201226314 六、發明說明： 【發明所屬之技術領域】 本發明是有關於-種製備石墨之方法，特別是指 用於製備石墨奈米片之方法。 a 種 【先前技術】201226314 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for preparing graphite, and more particularly to a method for preparing a graphite nanosheet. a species [prior art]
由於半導體及電子產業之電子元件曰益縮小化，為了 防止半導體s件或電子元件因電荷的累積而造成短路，j 抗靜電材料的開發為目前研究的課題之…一般抗靜電材： 的製作方法是將導電性材料（如金屬粉末、金屬纖維或石黑 纖維等）均句分散添加至環氧樹脂中，湘導電性材料的二 性來降低電荷累積，同時減少電子元件短路的發生。 該導電性材料例如奈米級之石墨，該石墨具有突出的 導熱性質（3〇〇〇W/m . K)和力學性質（1〇6〇 GPa)，以及室严 下高速電子遷移率（15000 cm2/v. s)，藉由該石墨之較佳電 子遷移率的特性來降低表面電阻值，使材料内部不易累積電 何，以減少靜電危害之產生。所以，複合材料及防靜電塗料 等領域已廣泛使用奈米級石墨做為導電性材料。 製備奈米級石墨的方法主要有電弧法（arc meth〇d)、雷 射蒸發法（laser vaporizati〇n)和氣相催化熱解法（phase catalytic pyrolysis)。電弧法係在一含有氦氣的真空室内， 利用電弧放電所產生的高溫（約3〇〇〇〜4〇〇〇〇c)，使固體碳 源蒸發氣化，並進行結構重排後沉積在一基材上，該方法常 伴有石墨微粒及煤灰等大量雜質，因而常需後續的純化處理 ，又因為電弧法之製造設備複雜，技術上需控制冷卻速率及 201226314 氦氣的μ力來達到成核的品質。雷射蒸發法與電弧法的原理 相^，係則高能雷射對焦^鉢材而使其表面碳材蒸發， 接者在催化劑的作用下’經冷卻後沉積在—基材上。雷射蒸 發法仍有存在與該法相m而氣相催化熱解法係 以易分解的有機物（如乙快或甲烧等）為碳源，在5〇〇〜 1200。。溫度範圍内，以及過渡金屬元素催化的作用下，使 碳，分解產生碳原子且吸附在金屬顆粒的晶面上，並沉積在 4曰曰面上’该方法需吸附在金屬顆粒上成核長晶，故金屬顆 粒的大小、分佈及投人量皆會影響成核的品質。氣相催化執 解法所製備出之奈米級石墨常有產量低、純度低且分佈不均 等問題。除了上述三種製法之外，其他之製法如電解法、球 磨法或擴散火焰法等，皆存在有製程技術條件較難控制、產 品品質低及產量低等問題。 由上述可知，現有的奈米級石墨之製備方法仍存在許 多：題’因此目前業界仍希望發展出一種兼具製程及設備 簡早、成本低及不耗能，且能製備出具有更佳抗靜電效果 之奈米級石墨的方法。 【發明内容】 因此，本發明之一目的，即在提供一種設備簡單、成 本低且能製備出更佳抗靜電效果之石墨奈米片之方法。 於是，本發明用於製備石墨奈米片之方法，包含：將 -第-氧化劑與-石墨進行氧化反應，以獲得一反應物； 將該反應物、-第二氧化劑、一插層劑與水進行混合，以 獲得一混合物；於—密閉環境下，使該混合物進行加敎， 201226314 以製得一膨脹型石墨；以及將該膨脹型石墨進行高溫處理 及脫層處理，以獲得一石墨奈米片。As the electronic components of the semiconductor and electronics industries have been reduced, in order to prevent semiconductor devices or electronic components from being short-circuited due to the accumulation of electric charges, the development of antistatic materials is a subject of current research... General antistatic materials: The conductive material (such as metal powder, metal fiber or stone black fiber) is uniformly dispersed into the epoxy resin, and the duality of the conductive material reduces the charge accumulation and reduces the occurrence of short circuit of the electronic component. The conductive material is, for example, nano-scale graphite having outstanding thermal conductivity (3 〇〇〇 W/m . K) and mechanical properties (1 〇 6 〇 GPa), and high-speed electron mobility under room temperature (15000) Cm2 / v. s), by the characteristics of the preferred electron mobility of the graphite to reduce the surface resistance value, so that the inside of the material is not easy to accumulate electricity to reduce the occurrence of electrostatic hazards. Therefore, nano-scale graphite has been widely used as a conductive material in the fields of composite materials and antistatic coatings. The methods for preparing nano-scale graphite mainly include arc meth〇d, laser vaporizati, and phase catalytic pyrolysis. The arc method is a high temperature (about 3 〇〇〇 to 4 〇〇〇〇 c) generated by arc discharge in a vacuum chamber containing helium gas, and the solid carbon source is vaporized and vaporized, and the structure is rearranged and deposited. On a substrate, the method is often accompanied by a large amount of impurities such as graphite particles and coal ash, so that subsequent purification treatment is often required, and