PARTICLE TREATMENT METHOD IN WHICH PARTICLES FOR TREATMENT ARE SUBMITTED TO PLASMA TREATMENT IN A TR

专利摘要:
particulate materials, composites comprising them, preparation and uses thereof. the present invention relates to methods of processing particulate carbon material, such as graphical particles or carbon nanoparticle clusters such as cnts. the starting material is agitated in a treatment vessel in the presence of low pressure plasma (luminescence) generated between the electrodes. preferably the material is agitated in the presence of conductive contact bodies such as metal balls or other contact formations with surface area relatively high specificity, on the surface on which the luminescent plasma is present and between which the material to be treated moves. it was observed that the methods effectively de-agglomerate the nanoparticles and exfoliate graphitic material producing very thin graphical sheets showing graphene-like characteristics. the resulting disaggregated or exfoliated carbon nanomaterials are an aspect of the present description, as is the use of them dispersed in composite materials. the particle surfaces can be functionalized by choosing the appropriate gas to form the plasma. the invention is advantageous in safe, dry and moderate conditions achieving a high degree of disintegration or exfoliation compared to previous chemical methods
公开号:BR112013014376B1
申请号:R112013014376-2
申请日:2011-12-08
公开日:2020-12-15
发明作者:Ian Walters；Martin Williams
申请人:Haydale Graphene Industries Plc；
IPC主号:

专利说明:

[001] The present invention relates to particulate materials, treatment and preparation of particulate materials, composite materials that comprise said particulate materials, articles and devices that comprise said composites, methods for their preparation and uses thereof.
[002] The proposals presented here have a particular application for the processing of inorganic or mineral particle material, in which some or all the particles comprise, consist of (or consist essentially of) agglomerated, entangled or become mutually cohesive and subsidiary or component particles or structures, such as nanoparticles or atomic layers.
[003] In particular, the preferred embodiments refer to carbon or carbon-containing materials, in which the aforementioned particles of the mentioned components or structures may be special allotropes of carbon, such as fullerenes (notably tubular, that is, nanotubes), or composed of graphitic graphene or in stacked graphene bodies. The special proposals inserted here contribute to disaggregate or separate the component particles or structures, such as the untangling and separation of CNTs or exfoliating graphenes, preferably with the subsequent dispersion in a liquid vehicle or in matrix material. BACKGROUND CNTs
[004] Carbon nanotubes (CNT), their remarkable properties and potentials, and methods for their preparation have been known for many years. However, its industrial uses are still very limited, largely because of processing and handling problems. They can be produced by several processes, but the main ones are the discharge of electrode arc containing carbon, and deposition in carbon vapor phase, by laser ablation or CVD, on the metal catalyst particles. Said methods can make single wall CNTs and several types of wall (S CNTs and M CNTs) and are well known to those skilled in the art.
[005] The resulting CNTs are generally contaminated with residues of one or more of catalyst, amorphous carbon and closed (usually unwanted) fullerenes and these residues tend to bind the CNTs together. In addition, CNTs, like most nanoparticles, have a strong tendency to cluster under the influence of van der waals forces, because of their extremely high specific surface area. With CNTs this is exacerbated by its very high aspect ratio leading to extensive tangling and tangling and structures such as nodules, granules, tangled bundles or "strings" of braided CNTs. Production batches with the highest volume of CNT produced by the methods mentioned above consist essentially of the said entangled and contaminated aggregate structures.
[006] Many of the important uses foreseen to explore the special properties of CNTs involve their dispersion in matrix or in binder materials. As an intermediate stage of manipulation, dispersion is expected in a liquid vehicle such as water or an organic solvent (especially in view of the health risks posed by dry particles). However, the routine existence of the bulk product in the form of tangled agglomerates and its lack of chemical affinity with the vehicle or matrix presents a major obstacle to dispersion. Where dispersions can be formed these tend to be dispersions of agglomerates, so that the properties of the CNTs themselves are hardly available.
