺失，而且所具體界定於請求項之特徵，未見於同類物品，故而具實用性與進步性，已符合新型專利要件，爰依法具文提出申請，謹請 鈞局依法核予專利，以維護本申請人合法之權益。The above is only one of the possible embodiments of the present invention, and is not intended to limit the scope of the patents of the present invention, and the equivalent implementations of other changes according to the contents, features and spirits of the following claims are It should be included in the scope of this creation patent. In addition to the above advantages, this creation has deep industrial applicability, can effectively improve the lack of use, and is specifically defined in the characteristics of the request item, not found in similar items, so it is practical and progressive, and has been in line with the new type. For patents, the application shall be filed in accordance with the law. The Bureau shall be required to approve the patent in accordance with the law to protect the lawful rights and interests of the applicant.
(a)．．．準備原料(a). . . Preparing raw materials
(a1)．．．備妥一預定量的單壁奈米碳管(a1). . . Prepare a predetermined amount of single-walled carbon nanotubes
(a11)．．．純化改質(a11). . . Purification and upgrading
(a12)．．．過濾分離(a12). . . Filter separation
(a13)．．．中性化處理(a13). . . Neutralization
(a14)．．．烘乾處理(a14). . . Drying treatment
(a2)．．．備妥一預定量的純化愛玉果膠(a2). . . Prepare a predetermined amount of purified Ai Pectin
(a21)．．．稀釋處理(a21). . . Dilution treatment
(a22)．．．攪拌(a22). . . Stir
(b)．．．分散化處理(b). . . Decentralized treatment
(c)．．．過濾處理(c). . . Filter processing
(d)．．．烘乾處理(d). . . Drying treatment
圖1為本發明之流程示意圖。Figure 1 is a schematic flow chart of the present invention.
附件一：為本發明之實驗裝置圖。Annex I: Figure of the experimental device of the present invention.
附件二：Annex II:
圖1(a)為未經愛玉果膠處理的單壁奈米碳管；及Figure 1 (a) is a single-walled carbon nanotube treated without jade pectin; and
圖1(b)為本發明經超音波震盪分散及愛玉果膠包覆下的單壁奈米碳管。Fig. 1(b) shows a single-walled carbon nanotube under the ultrasonic vibration dispersion and the jade pectin coating.
附件三：Annex III:
圖1(a)為本發明經超音波震盪處理1小時純化後之單壁奈米碳管水溶液，於室溫下放置超過6個月照片；及1(a) is a single-walled carbon nanotube aqueous solution purified by ultrasonic vibration treatment for 1 hour, and is placed at room temperature for more than 6 months; and
圖1(b)為本發明添加愛玉果膠後經超音波震盪1小時，於室溫下放置超過6個月。Fig. 1(b) shows the addition of jade pectin in the present invention, which is subjected to ultrasonic vibration for 1 hour and left at room temperature for more than 6 months.
(a)．．．準備原料(a). . . Preparing raw materials
(a1)．．．備妥一預定量的單壁奈米碳管(a1). . . Prepare a predetermined amount of single-walled carbon nanotubes
(a11)．．．純化改質(a11). . . Purification and upgrading
(a12)．．．過濾分離(a12). . . Filter separation
(a13)．．．中性化處理(a13). . . Neutralization
(a14)．．．烘乾處理(a14). . . Drying treatment
(a2)．．．備妥一預定量的純化愛玉果膠(a2). . . Prepare a predetermined amount of purified Ai Pectin
(a21)．．．稀釋處理(a21). . . Dilution treatment
(a22)．．．攪拌(a22). . . Stir
(b)．．．分散化處理(b). . . Decentralized processing
(c)．．．過濾處理(c). . . Filter processing
(d)．．．烘乾處理(d). . . Drying treatment
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040131859A1 (en) * | 2001-03-26 | 2004-07-08 | Rachel Yerushalmi-Rozen | Method for the preparation of stable suspensions and powders of single carbon nanotubes |
| TW201038472A (en) * | 2009-03-04 | 2010-11-01 | Toray Industries | Carbon nanotube-containing composition, catalyst for carbon nanotube production and carbon nanotube aqueous dispersion liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20040131859A1 (en) * | 2001-03-26 | 2004-07-08 | Rachel Yerushalmi-Rozen | Method for the preparation of stable suspensions and powders of single carbon nanotubes |
| TW201038472A (en) * | 2009-03-04 | 2010-11-01 | Toray Industries | Carbon nanotube-containing composition, catalyst for carbon nanotube production and carbon nanotube aqueous dispersion liquid |
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