because the manufacturing equipment of the arc method is complicated, it is technically required to control the cooling rate and the μ force of 201226314 helium. Achieve the quality of nucleation. The principle of the laser evaporation method and the arc method is that the high-energy laser focuses on the coffin and the surface carbon material is evaporated, and the carrier is deposited on the substrate by cooling under the action of the catalyst. The laser evaporation method still exists in the phase of the gas phase, and the gas phase catalytic pyrolysis method uses a readily decomposable organic substance (such as B-speed or A-burn) as a carbon source at 5 〇〇 to 1200. . Under the temperature range and the catalysis of transition metal elements, the carbon is decomposed to generate carbon atoms and adsorbed on the crystal faces of the metal particles, and deposited on the surface of the metal. The method needs to be adsorbed on the metal particles to form a nucleation length. Crystal, so the size, distribution and investment of metal particles will affect the quality of nucleation. The nano-scale graphite prepared by the gas phase catalytic decomposition method often has problems of low yield, low purity and uneven distribution. In addition to the above three methods, other methods such as electrolysis, ball milling or diffusion flame have problems such as difficult process control, low product quality and low yield. It can be seen from the above that there are still many preparation methods for the existing nano-scale graphite: "Therefore, the industry still hopes to develop a combination of process and equipment, low cost and no energy consumption, and can produce better resistance. A method of electrostatically acting nanoscale graphite. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method of a graphite nanosheet which is simple in equipment, low in cost, and capable of producing a better antistatic effect. Thus, the method of the present invention for preparing a graphite nanosheet comprises: oxidizing a -first oxidant with - graphite to obtain a reactant; the reactant, - a second oxidizing agent, an intercalating agent and water Mixing to obtain a mixture; in a closed environment, the mixture is twisted, 201226314 to obtain an expanded graphite; and the expanded graphite is subjected to high temperature treatment and delamination treatment to obtain a graphite nanometer. sheet.
本發明用於製備石墨奈米片之方法是利用該第一氧化 Μ的強氧化特性’與該石墨進行氧化反應，將該石墨轉變 為T電之反應物’使得經該第—氧化劑氧化之反應物的層 ’距大m墨之層間距；且相較於該石墨，該反應物可 更谷易地插入其他的原子、分子或離子，更可有效地提高 後續進行插層的效率。接著將該反應物與插層劑、第二氧 化劑與水進仃充分地混合後，置於一密閉的環境中，透過 u的處理及在適當的條件控制下，使得該插層劑分解 成活化離子’ $活化離子可以有序地以插層方式重新排 列於該反應物之層與層之間，而獲得該膨脹型石墨。 、X息脹31石墨透過高溫處理，使該膨脹型石墨的體積 二遽^脹’增加其層間距，再經由脫層處理後可更容易地 形成奈米等級的石墨片。 本發明用於製備；g m太虫μ ’土；Γ、未片之方法的功效在於：相較 於傳統的製備方法，嗲 。哀方法不僅§又備上及製程上皆簡單， 且藉由該膨脹型石墨經由高溫及脫層處理，可製備出更佳 抗靜電效果且具有奈米級之石墨片。 【實施方式】 …Ϊ明用於製備石墨奈米片之方法，包含：將-第-::劑與-石墨進行氧化反應，以獲得一反應物；將該反 化劑、—插層劑與水進行混合，以獲得-“物；於一密閉環境下，使該混合物進行加熱，以製得 201226314 一膨脹型石墨；以及將該膨脹型石墨進行高溫處理及脫層 處理，以獲得一石墨奈米片。 較佳地，該第一氧化劑是擇自於臭氧、過猛酸鉀、雙 氧水、重絡酸鉀、氯酸卸、過氯酸鉀、确酸鉀、氯酸鈉。 更佳地’該第一氧化劑是臭氧。 較佳地’該氧化反應的溫度範圍為〇〜3 0〇C。 較佳地’該方法選擇地更包含一步驟，該步驟係將該 石墨、第一氧化劑及一溶劑混合形成一溶液。 本發明之一具體例中，該溶劑是水。 當該氧化反應於該溶液下進行時，較佳地，該第一氧 化劑的含量範圍為0.25〜5mg/l。 