TW201622808A - Process for modification of particles - Google Patents
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/006—Separating solid material from the gas/liquid stream by filtration
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/003—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor in a downward flow
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/005—Separating solid material from the gas/liquid stream
- B01J8/0055—Separating solid material from the gas/liquid stream using cyclones
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/16—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with particles being subjected to vibrations or pulsations
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/40—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed subjected to vibrations or pulsations
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- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
- B01J8/42—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed subjected to electric current or to radiations this sub-group includes the fluidised bed subjected to electric or magnetic fields
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
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- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00433—Controlling the temperature using electromagnetic heating
- B01J2208/00442—Microwaves
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00433—Controlling the temperature using electromagnetic heating
- B01J2208/00469—Radiofrequency
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00893—Feeding means for the reactants
- B01J2208/00902—Nozzle-type feeding elements
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00796—Details of the reactor or of the particulate material
- B01J2208/00893—Feeding means for the reactants
- B01J2208/00929—Provided with baffles
Abstract
Description
本發明係關於一種用於在具有兩種氣態物料流之設備中對顆粒進行改質的方法。 The present invention relates to a method for modifying particles in an apparatus having two gaseous streams.
在工業應用中用作固體方法材料之顆粒的特性改質為許多技術領域中所關注之科學及技術範圍：製造整體式或複合零件、機械、運輸(車輛結構及馬達)、催化、能量產生、微電子學、光電子學、休閒產業等。 The characterization of particles used as solid process materials in industrial applications is a scientific and technical area of interest in many technical fields: manufacturing monolithic or composite parts, machinery, transportation (vehicle structures and motors), catalysis, energy generation, Microelectronics, optoelectronics, leisure industry, etc.
適用於此類方法的為可由聚合物、陶瓷、金屬半導體及金屬氧化物製成之顆粒(P1)以及包括(但不限於)過渡金屬氧化物或硫屬化物之分層材料。 Suitable for such processes are particles (P1) which can be made of polymers, ceramics, metal semiconductors and metal oxides, and layered materials including, but not limited to, transition metal oxides or chalcogenides.
此外，亦適用於此類方法的為可由不同形式之碳(如石墨(來自天然及合成性來源)、可膨脹(例如夾層型(intercalated))石墨、氧化石墨、膨脹石墨、碳黑、活性碳、碳纖維、碳奈米管、富勒烯、石墨烯、石墨烯奈米小片(nanoplatelets)、煤及焦炭)製成的顆粒(P1)。 Also suitable for such methods are carbons of different forms (eg graphite (from natural and synthetic sources), expandable (eg intercalated) graphite, graphite oxide, expanded graphite, carbon black, activated carbon Particles (P1) made of carbon fiber, carbon nanotubes, fullerenes, graphene, nanoplatelets, coal and coke.
已知在此等方法中可進行兩種類型之顆粒改質：形態改質，其可體現為物質之尺寸、縱橫比、形狀、光學外觀或相疇形式的改變(例如分層材料之膨脹)；及改變材料化學構成之至少一個特徵的化學改質(官 能化)，其包括向材料引入官能基(例如含O、N、S、P、Si、H、C之基團)及/或功能性塗層或向材料之原子結構中引入雜原子(例如B或N)。此可通常在用於相應方法之設備的反應區中進行。在反應區中，可以不同方式達到氣相及/或起始材料之活化，例如熱、反應性電漿、化學、射頻加熱、雷射加熱、火焰熱解(flame pyrolysis)、微波加熱、其組合等。 It is known that two types of particle modifications can be made in such methods: morphological modification, which can be manifested as a change in the size, aspect ratio, shape, optical appearance, or domain form of the material (eg, expansion of the layered material). And chemical modification that changes at least one of the chemical constituents of the material Capable of introducing a functional group (eg, a group containing O, N, S, P, Si, H, C) and/or a functional coating into a material or introducing a hetero atom into the atomic structure of the material (eg B or N). This can usually be carried out in the reaction zone of the apparatus used in the corresponding process. In the reaction zone, activation of the gas phase and/or starting materials can be achieved in different ways, such as heat, reactive plasma, chemical, radio frequency heating, laser heating, flame pyrolysis, microwave heating, combinations thereof Wait.
對於一些方法，需要形態改質，然而對於其他方法，需要化學改質，且又其他方法甚至需要連續或組合之形態及化學改質步驟。 For some methods, morphological upgrading is required, while for other methods, chemical upgrading is required, and other methods require even continuous or combined morphological and chemical upgrading steps.
US 2012/0145041 A1描述小顆粒之電漿處理，諸如懸浮於電容性輝光放電中之轉鼓中的碳奈米管。 US 2012/0145041 A1 describes plasma treatment of small particles, such as carbon nanotubes suspended in a drum in a capacitive glow discharge.
US 2011/0300056 A1描述一種用於產生奈米結構之方法，其涉及提供包含石墨烯層之石墨片、夾入該石墨片以形成石墨夾層化合物及藉由將該石墨夾層化合物暴露於介於約1600℃與約2400℃之間的溫度下來使之剝離，以使得多個個別石墨烯層自該石墨夾層化合物分離。 US 2011/0300056 A1 describes a method for producing a nanostructure, which involves providing a graphite sheet comprising a graphene layer, sandwiching the graphite sheet to form a graphite interlayer compound, and exposing the graphite interlayer compound to about The temperature between 1600 ° C and about 2400 ° C is stripped to separate a plurality of individual graphene layers from the graphite interlayer compound.
US 2013/0022530 A1描述一種用於產生剝離型石墨之方法，其涉及提供石墨夾層化合物及經由處於至少6000℃下之電漿使該石墨夾層化合物達到介於約1600℃與約3400℃之間的溫度來使該石墨夾層化合物剝離。 US 2013/0022530 A1 describes a method for producing exfoliated graphite, which relates to providing a graphite interlayer compound and bringing the graphite interlayer compound between about 1600 ° C and about 3400 ° C via a plasma at at least 6000 ° C. The temperature is used to peel off the graphite interlayer compound.