[007] It is known that in order to functionalize and disperse nanoparticle aggregates in general, and CNTs in particular, an aggressive combination of mechanical and chemical treatments is used, for example, by boiling in acid to decompose contaminants and functionalize the surface of the carbon, and breaking the aggregates using high shear methods, such as crushing, grinding or ultrasound. The dispersion can then be stabilized to some extent, in a liquid vehicle by means of surfactants or other methods of colloid chemistry. This has been somewhat successful, but these techniques for particle functionalization remain highly inefficient, costly and inconvenient as far as industrial application is concerned. In addition, they still reach only the modest breakdown levels of individual CNTs. Typically, CNTs are still twisted into cables, and often have very serious structural damage to the carbon layers (layers of graphite on the CNT wall), as well as shortening of the tubes, with the consequent loss of valuable properties of the CNT. Each chemically modified (functionalized) field represents a structural defect, with a missing carbon atom or rearrangement of the bond.
[008] CNTs also present a health risk, real or perceived, if inhaled or in general, if they come into contact with permeable membranes of the body. Thus, despite their extensive knowledge of their potential properties and ways of producing them, they have found limited industrial application. Graphene
[009] Separately, graphene is known as the hexagonal form of a single layer of carbon, which corresponds to a single layer of graphite structure, but with superior properties of graphite due to the absence of neighboring layers. Graphene layers can be produced in large dimensions by careful mechanical "spoliation" or intercalation using an oxidizer, such as concentrated sulfuric acids and nitric acid, from graphite, by reducing exfoliated graphene oxide, or by growth epitaxial on substrates of other materials. However, the known methods are laborious and expensive.
[0010] The use of graphite-based materials, with their characteristic layer structure (a graphene sheet being a hexagonal structure of carbon atoms and graphite being a series of said stacked sheets) becomes relatively attractive, taking into account the disadvantages of CNTs. Even when extremely thin (one or a few layers) they are more like CNT particles and, therefore, safer and less difficult to handle and disperse. Even more so than with CNTs, however, there was no easy commercial-scale source of readily usable graphene material. While CNTs have been known for many years, the first successful preparations of true graphene occurred only recently. Synthetic graphene developed in the laboratory is only available in small quantities at enormous cost. There are a number of important practical applications, but their implementation is necessarily very limited.
[0011] The other methods available to produce a graphene material are as follows. Mined graphite is used as a starting material. An intercalation step to allow exfoliation can be chemically intercalated, electrochemical intercalation, gas phase intercalation, liquid phase intercalation, intercalated with supercritical fluid, or by a combination thereof. Chemical intercalation can expose graphite to sulfuric acid, sulfonic acid, nitric acid, carboxylic acid, to a metal chloride solution, to a metal-halogen compound, to a liquid or vapor halogen, to a permanganate of potassium, an alkaline nitrate, an alkaline perchlorate, an oxidizing agent, or a combination thereof. Allogens can also be used to intercalate, for example, from bromine, iodine, iodine chloride, iodine bromide, bromine chloride, iodine pentafluoride, bromine trifluoride, chlorine trifluoride, phosphorus trichloride, tetrachloride, tribromide, triiodide, or a combination thereof.
[0012] Electrochemical intercalation can use nitric acid or a carboxylic acid, both as electrolyte and intercalated source, with a current density in the range of 50 to 600 A / m2 in graphite, which is used as an electrode.
[0013] The step of exfoliating the interleaved graphite may include exposing the interleaved structure to a temperature in the range of 150 ° C to 1100 ° C. When intercalation uses an acid as an intercalate, the exfoliator typically comprises exposing the intercalated graphite to a temperature in the range of 600 ° C to 1100 ° C. When intercalation uses an alogen compound or an alogen, the exfoliating typically comprises exposing the intercalated graphite to a temperature in the range of 50 ° C to 350 ° C. THE INVENTION
[0014] The objective here is to provide new and useful particulate materials, composite materials that comprise said particulate materials, articles and devices that comprise said composites, methods for their preparation and uses thereof.