較佳地’該第二氧化劑是擇自於硝酸、過猛酸鉀、雙 氧水、重鉻酸鉀、臭氧、氯酸鉀、過氣酸鉀、硝酸鉀或此 等之一組合。更佳地，該第二氧化劑是硝酸。 較佳地’該插層劑是擇自於硫酸、過氣酸、磷酸、鹽 酸、雙氧水或此等之一組合。更佳地，該插層劑是硫酸。 較佳地，該插層劑與第二氧化劑的莫耳數比範圍為M. :1〜22.6 : 1。更佳地，該插層劑與該第二氧化劑的莫耳數 比範圍為3 : 1〜5 : 1。 較佳地，該插層劑及第一氧化劑可先分別溶於水中， 例如當插層劑為硫酸且第二氧化劑為硝酸時，所使用的硫 酸水溶液及硝酸水溶液之濃度分別是介於75〜98加％及65 〜85 wt%之間，且該硫酸水溶液與硝酸水溶液之體積比例 是介於1 : 1〜20 : i之間。更佳地，所使用的硫酸水溶液 201226314 及硝酸水溶液之濃度分別是介於93〜98 wt%及68〜73 wt% 之間，且該硫酸水溶液與硝酸水溶液之體積比例是4 : i。 較佳地’該插層劑及第二氧化劑於水的存在下進行混 合時會有放熱的現象產生，為避免於混合的過程中因溫产 增加而使得該反應物產生部分氧化，較佳地，該進行混人 的溫度範圍為0〜40°C。 較佳地，該反應物係先加入插層劑及水，待混合均句 後，再加入第二氧化劑，以降低該反應物於混合過程中可 能產生的部分氧化之機率。 較佳地，該混合物是利用超音波震盪的方式進行混合 〇 較佳地’該加熱步驟是在一高壓釜中進行，以形成— 密閉之環境。 較佳地，該加熱溫度範圍為8〇〜2〇〇C3C。更佳地該加 熱的溫度範圍為80〜140°C。 透過尚溫處理可使該膨脹型石墨的體積急遽膨脹，增 加其層間距。較j圭地，言亥冑溫處理的温度範圍為觸〜 1000。。。 透過脫層處理可使該膨脹型石墨震碎並且同時達到脫 層的效果’形成奈米級石墨片。較佳地，該脫層處理是加 入一溶劑並施予一形成石墨奈米片之能量。 較佳地’該溶劑是擇自於醇類、__、酸類、苯、甲 苯、二甲苯、四氫呋喃。更佳地，該溶劑是乙醇。 較佳地，S亥能量是由超音波震盪器產生。 201226314 較佳地’該石墨奈米片的平均厚度範圍為100nrn以下 本發明將就以下實施例來作進一步說明，但應瞭解的 是，該等實施例僅為例示說明之用，而不應被解釋為本發明 實施之限制。 <實施例> 【膨脹型石墨之製備】 取l〇g的天然鱗片石墨（natural flake graphite，純度 99%，粒徑大小為192·5 ，由國碳公司提供），放置於含 有400g去離子水溶液的燒杯中，利用臭氧產生機以電暈放 電方式，通入100V電壓將氧氣形成臭氧，該石墨均勻曝氣 1〇分鐘後過濾並清洗，以獲得一反應物。 取20mL濃度為95wt%之硫酸水溶液先行與5g之該反 應物混合攪拌5分鐘後，在低於40°C的溫度下逐漸滴入 5mL濃度為70 wt%之硝酸水溶液，以獲得一混合物。如圖 1所示，將該混合物倒入一鐵II龍（Teflon®)製的容器1中， 再利用超音波震盪器以600 W之功率震盪30分鐘之後，將 該鐵氟龍容器1鎖緊上蓋11，放入一高壓釜（aut〇clave)2中 並密封’接著再置於加熱溫度設定為80。(：之烘箱内，且將 反應時間設定為60分鐘來進行插層反應，待反應結束，移 出該高壓釜2並置於室溫下冷卻，待冷卻後加入大量之去 離子水進行過濾清洗’以移除未反應之多餘的酸液，之後 於室溫（約25。〇下靜置1天，再放入溫度設定為8〇qC之烘 箱内乾燥1小時後，即獲得膨脹型石墨。 201226314 [石墨奈米片之製備] 將上述該膨脹型石墨置入於1〇〇〇〇C高溫爐内3〇秒後 ’再改泡於75〇/〇乙醇中’利用6〇0 w超音波震盪震盪8小 日守以上’並以過濾方式去除酒精後，放置於80°C的真空烘 箱内，以去除殘餘酒精溶劑，即獲得該石墨奈米片。The method for preparing a graphite nanosheet of the present invention is to utilize the strong oxidation characteristic of the first cerium oxide to undergo an oxidation reaction with the graphite, and convert the graphite into a T-electrode reactant to cause oxidation of the first oxidant. The layer of the object is spaced from the layer of the large ink; and compared with the graphite, the reactant can be inserted into other atoms, molecules or ions more conveniently, and the efficiency of subsequent intercalation can be effectively improved. Then, the reactant is thoroughly mixed with the intercalating agent, the second oxidizing agent and the water, and then placed in a closed environment, and the intercalating agent is decomposed into activated by the treatment of u and under the control of appropriate conditions. The expanded graphite can be obtained by orderly intercalating between the layers of the reactants in an intercalated manner to obtain the expanded graphite. X-ray expansion 31 graphite is treated by high temperature, so that the volume of the expanded graphite is increased, and the layer spacing is increased, and then the graphite sheet of nanometer grade can be formed more easily by the delamination treatment. The invention is useful for preparing; g m worms μ ' soil; the effect of the Γ, 片片 method is: compared to the conventional preparation method, 嗲. The sorrow method is not only § but also simple in preparation and process, and the graphite sheet having a better antistatic effect and having a nanometer level can be prepared by the high temperature and delamination treatment of the