現有技術水平中所描述之此等方法適合於可變反應時間下之低能電漿(例如電容性輝光放電)改質或適合於使用持續較短反應時間(通常小於一秒)之電漿炬的高能電漿改質。雖然在前一情況下不可能進行需要高激發能量之材料改質，但在後一情況下材料可僅在其通過反應區之自然飛行時間期間進行電漿處理。 The methods described in the state of the art are suitable for upgrading low energy plasma (e.g., capacitive glow discharge) at variable reaction times or for use with a plasma torch that lasts for a short reaction time (typically less than one second). High-energy plasma is upgraded. Although it is not possible to carry out a material modification requiring high excitation energy in the former case, in the latter case the material may be subjected to plasma treatment only during its natural flight time through the reaction zone.
舉例而言，US 2013/0022530 A1陳述經處理材料在反應區中之滯留時間不應超過0.2s。一旦材料離開反應區，不可能進行進一步改質。因此，此類材料處理方法之彈性有限。特定言之，在US 2011/0300056 A1及US 2013/0022530 A1之情況下，多步驟方法為不可能的。 For example, US 2013/0022530 A1 states that the residence time of the treated material in the reaction zone should not exceed 0.2 s. Once the material leaves the reaction zone, no further modification is possible. Therefore, the flexibility of such material processing methods is limited. In particular, in the case of US 2011/0300056 A1 and US 2013/0022530 A1, a multi-step method is not possible.
原則上，流體化床系統提供在所選擇之激發能量及處理時間範圍內處理顆粒的可能性。然而，待處理之材料必須為可流體化的，其在較小粒度(微米尺度或低於微米尺度)或輕型中尺度顆粒的情況下，對於在反應期間展現高顆粒間內聚力、聚結趨勢、不合適縱橫比或明顯形態變化(例如產生極疏鬆顆粒)(全部導致不良流體化或根本無流體化)之顆粒可能為嚴重挑戰。在該情況下，顆粒不再混合，導致極不良且不均勻之材料處理。然而，不存在可供用於對此類不充分地可流體化之材料進行處理的組合廣泛範圍之激發能量、處理時間及化學與形態改質(官能化)的選項。 In principle, the fluidized bed system provides the possibility of processing the particles over the selected excitation energy and processing time. However, the material to be treated must be fluidizable, exhibiting high interparticle cohesion, coalescence tendency during the reaction, in the case of smaller particle sizes (microscale or submicron scale) or light mesoscale particles, Particles that are not suitable for aspect ratio or significant morphological changes (eg, producing extremely loose particles) that all result in poor fluidization or no fluidization at all can be a serious challenge. In this case, the particles no longer mix, resulting in extremely poor and uneven material handling. However, there is no option to combine a wide range of excitation energies, processing times, and chemical and morphological modifications (functionalizations) that can be used to treat such inadequately fluidizable materials.
在現有技術水平中沒有揭示允許將顆粒(P1)運載(使之流體化)至反應區中且用脈衝氣流將其固定在反應區中來進行化學及/或形態改質以同時提供可處理之材料、處理時間、活化方法(及因此亦活化能量)之高彈性與多步驟方法之可能性的方法。 It is not disclosed in the state of the art that the particles (P1) are allowed to be carried (fluidized) into the reaction zone and fixed in the reaction zone with a pulsed gas stream for chemical and/or morphological upgrading to provide a treatable A method of high flexibility and the possibility of a multi-step process for materials, processing times, activation methods (and thus also energy activation).
本發明之一個目標為提供一種用於對顆粒(尤其石墨、夾層型石墨及可膨脹石墨)進行改質之新穎方法。 It is an object of the present invention to provide a novel process for modifying particles, particularly graphite, sandwich graphite and expandable graphite.
該目標藉由一種用於在設備(A1)內對顆粒(P1)進行改質之方法來進行，該設備(A1)包含氣態物料流(G1)及(G2)之至少兩 個入口、氣體入口區(inlet zone；IZ)、位於該氣體入口區(IZ)下方之反應區(reactive zone；RZ)、位於該反應區(RZ)下方之樣品保持器(sample holder；SH)及位於(A1)底部處之出口(O1)，其中該方法包含以下步驟a)至e)：a)將包含至少一種惰性氣體及/或反應氣體之氣態物料流(G1)饋入至設備(A1)中，其中(G1)在該設備(A1)內部之流動方向為自頂部至底部通過該反應區(RZ)，b)在設備(A1)之該樣品保持器(SH)上提供顆粒(P1)，c)饋入包含至少一種惰性氣體及/或反應氣體之氣態物料流(G2)的至少一個脈衝以將顆粒(P1)運載至該反應區(RZ)中，且在該樣品保持器(SH)下方之位置處將(G2)饋入至設備(A1)中，d)在該反應區(RZ)中對顆粒(P1)進行改質，及e)經由該出口(O1)自設備(A1)排出該氣態物料流(G1)及/或該氣態物料流(G2)。 The object is carried out by a method for modifying particles (P1) in a device (A1) comprising at least two of gaseous streams (G1) and (G2) Inlet, gas inlet zone (IZ), reaction zone (RZ) located below the gas inlet zone (IZ), sample holder (SH) located below the reaction zone (RZ) And an outlet (O1) at the bottom of (A1), wherein the method comprises the following steps a) to e): a) feeding a gaseous stream (G1) comprising at least one inert gas and/or a reactive gas to the apparatus ( In A1), wherein (G1) flows through the reaction zone (RZ) from the top to the bottom in the apparatus (A1), and b) provides particles on the sample holder (SH) of the apparatus (A1) ( P1), c) feeding at least one pulse of a gaseous stream (G2) comprising at least one inert gas and/or a reactive gas to carry the particles (P1) into the reaction zone (RZ), and in the sample holder (G2) is fed into the device (A1) at the position below (SH), d) the particles (P1) are modified in the reaction zone (RZ), and e) the device is (O1) via the outlet (O1) (A1) discharging the gaseous stream (G1) and/or the gaseous stream (G2).
主要優點為形態改質(例如連續膨脹)及化學改質可在同一設備中以組合方式確立。在連續方法中組合形態及化學改質允許在單個設備之設置內進行多功能材料處理，且產生較均勻之材料處理。 The main advantage is that morphological upgrading (eg continuous expansion) and chemical upgrading can be established in combination in the same device. Combining morphology and chemical modification in a continuous process allows for multifunctional material processing within a single device setup and produces a more uniform material treatment.