[0015] Aspects of the invention include the following.
[0016] A first aspect is a treatment method to de-aggregate, de-agglomerate, exfoliate, clean or functionalize the particles, in which the particles for treatment are subjected to a plasma treatment, in a treatment chamber containing or comprising several solid bodies of electrically conductive contact or contact formations, the particles being agitated with said contact bodies or contact formations and in contact with plasma in the treatment chamber.
[0017] The particles to be treated are preferably carbon particles, such as particles, which consist of or comprise graphite, carbon nanotubes (CNTs) or other nanoparticles.
[0018] Preferably, said contact bodies are films in the treatment chamber. The treatment chamber can be a drum, preferably a rotating drum, in which a plurality of contact bodies are polished or agitated with the particles to be treated. The treatment vessel wall can be conductive and form a counter electrode for an electrode that extends into an interior space of the treatment chamber.
[0019] During treatment, the luminous plasma desirably forms on the surfaces of the contact bodies or in the contact formations.
[0020] Suitable contact bodies are metal balls or metal-coated balls. The contact bodies or contact formations can have a shape of a diameter, and the diameter is desirably at least 1 mm and not more than 60 mm.
[0021] The pressure in the treatment tank is generally less than 500 Pa. Desirably, during treatment, the gas is fed into the treatment chamber and the gas is removed from the treatment chamber through a filter. This means that it is fed by maintaining the chemical composition, if necessary, and / or to prevent the accumulation of any contamination.
[0022] The treated material, that is, the particles or components disintegrated, de-agglomerated or exfoliated from it resulting from the treatment, can be components chemically functionalized by components of the plasma-forming gas, for example, forming functionalities of carboxy, carbonyl, OH, amine, amide or halogen on their surfaces. The plasma-forming gas in the treatment chamber can be, or include, for example, any oxygen, water, hydrogen peroxide, alcohol, nitrogen, ammonia, organic amino-supporting compounds, halogen such as fluorine, halogenated hydrocarbon such as noble gas and CF4.
[0023] In important aspects the particles to be treated consist of or comprise graphitic carbon, such as extracted graphite, which is exfoliated by the treatment. After treatment, the treated material may comprise or consist of different graphene platelets or graphites with a platelet thickness less than 100 nm and a larger dimension perpendicular to the thickness which is at least 10 times the thickness.
[0024] The treatment can be continued for at least 30 minutes and / or until the treated carbon material comprises, by weight, at least 90% of platelets less than 100 nm thick and where the largest dimension is at least 10 times the thickness, preferably at least 100 times the thickness. More preferably, the treatment is continued until the treated carbon material comprises by weight, at least 80%, preferably at least 90%, of platelets less than 30 nm in thickness, preferably less than 20 nm in thickness, and in that the main dimension is at least 10 times the thickness, preferably at least 100 times the thickness.
[0025] Another aspect inserted here is a method of preparing a dispersion of particles or a composite material, which comprises
[0026] treating the particles by any particle treatment method defined or described here, and,
[0027] disperse the treated material in a liquid vehicle or matrix material.
[0028] The particles can be dispersed in a polymer-polymer material, for example, epoxy resin, polyolefin, polyurethane, polyester, polyamide or poly (meth) acrylic material or mixture or copolymer of said types of polymer, or it is a precursor, for example, of oligomer or monomer, of said polymer.
[0029] Especially in this aspect the treated material may comprise carbon nanotubes, or graphite or graphene platelets as defined in any preferred aspect or aspect included here, dispersed in said polymer matrix material, preferably at least 10% by weight of the composite material, to make an electrically conductive composite material.
[0030] Another aspect seen here is the new particulate carbon material as described in any aspect, such as the material obtained or obtainable by any method defined or described here, comprising platelets of distinct graphite and / or carbon nanotubes.