expanded graphite. [Embodiment] The method for preparing a graphite nanosheet comprises: oxidizing a -:: agent with - graphite to obtain a reactant; the resolving agent, the intercalating agent and Mixing water to obtain - "the material; in a closed environment, the mixture is heated to obtain 201226314 an expanded graphite; and the expanded graphite is subjected to high temperature treatment and delamination treatment to obtain a graphite naphthalene Preferably, the first oxidant is selected from the group consisting of ozone, potassium perchlorate, hydrogen peroxide, potassium hydroxyacid, chloric acid, potassium perchlorate, potassium silicate, sodium chlorate. More preferably An oxidizing agent is ozone. Preferably, the temperature of the oxidation reaction is in the range of 〇~3 0 〇 C. Preferably, the method optionally further comprises a step of mixing the graphite, the first oxidizing agent and a solvent. A solution is formed. In one embodiment of the invention, the solvent is water. When the oxidation reaction is carried out under the solution, preferably, the content of the first oxidant ranges from 0.25 to 5 mg/l. The second oxidant is selected from nitric acid Potassium acid, hydrogen peroxide, potassium dichromate, ozone, potassium chlorate, potassium peroxylate, potassium nitrate or a combination thereof. More preferably, the second oxidizing agent is nitric acid. Preferably, the intercalating agent is selected from In combination with sulfuric acid, peroxyacid, phosphoric acid, hydrochloric acid, hydrogen peroxide or one of these, more preferably, the intercalating agent is sulfuric acid. Preferably, the molar ratio of the intercalating agent to the second oxidizing agent is in the range of M :1~22.6 : 1. More preferably, the molar ratio of the intercalant to the second oxidant ranges from 3:1 to 5: 1. Preferably, the intercalant and the first oxidant are first Dissolving separately in water, for example, when the intercalating agent is sulfuric acid and the second oxidizing agent is nitric acid, the concentration of the aqueous sulfuric acid solution and the aqueous nitric acid solution used is between 75 and 98% by weight and between 65 and 85 to 85% by weight, respectively. The volume ratio of the aqueous solution of sulfuric acid to the aqueous solution of nitric acid is between 1: 1 and 20: i. More preferably, the concentrations of the aqueous solution of sulfuric acid 201226314 and the aqueous solution of nitric acid are between 93 and 98 wt% and 68 to 73 wt, respectively. Between %, and the volume ratio of the aqueous sulfuric acid solution to the aqueous solution of nitric acid is 4: i. Preferably' When the intercalating agent and the second oxidizing agent are mixed in the presence of water, an exothermic phenomenon occurs, and in order to avoid partial oxidation of the reactant due to an increase in temperature during the mixing process, preferably, the mixing is performed. The temperature ranges from 0 to 40 ° C. Preferably, the reactant is first added with an intercalating agent and water, and after mixing, a second oxidizing agent is added to reduce the possibility that the reactant may be produced during the mixing