另一個優點為由於設備(A1)中之氣流因(G2)之脈衝而不再連續，顆粒(P1)在此等條件下較均勻地暴露於反應區(RZ)中之反應氣相中，以防止顆粒形成如上文所描述之多孔聚結物。 Another advantage is that since the gas flow in the device (A1) is no longer continuous due to the pulse of (G2), the particles (P1) are more uniformly exposed to the reaction gas phase in the reaction zone (RZ) under these conditions, The particles are prevented from forming a porous agglomerate as described above.
除此之外，由於氣態物料流(G2)之脈衝模式，顆粒(P1)之混合得到保證，以使得多得多的顆粒(P1)暴露於電漿中且因此可得到 改質。 In addition to this, due to the pulse mode of the gaseous stream (G2), the mixing of the particles (P1) is ensured so that much more particles (P1) are exposed to the plasma and are therefore available Upgraded.
另一個優點為在至少一種氣態物料流(G2)之脈衝期間，材料淘析因為不同流動方向而減少。 Another advantage is that during the pulse of at least one gaseous stream (G2), material elutriation is reduced due to different flow directions.
另一個優點為脈衝之間的間隔、脈衝頻率、脈衝長度、脈衝強度(其可藉由脈衝之氣流速率以及脈衝之氣體壓力來控制)及實驗持續時間為可自由調節的。此外，激發能量可在實驗期間之任何時刻變化，例如可實現不同激發能量概況(profiles)，例如恆定值、勻變(ramps)、躍階(step)概況及/或脈衝概況。此外，氣態物料流(G1)及(G2)中之氣體可在實驗期間之任何時刻變化。 Another advantage is the spacing between pulses, the pulse frequency, the pulse length, the pulse intensity (which can be controlled by the pulsed gas flow rate and the pulsed gas pressure) and the experimental duration is freely adjustable. Moreover, the excitation energy can be varied at any time during the experiment, for example, different excitation energy profiles can be achieved, such as constant values, ramps, step profiles, and/or pulse profiles. In addition, the gases in the gaseous streams (G1) and (G2) can be varied at any time during the experiment.
在下文中詳細界定用於在設備(A1)內對顆粒(P1)進行改質之本發明方法。 The method of the invention for modifying the particles (P1) within the apparatus (A1) is defined in detail below.
設備(A1)包含氣態物料流(G1)及(G2)之至少兩個入口、氣體入口區(IZ)、位於該氣體入口區(IZ)下方之反應區(RZ)、位於該反應區(RZ)下方之樣品保持器(SH)及位於(A1)底部處之出口(O1)。 The apparatus (A1) comprises at least two inlets of a gaseous stream (G1) and (G2), a gas inlet zone (IZ), a reaction zone (RZ) located below the gas inlet zone (IZ), and located in the reaction zone (RZ) ) The sample holder (SH) below and the outlet (O1) at the bottom of (A1).
設備(A1)及視情況選用的根據本發明之設備(A2)可例如見於圖1及3中，且可視情況在出口(O1)及/或出口(O2)處含有泵。設備(A1)及視情況選用之設備(A2)的所有零件為熟習此項技術者已知的。為了完整性，在圖1及3中箭頭位置處提及存在相應入口及出口。圖1及3僅顯示設備(A1)及視情況選用之設備(A2)的示意性設定。 The apparatus (A1) and optionally the apparatus (A2) according to the invention can be seen, for example, in Figures 1 and 3, and optionally with a pump at the outlet (O1) and/or the outlet (O2). All parts of the device (A1) and optionally the device (A2) are known to those skilled in the art. For completeness, reference is made to the presence of corresponding inlets and outlets at the locations of the arrows in Figures 1 and 3. Figures 1 and 3 only show schematic settings of the device (A1) and optionally the device (A2).
在本發明之上下文內，反應區(RZ)為設備(A1)內部進行顆粒(P1)反應之區域。此區域可佔設備(A1)內部較大區域。 In the context of the present invention, the reaction zone (RZ) is the zone in which the interior of the apparatus (A1) undergoes a particle (P1) reaction. This area can occupy a large area inside the device (A1).
需要反應區(RZ)上方之氣體入口區(IZ)作為真空儲槽以容納因氣流及/或氣體脈衝所致之額外氣體。 A gas inlet zone (IZ) above the reaction zone (RZ) is required as a vacuum reservoir to accommodate additional gases due to gas and/or gas pulses.
此外，設備(A1)中之樣品保持器相對於所需條件可自由調節，且可為玻璃料或在熟習此項技術者已知之任何意義上適合之任何東西。 Furthermore, the sample holder in device (A1) is freely adjustable relative to the desired conditions and may be a frit or anything suitable in any sense known to those skilled in the art.
根據本發明之顆粒(P1)可含有(但不限於)聚合物、陶瓷(例如SiC、WC、TiN)、金屬、半導體(例如Si)、金屬氧化物(例如Al2O3)、分層材料(例如過渡金屬氧化物、過渡金屬硫屬化物)、不同形式之碳(例如天然石墨、合成石墨、氧化石墨、膨脹石墨、可膨脹石墨、夾層型石墨、碳黑、活性碳、碳纖維、碳奈米管、富勒烯、石墨烯、煤或焦炭)，其中前述材料之任何混合物及複合物為可能的，且其中此等顆粒(P1)可以各種形式及形狀加以使用，該等形式及形狀包括(但不限於)可膨脹及/或夾層型材料、球形顆粒、纖維或小片，該等顆粒(P1)較佳為天然石墨、合成石墨、氧化石墨、膨脹石墨、可膨脹石墨、夾層型石墨、碳黑、活性碳、碳纖維、碳奈米管、富勒烯、石墨烯、煤或焦炭，該等顆粒(P1)最佳為 天然石墨、合成石墨、可膨脹或夾層型石墨。 The particles (P1) according to the invention may contain, but are not limited to, polymers, ceramics (for example SiC, WC, TiN), metals, semiconductors (for example Si), metal oxides (for example Al 2 O 3 ), layered materials (eg transition metal oxides, transition metal chalcogenides), different forms of carbon (eg natural graphite, synthetic graphite, graphite oxide, expanded graphite, expandable graphite, sandwich graphite, carbon black, activated carbon, carbon fiber, carbon naphthalene) Rice tubes, fullerenes, graphene, coal or coke), wherein any mixtures and composites of the foregoing materials are possible, and wherein such particles (P1) can be used in a variety of forms and shapes, including (but not limited to) expandable and / or sandwich type materials, spherical particles, fibers or small pieces, such particles (P1) are preferably natural graphite, synthetic graphite, graphite oxide, expanded graphite, expandable graphite, sandwich graphite, Carbon black, activated carbon, carbon fiber, carbon nanotubes, fullerenes, graphene, coal or coke, and the particles (P1) are preferably natural graphite, synthetic graphite, expandable or sandwich graphite.