[0031] Another aspect is a dispersion of particles or a composite material comprising any particulate carbon material defined or described herein dispersed in a liquid carrier or matrix material. As mentioned above it can be a polymeric matrix material, which is, for example, an epoxy resin, polyolefin, polyurethane, polyester, polyamide or poly (meth) acrylic material or the mixture or copolymer of these types of polymer, or is a precursor of, for example, oligomer or monomer, of such a polymer.
[0032] An additional aspect is an article or device comprising an electrically driven element or a layer comprising or consisting of a composite material as defined above, or obtained by a method as defined or described here, such as a photovoltaic device, a field emission device, a hydrogen storage device, the battery or battery electrode.
[0033] Specifically in relation to the graphite material, it has been observed that by using the plasma processing methods described here, a starting graphite material can be separated effectively and with good yields on platelets, containing no more than than a few layers, and sometimes a single layer of graphene. It is essentially a dry method, at moderate temperatures. The product materials, thus available in significant quantities at a reasonable cost, are found to provide many or most of the highly desirable characteristics associated with true synthetic graphene. It has also been discovered that the nanomaterials produced can actually, especially because of their controllable and relatively uniform degrees of functionalization, be dispersed in matrix materials, especially polymer materials, providing excellent properties that can be implanted, for example, in devices photovoltaic, field emission devices, hydrogen fuel storage, rechargeable battery electrodes and (mechanically) reinforced composite materials.
[0034] It has been discovered that the plasma-processed particles of our invention are notable for the uniformity and controllability in general of the degree of functionalization of the surfaces of the particles in the process. They also exhibit effective functionalization when treating the surfaces of the starting particles that are initially unexposed, and offer excellent performance in this area.
[0035] As mentioned, this application proposes new materials in carbon particles, new composite materials that contain particulate materials, products and devices containing, comprising or produced from said composite materials and the methods of manufacturing and using all of these.
[0036] In another aspect, the invention provides a carbon particulate material comprising or consisting of distinct graphite platelets or graphene with a platelet thickness less than 100 nm and a larger dimension (length or width) perpendicular to the thickness .
[0037] The thickness of the platelets is preferably less than 70 nm, preferably less than 50 nm, preferably less than 30 nm, preferably less than 20 nm, preferably less than 10 nm, preferably less than 5 nm. The large dimension is preferably at least 10 times, more preferably at least 100 times, more preferably at least 1000 times, more preferably at least 10,000 times the thickness.
[0038] The length can be at least 2 times, at least, 3 times, at least 5 times or at least 10 times the width, for example, depending on the starting material from which the platelets are produced.
[0039] The particulate material may comprise other than platelet particles, for example, nanotubes or nanobonds mixed with it. Desirably, the mass or population of particulate carbon material comprises, by weight, at least 10%, more preferably at least 20%, more preferably at least 30%, more preferably at least 40%, most preferably at least 50%, more preferably at least 60%, more preferably at least 70%, more preferably at least 80% and, perhaps, at least 90%, all or substantially all platelets with any combination of general and preferred dimensions and ratios dimension specified above, provided that said percentage is only evaluated on particles where the main dimension is at least 10 times, more preferably only on particles where the main dimension is at least 50 times or at least 100 times the thickness. Additionally or alternatively it can be evaluated only on particles whose size is at least 500 nm. This means that occasionally very large or very small particles can be ignored.
[0040] In particular, it is preferred that at least 90%, all or substantially all of the platelets are less than 100 nm thick, more preferably less than 70 nm thick.
[0041] The percentages can alternatively be determined based on the numbers of particles, instead of the weight, if a counting method is used for the measurement. Laser diffractometry is well known as a means of measuring particle sizes and size profiles, and can be used, or allow adjustment to the flat shape of platelets. Counting and measurement can, however, be produced in sets of particle samples in electron microscopy images, for example, at least 20, 50 or at least 100 measured particles.