process. Preferably, the mixture is mixed by means of ultrasonic vibration. Preferably, the heating step is carried out in an autoclave to form a closed environment. Preferably, the heating temperature The range is 8 〇 2 〇〇 C 3 C. More preferably, the heating temperature ranges from 80 to 140 ° C. The volume of the expanded graphite is rapidly expanded by the treatment at room temperature, and the layer spacing is increased. Compared with J Guidi, the temperature range of the treatment is ～1000. . . The expanded graphite can be pulverized by the delamination treatment and at the same time achieve the effect of delamination, forming a nano-scale graphite sheet. Preferably, the delamination treatment is the addition of a solvent and the application of an energy to form a graphite nanosheet. Preferably, the solvent is selected from the group consisting of alcohols, __, acids, benzene, toluene, xylene, tetrahydrofuran. More preferably, the solvent is ethanol. Preferably, the energy of S is generated by an ultrasonic oscillator. 201226314 Preferably, the average thickness of the graphite nanosheets is 100 nrn or less. The present invention will be further illustrated by the following examples, but it should be understood that the examples are for illustrative purposes only and should not be It is to be construed as limiting the implementation of the invention. <Examples> [Preparation of expanded graphite] 1 g of natural flake graphite (purity 99%, particle size 192·5, supplied by National Carbon Corporation) was placed, and it was placed in a 400 g In the beaker of the ionic aqueous solution, oxygen was formed into a plasma by a corona discharge method using a ozone generator, and the graphite was uniformly aerated for 1 minute, filtered and washed to obtain a reactant. 20 mL of a 95 wt% aqueous sulfuric acid solution was first mixed with 5 g of the reaction mixture for 5 minutes, and then 5 mL of a 70 wt% aqueous solution of nitric acid was gradually added dropwise at a temperature lower than 40 ° C to obtain a mixture. As shown in Fig. 1, the mixture was poured into a vessel 1 made of Teflon®, and then vortexed at 600 W for 30 minutes using an ultrasonic oscillator, and the Teflon container 1 was locked. The upper cover 11, placed in an autoclave 2 and sealed 'and then placed at a heating temperature set to 80. (In the oven, and set the reaction time to 60 minutes to carry out the intercalation reaction, after the reaction is finished, remove the autoclave 2 and let it cool at room temperature, and add a large amount of deionized water for filtration after cooling. The unreacted excess acid solution was removed, and then expanded at room temperature (about 25 Torr for 1 day, and then placed in an oven set to 8 〇 q C for 1 hour to obtain expanded graphite. 201226314 [ Preparation of Graphite Nanosheets] The above-mentioned expanded graphite was placed in a 1 〇〇〇〇C high temperature furnace for 3 〇 seconds and then changed to 75 〇/〇 ethanol. Using 6 〇 0 w ultrasonic shock concussion After 8 hours of the above and removing the alcohol by filtration, it was placed in a vacuum oven at 80 ° C to remove the residual alcohol solvent, and the graphite nanosheet was obtained.