在本發明之上下文內，夾層型石墨在夾層步驟之後自石墨獲得，且可為例如具有不同夾層程度的基於硫酸石墨或硝酸石墨之夾層化合物或含有其他夾層物之石墨，以產生具有可變化學計量之化合物。此夾層型石墨隨後可膨脹。 In the context of the present invention, sandwich graphite is obtained from graphite after the sandwiching step and may be, for example, graphite or graphite nitrate based sandwich compounds having different degrees of interlayer or graphite containing other interlayers to produce variable chemistry The compound being metered. This sandwich type graphite is then expandable.
在本發明之上下文內，改質如下定義：形態改質，其可體現為物質之尺寸、縱橫比、形狀、光學外觀或相疇形式的改變(例如分層材料之膨脹)且主要視為在不實質上改變化學構成之情況下引起顆粒(P1)之結構性變化。 Within the context of the present invention, a modification is defined as a morphological modification which can be embodied as a change in the size, aspect ratio, shape, optical appearance or phase form of the substance (eg expansion of the layered material) and is mainly regarded as The structural change of the particles (P1) is caused without substantially changing the chemical composition.
化學改質(官能化)為改變材料化學構成之至少一個特徵，其包括向材料交換或引入官能基(例如含O、N、S、P、Si、H、C及鹵素之官能基)及/或功能性塗層或在材料之表面上或向其原子結構中引入雜原子(例如O、C、S、B、鹵素或N)。 Chemical upgrading (functionalization) is at least one characteristic that alters the chemical composition of a material, including exchanging or introducing functional groups (eg, functional groups containing O, N, S, P, Si, H, C, and halogen) and/or Or a functional coating or the introduction of a hetero atom (for example O, C, S, B, halogen or N) on the surface of the material or into its atomic structure.
在本發明之上下文內，可在樣品保持器(SH)下方若干位置處同時將氣態物料流(G2)饋入至設備(A1)中。 Within the context of the present invention, a gaseous stream (G2) can be simultaneously fed into the apparatus (A1) at several locations below the sample holder (SH).
在本發明之上下文內，氣態物料流(G1)及(G2)可來源於同一儲槽或來源於不同儲槽。 In the context of the present invention, the gaseous streams (G1) and (G2) may be derived from the same tank or from different tanks.
在本發明之上下文內，氣態物料流(G1)及(G2)可為具有相同組成之氣體混合物。其亦可為具有不同組成之氣體混合物。此外，氣態物料流(G1)及(G2)之流量可具有至多50000sccm，較佳地至多2000sccm，更佳地至多500sccm，且對(G1)及(G2)可處於不同範圍內。原則上，不存在氣體流量上限。 In the context of the present invention, the gaseous streams (G1) and (G2) may be a gas mixture having the same composition. It can also be a gas mixture having a different composition. Furthermore, the flow rates of the gaseous streams (G1) and (G2) may have up to 50,000 sccm, preferably up to 2000 sccm, more preferably up to 500 sccm, and the pairs (G1) and (G2) may be in different ranges. In principle, there is no upper gas flow limit.
在本發明之上下文內，提供在步驟a)中，將包含至少一種惰性氣體及/或反應氣體之氣態物料流(G1)饋入至設備(A1)中，其中(G1)在設備(A1)內部之流動方向為自頂部至底部通過反應區(RZ)。此處，表述「饋入氣態物料流」理解為意謂通過反應區(RZ)之惰性及/或反應氣體連續流。 In the context of the present invention, in step a), a gaseous stream (G1) comprising at least one inert gas and/or a reaction gas is fed into the device (A1), wherein (G1) is in the device (A1) The internal flow direction is from the top to the bottom through the reaction zone (RZ). Here, the expression "feeding gaseous material stream" is understood to mean a continuous flow of inert gas and/or reaction gas through the reaction zone (RZ).
在本發明之上下文內，如上文所提及之「連續流」可理解為並非脈衝且因此連續之(氣)流。然而，仍可能切斷氣態物料流(G1)。此可有助於例如將顆粒輸送至設備(A2)中。較佳地，氣態物料流(G1)之饋入為連續饋入，更佳在步驟a)至d)中連續饋入。在步驟e)(其中進行自設備(A1)排出氣態物料流(G1)及/或氣態物料流(G2))中，有可能切斷氣態物料流(G1)。 Within the context of the present invention, "continuous flow" as referred to above is understood to mean not a pulse and thus a continuous (gas) flow. However, it is still possible to shut off the gaseous stream (G1). This can help, for example, transport the particles into the device (A2). Preferably, the feed of the gaseous stream (G1) is continuously fed, more preferably continuously fed in steps a) to d). In step e), in which the gaseous material stream (G1) and/or the gaseous stream (G2) are discharged from the apparatus (A1), it is possible to shut off the gaseous stream (G1).
在本發明之上下文內，惰性氣體可含有(但不限於)Ar及He。 In the context of the present invention, the inert gas may contain, but is not limited to, Ar and He.
在本發明之上下文內，反應氣體可含有(但不限於)H2、N2、CO2；在顆粒(P1)上生成含O、N、S、P、Si、H、C或鹵素之官能基的氣體；在顆粒(P1)中引入B或N之氣體；或其混合物，較佳H2、N2或CO2。 In the context of the present invention, the reaction gas may contain, but is not limited to, H 2 , N 2 , CO 2 ; a functional group containing O, N, S, P, Si, H, C or halogen on the particle (P1) a gas of a base; a gas of B or N introduced into the particles (P1); or a mixture thereof, preferably H 2 , N 2 or CO 2 .