[0042] The present invention can cause the particles through the processing of a coarse starting carbon material, such as particles and / or graphite or carbon fibers, to divide by exfoliation and / or intercalation as different from the development platelets synthetically. Thus, the material comprises particles of varying thickness and large dimensions, indicating that it is obtained or may be obtained by said process. Desirably, it includes at least some single-layer graphene sheets in which the largest perpendicular dimension is at least 10 times, more preferably at least 100 times the thickness.
[0043] Graphite / graphene sheets can be flat, curved or rolled.
[0044] The particles can carry functional groups on the surfaces and / or edges of the platelets. These can be, for example, functional groups containing oxygen, such as carboxyl, carbonyl or hydroxy, groups containing nitrogen, such as amine or amide, or halogen, such as F. Desirably, however, the material contains at least 80% , more preferably at least 85%, more preferably at least 90% carbon.
[0045] Another aspect of the present invention is a process of manufacturing a particulate carbon material according to any of the general or preferred definitions set out above, by treating a carbon atom in particles of fibrous or starting material, especially a graphite starting material (which can be natural graphite) in a plasma according to any method described below, thus separating the layers of the graphite structure by intercalating plasma species and / or by exfoliation in the environment of the plasma.
[0046] The gas in which the plasma is formed can be selected to cause the corresponding functionalization of the platelet surfaces, for example, as described above. Relevant components of the plasma-forming gas for this purpose can be, for example, oxygen, water, hydrogen peroxide, alcohols, nitrogen, ammonia, organic amino-supporting compounds such as ethylene diamine, halogens, or halogenated hydrocarbons, such as CF4. Noble gas such as Ar can be used to prevent or limit the degree of functionalization, for example, by diluting an active gas and / or by being used in a separate phase so that during this exfoliation phase it continues without functionalization.
[0047] The particular virtue of current plasma-based processes, especially those using moving contact bodies, as described below, is that not only do they allow for extremely easy production of highly exfoliated graphite sheets, with few layers of graphene and similar behavior , but they also lead to uniform and controllable functionalization, compared to, for example, the prior art technique, in which some of the exfoliations are mechanically activated by grinding or grinding after chemical treatment with acid that functionalizes only exposed surfaces at that time.
[0048] If desired, the processed material can be the object of size or form of classification to select particles of a particularly desired shape, for example, the finest. This classification can be, for example, a sedimentation method.
[0049] Another aspect of the present proposals is a composite or nanocomposite material comprising any material in carbon particles as defined previously dispersed as a discontinuous or substantially discontinuous phase in a continuous matrix material, desirably, a solid matrix material. In addition, a method of making said composition comprising dispersing the particulate carbon material in the matrix or liquid precursor fluid thereon, optionally with the prior preparation of the particulate carbon material by a method as described herein.
[0050] The matrix is preferably polymeric, thermoplastic or heat-healing. It can be, for example, epoxy resin, polyolefins (for example polyethylene or polypropylene), polyurethane, polyester, polyamide, poly (meth) acrylic or other polymer. It can be a petroleum-based polymer or a natural / biopolymer.
[0051] Plasma-functionalized carbon particles in nanoscale with high aspect ratios have a high specific surface area, providing superior reinforcement properties when compared to traditional fillers. In addition to the effects of norepowers, a region of reduced mobility interphase around each plasma functionalized nanoparticle results in a percolation interphase network in the composite, which can play an important role in improving properties.
[0052] The nanometric plasma-functionalized carbon particles can improve the mechanical and barrier properties of polymers. When incorporated into polymeric matrices, they can provide active or intelligent properties for packaging systems, potentially improving food safety / stability or information about the status of a safety / stability product.
[0053] Said polymeric nanocomposites generally have much better addition polymer interactions than traditional composites. A uniform dispersion of plasma-functionalized nanometric carbon particles in a matrix polymer results in a large matrix / interfacial fill area. This restricts the mechanical mobility of the matrix, improving its mechanical and thermal profile, increasing its Tg and its barrier properties.