Si試及、ϋSi test, ϋ
[掃描式電子顯微鏡（SEM)J # 藉由掃描式電子顯微鏡（JEOL-JSM-7401F)可觀察到石 墨奈米片之表面外觀形態（m〇rph〇1〇gy)(拍攝倍率為2,〇〇〇倍 、l〇k、30k或50k倍）’所得結果如圖2所示，其中圖2⑷ 為石墨奈米片的表面形態；目2(b)、圖2⑷及圖2⑷為圖 2(a)在放大倍率依序為1〇k、3〇k及5〇k下的表面形態。由 圖2(a)〜（d)可觀察到大量之奈米級石墨碎片，並經由逐漸 之放大倍率可以明顯看到該石墨奈米片平均厚度範圍約為 2〇〜3〇nm内，屬於奈米等級，因此証明本製備方法確實獲 φ 得該石墨奈米片。 、又 [穿透式電子顯微鏡(TEM)】 藉由穿透式電子顯微鏡[(JEOL-JEM-2100(HT))利用不门 陰極燈源發射電子源照射該石墨奈米片，捕捉彈性散射電 子机號來做像顯影’由此可觀察到石墨奈米片 '1〜衣由型態 ，所得結果如圖3所示，其中，圖3(a)及圖3(b)為石墨卉米 片的表面形態。圖3(a)及圖3(b)呈現不規則薄片形狀、2明 顯聚集狀且具分散性，再藉由光學可穿透角度判斷，此 201226314 墨片厚度應小於1 〇〇nm以下，才具有如此透明性質，因此 証明本製備方法確實獲得該石墨奈米片。 【X-光粉末繞射分析（x_ray powder diffraction，XRD)】 將該石墨奈米片進行χ·光粉末繞射分析（x_ray光源為 銅靶材，操作電壓35 kV’操作電流為3〇 mA，繞射角從2 度掃瞄到80度）以測定晶體結構的層間距，利用 /2d之公式（η為正整數，且，入=〇 ΐ54η^經計算可得 層間距（d，nm)。由表！之結果可以得知，相對於天然鱗片 石墨之角度及層間距，石墨奈米片的偏移角度最多且層間 距較大，因此註明本發明之製備方法確實獲得該石墨奈米 片。再者，由石墨特性峰之強度來看，強度越大代表具有 整齊規律排列的特性，亦即其結晶性越佳，代表其排列具 有規則性，故以本發明之製備方法所獲得之石墨奈米片石 墨特性峰之強度為最弱，其石墨排列之規則性皆已破壞， 已分散為石墨奈米片。 [表面電性分析] 分別將膨脹石墨與石墨奈米片依不同重量百分率（即，2 、4、6、8及l〇wt%)添加至環氧樹酯中塗佈成薄片以四 點碳針與高阻計測試電阻。一般具有良好抗靜電材料 值範圍為10〜10 Q/cm2，更佳地，讓靜電消散則其電 ，值1G5〜心/⑽2。由表i之結果可以得知，除了 是良好的抗靜電材料外，該石墨奈米片添加至_科就於 達到靜電消散之效果，因此註明本製備方法所獲得該石墨" 奈米片具有更佳的抗靜電效果。 10 201226314[Scanning Electron Microscopy (SEM) J # The surface appearance of the graphite nanosheets (m〇rph〇1〇gy) can be observed by a scanning electron microscope (JEOL-JSM-7401F) (photographing magnification is 2, 〇 〇〇, l〇k, 30k or 50k times) 'The results obtained are shown in Figure 2, where Figure 2 (4) is the surface morphology of the graphite nanosheet; Item 2 (b), Figure 2 (4) and Figure 2 (4) is Figure 2 (a The surface morphology under the order of magnification of 1〇k, 3〇k and 5〇k. A large number of nano-scale graphite fragments can be observed from Fig. 2(a) to (d), and it can be clearly seen through the gradual magnification that the average thickness of the graphite nanosheet ranges from about 2 〇 to 3 〇 nm. The nanometer grade, therefore, proves that the preparation method does obtain the graphite nanosheet. [Transmissive Electron Microscopy (TEM)] The graphite nanosheet is irradiated by a transmission electron microscope [(JEOL-JEM-2100(HT)) using a non-gate cathode light source to capture elastic scattering electrons. The machine number is used for image development. Thus, the graphite nanosheets can be observed in the form of '1~ clothes. The results are shown in Fig. 3. Among them, Fig. 3(a) and Fig. 3(b) are graphite plants. Surface morphology. Figure 3 (a) and Figure 3 (b) show irregular sheet shape, 2 obvious aggregation and dispersibility, and then judged by the optically transparent angle, the 201226314 ink sheet thickness should be less than 1 〇〇 nm. It has such a transparent property that it is proved that the present preparation method does obtain the graphite nanosheet. [X-ray powder diffraction (XRD)] The graphite nanosheet was subjected to χ·light powder diffraction analysis (x_ray source is a copper target, and the operating voltage is 35 kV, the operating current is 3 mA, The diffraction angle is scanned from 2 degrees to 80 degrees to determine the layer spacing of the crystal structure, using the formula of /2d (η is a positive integer, and the input = 〇ΐ 54η^ is calculated to obtain the layer spacing (d, nm). As can be seen from the results of Table!, the graphite nanosheet has the most offset angle and a large interlayer spacing with respect to the angle and layer spacing of the natural flake graphite, and therefore it is noted that the preparation method of the present invention does obtain the graphite nanosheet. Furthermore, from the viewpoint of