在本發明之上下文內，在步驟b)中在設備(A1)之樣品保持器(SH)上提供如上文所定義之顆粒(P1)。 Within the context of the present invention, the particles (P1) as defined above are provided on the sample holder (SH) of the device (A1) in step b).
在本發明之上下文內，提供在步驟c)中饋入包含至少一種惰性氣體及/或反應氣體之氣態物料流(G2)的至少一個脈衝以將顆粒(P1)運載至反應區(RZ)中，且在樣品保持器(SH)下方之位置處將(G2)饋 入至設備(A1)中。此處，表述「饋入氣態物料流之至少一個脈衝」理解為意謂氣流脈衝。因此，脈衝由受時間限制之流動組成。此種脈衝在不同設置中可為極短的(<10s)及達到至多幾分鐘(<10min)或更長。較佳為不長於30min之脈衝，更佳為不長於5分鐘之脈衝，最佳為不長於1分鐘之脈衝。脈衝之間的時間可與脈衝自身一樣長，以及更長或更短。脈衝之間的間斷通常不長於60min，較佳短於10min，更佳短於5min，最佳短於1min。 In the context of the present invention, at least one pulse feeding a gaseous stream (G2) comprising at least one inert gas and/or a reactive gas in step c) is provided to carry the particles (P1) into the reaction zone (RZ) And (G2) feed at the position below the sample holder (SH) Go to the device (A1). Here, the expression "at least one pulse fed into the gaseous material stream" is understood to mean a gas flow pulse. Therefore, the pulse consists of a time-limited flow. Such pulses can be extremely short (<10 s) and up to a few minutes (<10 min) or longer in different settings. Preferably, the pulse is no longer than 30 minutes, more preferably no longer than 5 minutes, and most preferably no longer than 1 minute. The time between pulses can be as long as the pulse itself, as well as longer or shorter. The discontinuity between pulses is typically no longer than 60 min, preferably less than 10 min, more preferably less than 5 min, and most preferably less than 1 min.
在本發明之上下文內，表述「以將顆粒(P1)運載至反應區(RZ)中」理解為意謂經由氣態物料流(G2)之一個或多個脈衝使該等顆粒向上進入反應區(RZ)中且將其保持在此處且使其混合(參見例如實施例3)。描述此程序之另一種方式將為使顆粒(P1)流體化且將其浸入至反應區(RZ)中。 In the context of the present invention, the expression "to carry particles (P1) into the reaction zone (RZ)" is understood to mean that the particles are moved upward into the reaction zone via one or more pulses of the gaseous stream (G2) ( RZ) and keep it here and mix it (see, eg, Example 3). Another way to describe this procedure would be to fluidize the particles (P1) and immerse them in the reaction zone (RZ).
在本發明之上下文內，提供在步驟d)中在反應區(RZ)中對顆粒(P1)進行改質。改質較佳在反應區(RZ)中進行。因此，重要的是使顆粒(P1)在此反應區中保持足夠長時間以實現較好且較完全之結果。此處，超過一個改質步驟及不同種類之改質(如上文所定義之形態及化學改質)為可能的，其可於例如實施例4-6中。亦有可能具有連續膨脹及化學改質，例如引入如例如N、O、C、S、B或鹵素之雜原子。 Within the context of the present invention, it is provided that the particles (P1) are modified in the reaction zone (RZ) in step d). The modification is preferably carried out in the reaction zone (RZ). Therefore, it is important to keep the particles (P1) in this reaction zone long enough to achieve better and more complete results. Here, more than one upgrading step and different types of modifications (such as the morphologies and chemical modifications defined above) are possible, which can be, for example, in Examples 4-6. It is also possible to have continuous expansion and chemical upgrading, such as introducing heteroatoms such as, for example, N, O, C, S, B or halogen.
在本發明之一個具體實例中，在步驟d)中以不同方式對顆粒(P1)進行改質，該等方式例如熱活化、電漿活化、電漿及電學高頻場活化、與反應氣體或氣體組合之化學反應、射頻加熱、雷射加熱、火焰熱解、微波加熱以及其組合，較佳藉由視情況包括與反應氣體或氣體組合之 化學反應的電漿活化來進行。 In a specific embodiment of the invention, the particles (P1) are modified in different ways in step d), such as thermal activation, plasma activation, plasma and electrical high frequency field activation, and reactive gases or The chemical reaction of the gas combination, radio frequency heating, laser heating, flame pyrolysis, microwave heating, and combinations thereof, preferably by combination with a reactive gas or gas, as appropriate The plasma reaction of the chemical reaction is carried out.
在本發明之上下文內，提供在步驟e)中經由出口(O1)自設備(A1)排出氣態物料流(G1)及/或氣態物料流(G2)。 Within the context of the present invention, it is provided in step e) that the gaseous material stream (G1) and/or the gaseous material stream (G2) are discharged from the plant (A1) via the outlet (O1).
在本發明之上下文內，出口(O1)理解為意謂排出氣態物料流(G1)及(G2)之開口。出口(O1)可視情況連接至泵上。用此泵在設備(A1)內提供減壓條件，其中該方法可在大氣壓下，較佳在小於200毫巴下，更佳在小於50毫巴下，最佳在小於10毫巴下進行。此減壓條件(與不用泵之條件相比較)使得能夠甚至在大氣壓力的情況下操作泵，因為此壓力比存在於設備(A1)中之壓力小，其使得能夠排出氣態物料流(G1)及(G2)。 In the context of the present invention, the outlet (O1) is understood to mean the opening of the gaseous material streams (G1) and (G2). The outlet (O1) can be connected to the pump as appropriate. The pump is used to provide reduced pressure conditions in the apparatus (A1), wherein the process can be carried out at atmospheric pressure, preferably at less than 200 mbar, more preferably at less than 50 mbar, and most preferably at less than 10 mbar. This reduced pressure condition (compared to the conditions without the pump) makes it possible to operate the pump even at atmospheric pressure, since this pressure is less than the pressure present in the device (A1), which enables the discharge of the gaseous material flow (G1) And (G2).
在本發明之上下文內，出口(O2)為視情況選用之開口，通過該開口可將顆粒及氣體(例如在步驟d)之反應之後)輸送(或例如吹出)至設備(A2)中，該設備(A2)含有例如儲槽、過濾器、旋風分離器(用於收集該等顆粒)及/或泵。 In the context of the present invention, the outlet (O2) is an optionally used opening through which particles and gases (for example after the reaction of step d) can be transported (or for example blown out) into the device (A2), which The device (A2) contains, for example, a storage tank, a filter, a cyclone (for collecting the particles) and/or a pump.
此外，在移除之前已於方法步驟d)中經改質之顆粒(P1)之後，可例如藉由熟習此項技術者已知且位於設備(A1)頂部處之粉末饋料器將新(新鮮、原始、未經改質)材料(顆粒(P1))饋入至設備(A1)中。 Furthermore, after removal of the modified particles (P1) prior to method step d), the powder feeders known to those skilled in the art and located at the top of the apparatus (A1) may be new (for example) Fresh, raw, unmodified material (particles (P1)) is fed into the device (A1).
在本發明之一個具體實例中，在氣相中進行步驟a)，且反應區(RZ)中之氣相可藉助於電漿來活化。可藉由電-磁場將必需之能量傳輸至氣相，其藉由偶合至反應區中之微波放電(2.45GHz、915MHz或任何其他適合之頻率)的偶合或藉由(由27.12MHz、13.56MHz或任何其他適 合之頻率)且在反應區(RZ)處生成的電感或電容偶合電漿來進行。 In a specific embodiment of the invention, step a) is carried out in the gas phase and the gas phase in the reaction zone (RZ) can be activated by means of a plasma. The necessary energy can be transferred to the gas phase by an electro-magnetic field by coupling or by coupling to a microwave discharge (2.45 GHz, 915 MHz or any other suitable frequency) in the reaction zone (by 27.12 MHz, 13.56 MHz) Or any other suitable Inductive or capacitive coupling generated at the reaction zone (RZ) is coupled to the plasma.
為提供在電漿活化下進行改質之能量而採用的產生器之適用輸出功率為熟習此項技術者已知的。較佳地，產生器為微波或射頻產生器，且能量並不限於上限值。若使用電漿活化，則產生器功率不超過500kW，產生器功率較佳不超過100kW，產生器功率更佳不超過30kW，且產生器功率最佳不超過5kW。產生器功率之下限較佳不低於1W。 Suitable output power for generators used to provide energy for upgrading under plasma activation is known to those skilled in the art. Preferably, the generator is a microwave or radio frequency generator and the energy is not limited to the upper limit. If plasma activation is used, the generator power does not exceed 500 kW, the generator power preferably does not exceed 100 kW, the generator power is better than 30 kW, and the generator power is optimally less than 5 kW. The lower limit of the generator power is preferably not less than 1 W.
在本發明之一個具體實例中，若使用電漿活化，則電磁激發頻率可低於100Hz、處於100Hz與10kHz之間的低頻範圍內、處於10kHz與300MHz之間的射頻範圍內、處於300MHz與300GHz之間的微波頻率範圍內及/或高於300GHz。 In a specific embodiment of the present invention, if plasma activation is used, the electromagnetic excitation frequency may be lower than 100 Hz, in a low frequency range between 100 Hz and 10 kHz, in a radio frequency range between 10 kHz and 300 MHz, at 300 MHz and 300 GHz. Between the microwave frequency range and / or higher than 300GHz.
在本發明之上下文內，氣態物料流(G2)可具有相對於氣態物料流(G1)在其個別流動方向上不同的角度α。角度α無法高於180°，因為180°意謂氣態物料流(G2)處於與氣態物料流(G1)相反的方向(參見圖2)。因此，例如200°之角度α將等於160°之角度α。 Within the context of the present invention, the gaseous stream (G2) may have an angle a different with respect to the gaseous stream (G1) in its individual flow direction. The angle α cannot be higher than 180° because 180° means that the gaseous material flow (G2) is in the opposite direction to the gaseous material flow (G1) (see Figure 2). Thus, for example, an angle α of 200° will be equal to an angle α of 160°.
在本發明之一個較佳具體實例中，氣態物料流(G2)之至少一個脈衝在設備(A1)內部的流動方向具有與(G1)之流動方向相差至少50°的角度α，較佳與氣態物料流(G1)之流動方向相差介於50°與180°之間，更佳相差介於80°與120°之間，最佳相差90°。 In a preferred embodiment of the present invention, at least one pulse of the gaseous material stream (G2) has an angle α within the apparatus (A1) that is at least 50° from the flow direction of (G1), preferably in a gaseous state. The flow direction of the material stream (G1) differs between 50° and 180°, and the better phase difference is between 80° and 120°, with an optimum phase difference of 90°.
然而，在此等所提及之角度中的任一者中，氣態物料流(G2)之脈衝可藉助於由氣態物料流(G1)及(G2)在設備(A1)中造成之亂流來容易地達到樣品保持器(SH)上之顆粒(P1)處。 However, in any of the mentioned angles, the pulse of the gaseous stream (G2) can be turbulent by means of the gaseous streams (G1) and (G2) in the apparatus (A1). It is easy to reach the particles (P1) on the sample holder (SH).
實施例： Example:
用於所有6個實施例中之起始材料(顆粒(P1))：夾層型可膨脹石墨(Graphit Kropfmühl ES350 F5，側向大小：80%>300μm) Starting material for all 6 examples (Particle (P1)): Sandwich type expandable graphite (Graphit Kropfmühl ES350 F5, lateral size: 80% > 300 μm)
實施例1-3：方法比較 Example 1-3: Method Comparison
藉由用設備(A1)中所填充之物質重量除以所填充之體積來計算材料之自由沉降/傾注體密度。 The free settling/pour body density of the material is calculated by dividing the weight of the material filled in the apparatus (A1) by the volume filled.
視下文實驗而定，反應產物可由膨脹材料以及非膨脹材料組成。 Depending on the experiment below, the reaction product may consist of an expanded material as well as a non-expanded material.