the intensity of the graphite characteristic peak, the greater the intensity, the characteristic of having a neat arrangement, that is, the better the crystallinity, representing the regularity of the arrangement thereof, and thus the graphite nanoparticle obtained by the preparation method of the present invention. The intensity of the graphite characteristic peak is the weakest, and the regularity of the graphite arrangement is destroyed, and it has been dispersed into graphite nanosheets. [Surface electrical analysis] The expanded graphite and the graphite nanosheet are respectively weight-dependent (ie, 2 4 , 6, 8 and l 〇 wt%) added to the epoxy resin coated into a thin sheet with a four-point carbon needle and a high resistance meter test resistance. Generally have a good antistatic material value range of 10~10 Q/cm2, more Good place, let the static dissipate its electric value, the value is 1G5~heart/(10)2. It can be known from the results of Table i that in addition to being a good antistatic material, the graphite nanosheet is added to the _ branch to achieve static dissipating. The effect, therefore, indicates that the graphite " nanosheet obtained by the preparation method has better antistatic effect. 10 201226314
--」表示無量測數值 ❿ 本發明方法採取先使該石墨經由氧化反應及水埶法處 理形成-膨脹型石‘墨’再透過高溫及脫層處理形成奈求級 的石墨片。相較於傳統的製備方法，該方法不僅設備上及 製輊上白簡單’且以本發明方法製備出之石墨奈米片作為 :靜電材料中的成分，可有效增強並改善靜電材料的抗靜 ^生對於運用在^靜電之複合材料及防靜電塗料中 貫可達到所需功效。 隹 惟以上所述者，僅在太欢nn 心、 僅為本發明之較佳實施例而已，當不 月匕以此限定本發明實施篇 〜 . 乾圍’即大凡依本發明申請專利 軏圍及發明說明内容所作 1 心間早的等效變化與修飾，皆 201226314 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1是一示意圖’說明裝有反應混合物的鐵氟龍容器i並 鎖緊上蓋11後’置於一高壓釜2中並密封； 圖2是一照片，說明運用掃瞄式電子顧微鏡測得之表面形 態，其中’（a)為放大倍率在2000倍下之石墨奈米片的表面 形態、（b)〜（d)為（a)在放大倍率為1〇k、3处及5攸下之結 果；及--" indicates the unmeasured value ❿ The method of the present invention adopts the graphite sheet which is formed by the oxidation reaction and the water hydrazine treatment to form an expanded stone 'ink' and then passes through a high temperature and delamination treatment to form a nano-grade. Compared with the conventional preparation method, the method not only simple and simple on the equipment and the graphite nanosheet prepared by the method of the invention is used as a component in the electrostatic material, and can effectively enhance and improve the antistatic of the electrostatic material. ^Life can achieve the desired effect in the composite materials and antistatic coatings used in the static electricity.以上 以上 以上 以上 以上 以上 以上 以上 nn nn nn 、 nn nn 、 、 、 、 nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn nn And the description of the contents of the invention 1 the early equivalent changes and modifications of the heart, all 201226314 is covered by the patent of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a Teflon container i containing a reaction mixture and locking the upper cover 11 and placed in an autoclave 2 and sealed; Fig. 2 is a photograph showing the use of a scanning The surface morphology measured by micro-mirror, where '(a) is the surface morphology of the graphite nanosheet at a magnification of 2000 times, and (b) ~(d) is (a) at a magnification of 1〇k , 3 and 5 results; and
•…•、片的表面形態。 圖3是一照片， 構形態，其中，（a) 201226314 【主要元件符號說明】 1 ...........鐵氟龍容器 2...........高壓釜 11·".......上蓋•...•, the surface morphology of the piece. Figure 3 is a photograph, configuration, in which (a) 201226314 [main component symbol description] 1 ........... Teflon container 2...........high voltage Kettle 11·".......上盖
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