材料之自由沉降/傾注體密度值為針對膨脹程度(顆粒(P1)膨脹的多少)以及針對膨脹材料量(起始材料膨脹的多少)之組合量度。 其在此上下文中用於評估用於可膨脹夾層型石墨之膨脹的三種不同方法(實施例1至3)的效率。在處理之前及之後測定材料之自由沉降/傾注體密度。 The free settling/pour body density values of the materials are a combined measure for the degree of expansion (how much the particles (P1) expand) and for the amount of expanded material (how much the starting material expands). It is used in this context to evaluate the efficiency of three different methods (Examples 1 to 3) for the expansion of expandable sandwich graphite. The free settling/pour body density of the material was determined before and after treatment.
實施例1(比較性) Example 1 (comparative)
此方法為標準流體化方法，其可見於文獻(例如在「Principles and applications of CVD powder technology」,C.Vahlas,B.Caussat,Ph.Serp,G.Angelopoulos,Mat.Sci.Eng.Reports,2006,53,1-72)中。在此方法中，使用一種氣態物料流。以正向方向(其在圖1中對應於連續流模式中之氣態物料流(G2))連續地供應氣態物料流，亦即氣流自樣品保持器(SH)下方進入系統且向上流動，由此使處於樣品保持器上之顆粒(P1)流體化至反應區中。自頂部，亦即在樣品保持器(SH)及顆粒(P1)上方進行氣體泵送。 This method is a standard fluidization method, which can be found in the literature (for example in "Principles and applications of CVD powder technology", C. Vahlas, B. Caussat, Ph. Serp, G. Angelopoulos, Mat. Sci. Eng. Reports, 2006. , 53, 1-72). In this method, a gaseous stream is used. The gaseous material stream is continuously supplied in the forward direction (which corresponds to the gaseous stream (G2) in the continuous flow mode in Figure 1), that is, the gas stream enters the system from below the sample holder (SH) and flows upwards, thereby The particles (P1) on the sample holder are fluidized into the reaction zone. Gas pumping is performed from the top, ie above the sample holder (SH) and the particles (P1).
實驗參數： Experimental parameters:
氬氣流量(G2)：100-900ml/min Argon flow rate (G2): 100-900ml/min
(流量在實驗期間逐漸增加以將更多起始材料運載至反應區中)； 反應時間：20min； 產生器功率：1.5-2kW (The flow is gradually increased during the experiment to carry more starting material into the reaction zone); Reaction time: 20 min; Generator power: 1.5-2kW
(產生器功率根據增加之氣體物料流而增加) (The generator power is increased according to the increased gas flow)
實施例2(比較性) Example 2 (comparative)
此方法為將未經攪動之顆粒標準暴露於RF電漿中，其可見於文獻(例如在「Plasma-assisted simultaneous reduction and nitrogen doping of graphene oxide nanosheets」,N.A.Kumar,H.Nolan,N.McEvoy,E.Rezvani,R.L.Doyle,M.E.G.Lyons及G.S.Duesberg,J.Mater.Chem.A,2013，第1卷，第4431-4435頁)中。在此方法中，僅使用一種氣態物料流。氣態物料流在頂部進入系統且向下流動(其在圖1中對應於連續流模式中之氣態物料流(G1))(例如在「Formation of silicon carbide and silicon carbonitride by RF-plasma CVD」,H.Sachdev,P.Scheid,Diamond and Related Materials，第10卷，第3-7期，第1160-1164頁中)，亦即針對樣品保持器(SH)向下按壓系統中之任何顆粒(P1)。自樣品保持器(SH)下方進行氣體泵送。由於與實施例1相比反向之氣流方向，未發生顆粒混合，且僅直接暴露於電漿中之顆粒表面經改質，使未直接暴露於電漿中之所有顆粒及顆粒區域未經處理。 This method exposes the unstirred particle standard to RF plasma, which can be found in the literature (eg, in "Plasma-assisted simultaneous reduction and nitrogen doping of graphene oxide nanosheets", NAKumar, H. Nolan, N. McEvoy, E. Rezvani, RL Doyle, MEGLyons and GS Duesberg, J. Mater. Chem. A, 2013, Vol. 1, pp. 4431-4435). In this method, only one gaseous stream is used. The gaseous stream enters the system at the top and flows downwards (which corresponds to the gaseous stream (G1) in the continuous flow mode in Figure 1) (for example, in "Formation of silicon carbide and silicon carbonitride by RF-plasma CVD", H .Sachdev, P. Schieid, Diamond and Related Materials, Vol. 10, Nos. 3-7, pp. 1160-1164), ie pressing down any particles (P1) in the system against the sample holder (SH) . Gas pumping is performed from below the sample holder (SH). Due to the reverse gas flow direction compared to Example 1, no particle mixing occurred, and only the surface of the particles directly exposed to the plasma was modified so that all particles and particle regions not directly exposed to the plasma were untreated. .
實驗參數： Experimental parameters:
氬氣流量(G1)：100ml/min； 反應時間：20min； 產生器功率：1.5kW。 Argon flow rate (G1): 100ml/min; Reaction time: 20 min; Generator power: 1.5 kW.
實施例3(本發明) Example 3 (present invention)
實驗安排顯示在圖1中。氣態物料流(G1)在頂部進入設備(A1)且向下流動，亦即針對樣品保持器(SH)向下按壓設備(A1)中之顆粒(P1)。自樣品保持器(SH)下方進行氣體泵送。藉由氣態物料流(G1)之連續壓力/氣流及氣態物料流(G2)之脈衝來保證顆粒(P1)之混合，該氣態物料流(G2)將顆粒(P1)運載至反應區(RZ)中，將其保持在此處且使其混合。向下流動(G1)減少顆粒(P1)之淘析。在氣態物料流(G2)之壓力脈衝數增加的情況下，使顆粒(P1)膨脹。 The experimental arrangement is shown in Figure 1. The gaseous stream (G1) enters the apparatus (A1) at the top and flows downwards, ie the particles (P1) in the apparatus (A1) are pressed down against the sample holder (SH). Gas pumping is performed from below the sample holder (SH). The mixing of the particles (P1) is ensured by the continuous pressure/gas flow of the gaseous stream (G1) and the pulse of the gaseous stream (G2), which carries the particles (P1) to the reaction zone (RZ) Keep it here and mix it. The downward flow (G1) reduces the elution of the particles (P1). In the case where the number of pressure pulses of the gaseous stream (G2) is increased, the particles (P1) are expanded.
實驗參數： Experimental parameters:
氬氣流量(G1)：100ml/min； 氬氣脈衝(G2)：10； 反應時間：10分鐘； 產生器功率：1.5kW。 Argon flow rate (G1): 100ml/min; Argon pulse (G2): 10; Reaction time: 10 minutes; Generator power: 1.5 kW.
實施例1-3之結果 Results of Examples 1-3
起始材料之自由沉降體密度為約570mg/cm3。 The free settler density of the starting material was about 570 mg/cm 3 .
實施例4-6：多步驟實驗(連續膨脹及化學改質) Example 4-6: Multi-step experiment (continuous expansion and chemical upgrading)
在第一步驟中在氬氣電漿中使可膨脹夾層型石墨膨脹，且隨後在第二步驟中進行改質。 The expandable sandwich type graphite is expanded in an argon plasma in the first step, and then reformed in the second step.
在實施例4中，亦在化學改質步驟期間使用惰性氣體氬氣以供應參考樣品。在實施例5中，在氬氣電漿膨脹之後進行氮氣電漿改質。在實施例6中，在氬氣電漿膨脹之後進行二氧化碳電漿改質。 In Example 4, an inert gas argon gas was also used during the chemical upgrading step to supply a reference sample. In Example 5, nitrogen plasma reforming was performed after argon plasma expansion. In Example 6, carbon dioxide plasma reforming was performed after argon plasma expansion.
使用化學改質步驟，在材料表面處引入例如氮之雜原子及/或形成例如含有氧或氮之官能基。 Using a chemical upgrading step, a hetero atom such as nitrogen is introduced at the surface of the material and/or a functional group such as oxygen or nitrogen is formed.
實施例4(本發明)：氬氣電漿連續膨脹及氬氣電漿化學改質，參考實驗 Example 4 (Invention): Continuous expansion of argon plasma and chemical modification of argon plasma, reference experiment
對於連續膨脹(形態改質)及化學改質兩者，使用惰性氣體氬氣。對改質步驟不使用反應氣體以便提供參考樣品。 For both continuous expansion (morphological upgrading) and chemical upgrading, an inert gas of argon is used. No reactive gas is used for the upgrading step to provide a reference sample.
用於連續膨脹(步驟1)之實驗參數：氬氣流量(G1)：100ml/min；氬氣脈衝(G2)：7；反應時間：7min；產生器功率：1.5kW Experimental parameters for continuous expansion (step 1): argon flow rate (G1): 100 ml/min; argon pulse (G2): 7; reaction time: 7 min; generator power: 1.5 kW
用於改質(步驟2)之實驗參數：氬氣流量(G1)：60ml/min；氬氣脈衝(G2)：8；反應時間：12分鐘；產生器功率：1kW Experimental parameters for upgrading (step 2): argon flow rate (G1): 60 ml/min; argon pulse (G2): 8; reaction time: 12 minutes; generator power: 1 kW
實施例5(本發明)：氬氣電漿連續膨脹及CO2電漿改質 Example 5 (Invention): continuous expansion of argon plasma and reformation of CO 2 plasma
用於連續膨脹(步驟1)之實驗參數：氬氣流量(G1)：100ml/min；氬氣脈衝(G2)：7；反應時間：7min；產生器功率：1.5kW。 Experimental parameters for continuous expansion (step 1): argon flow rate (G1): 100 ml/min; argon pulse (G2): 7; reaction time: 7 min; generator power: 1.5 kW.
用於連續膨脹(步驟2)之實驗參數：二氧化碳流量(G1)：60ml/min；氬氣脈衝(G2)：8；反應時間：12分鐘；產生器功率：1kW。 Experimental parameters for continuous expansion (step 2): carbon dioxide flow rate (G1): 60 ml/min; argon pulse (G2): 8; reaction time: 12 minutes; generator power: 1 kW.
實施例6(本發明)：氬氣電漿膨脹及N2電漿改質 Example 6 (Invention): Argon plasma expansion and N 2 plasma modification
用於膨脹(步驟1)之實驗參數：氬氣流量(G1)：100ml/min；氬氣脈衝(G2)：7；反應時間：7min；產生器功率：1.5kW。 Experimental parameters for expansion (step 1): argon flow rate (G1): 100 ml/min; argon pulse (G2): 7; reaction time: 7 min; generator power: 1.5 kW.
用於化學改質(步驟2)之實驗參數：氮氣流量(G1)：60ml/min；氬氣脈衝(G2)：8；反應時間：12分鐘；產生器功率：1kW。 Experimental parameters for chemical upgrading (step 2): nitrogen flow rate (G1): 60 ml/min; argon pulse (G2): 8; reaction time: 12 minutes; generator power: 1 kW.
實施例4-6之結果 Results of Examples 4-6
藉由進行氧化性電漿改質步驟，例如藉由使用CO2電漿(實施例5)，可增加經處理材料之氧含量(參見表2)。藉由應用使用含氮電漿、例如氮氣電漿(實施例6)之改質步驟，增加材料之氮含量(參見表2)。此外，根據XPS，形成不存在於起始材料中之新氮官能基(參見圖4)。 The oxygen content of the treated material can be increased by performing an oxidative plasma upgrading step, such as by using a CO 2 plasma (Example 5) (see Table 2). The nitrogen content of the material is increased by applying a upgrading step using a nitrogen-containing plasma, such as a nitrogen plasma (Example 6) (see Table 2). Further, according to XPS, a new nitrogen functional group which is not present in the starting material is formed (see Fig. 4).
此外，在圖4中顯示起始材料及實施例4-6之N 1s XPS細節光譜。光譜展示氮氣電漿改質步驟(實施例6)不僅增加經處理材料中之氮含畫，且亦導致形成新氮物質(其不存在於氮氣電漿改質之前的材料中)。 In addition, the starting materials and the N 1s XPS detail spectra of Examples 4-6 are shown in FIG. The spectral display nitrogen plasma upgrading step (Example 6) not only increased the nitrogen content in the treated material, but also resulted in the formation of a new nitrogen species (which was not present in the material prior to the nitrogen plasma modification).
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