[0054] Plasma-induced and electrically conductive nanoparticles composites are particularly useful for protecting sensitive electronic equipment against electromagnetic interference (EMI) and radio frequency interference (RFI), and for the dissipation of electrostatic charge.
[0055] The amount of plasma-functionalized carbon particles mixed with the matrix polymer depends naturally on practicality, compatibility and the effect sought. However, the very thin structure of the nanoparticles generally provides a great effect for a small amount added. The amount is generally less than 20%, by weight, of the composite, preferably less than 10%, less than 5% or even less than 1%.
[0056] Recently, there has been a growing interest in the development of graphene polymer / nanocomposites due to their drastically improved properties compared to conventionally charged polymers with a very low fraction of charge addition. Unique properties can be obtained by adding very small amounts of graphene flakes or nanoparticles. The properties can therefore be increased in the desired ratio without sacrificing the usual characteristics of the polymer, in other aspects, such as processability, mechanical properties and standard density.
[0057] The present invention also provides a nanocomposite reinforcing filler material comprising the aforementioned platelets with a high length-to-width ratio. The referred-donanocomposite can become electrically conductive with a small fraction of weight of platelets. Conductive composites are particularly useful for protecting sensitive electronic equipment against electromagnetic interference (EMI) and radio frequency interference (RFI), and for dissipating electrostatic charge. Another use is in photovoltaic devices, e.g. of the dye-sensitized type.
[0058] Normally, the dispersion of said materials is problematic due to agglomeration, but the high levels of initial dispersion (non-agglomeration) of the present materials combined with the possibility of effective and uniform chemical functionalization, which can be selected to give matrix compatibility, allows good dispersion in a matrix without much difficulty.
[0059] Examples of functionalization are as follows.
[0060] Treatment of tetrafluoride (CF4) with charcoal followed by ammonia (NH3). CF bonds can be replaced by amino (contains a carboxylic acid and amine group). Alkyl (C-H bonds), and hydroxyl. In XPS experiments (ESCA) it is shown that the use of FC gives a high level of fluorination after a short period of time (30 minutes gave 14.1%).
[0061] Fluorination before NH3 treatment increases NH3 functionality, providing access points for substitution of amine groups. Fluorine is also expected to react with the epoxy hardener at elevated temperatures with a catalyst.
[0062] Treatment of oxygen at higher pressure (0.6 torr / 80Pa) and longer time favors the formation of carboxylic groups and CNTs in graphite plates.
[0063] Fluorine + oxygen: fluorine can be easily displaced by groups of carboxylic acid.
[0064] Argon and nitrogen are known to show 10% nitrogen and 8% oxygen, peak amine (3.9%). Oxygen and amidation (COOH) + NH2-R-NH2 (eg ethylene diamine) creates an amide bond C-NH-R-NH2 treatment of oxygen followed by ammonia.
[0065] Treatment with oxygen, C = 0 forms bonds (more common than COOH), and reacts with NH3 (ammonia). In addition, it provides C-NH2 + H2O (provides an amide bond). Oxygen + ethanolamine (OH-COOH + R-NH2 = C-O-CR-NH2) + Oxygen ethylene diamine. (OH-COOH + R-NH2 = C-O-C-R-NH2). The hydrogen peroxide will contain the oxygen and hydrogen needed to create CO-OH and OH groups.
[0066] Plasma treatments allow ready control of the% functionalization of available locations on carbon, adjusting gas concentrations and treatment times. This is very important to achieve practical dispersibility of a given material in a given polymer. The effect of mixing a particular particle by changing the viscosity in the polymer matrix depends very strongly both on its specific surface area and on the% functionalization of its surface. Conventional methods are not able to reliably control these things, whereas present methods can. FINAL USES: COMPOSITES AND DEVICES / ARTICLES
[0067] In photovoltaic devices, ITO (tin indium oxide) is the industry standard material mixed in the polymer matrix of the device layers to make them electrically conductive. Graphene or low-layer graphitic platelets will naturally offer excellent flat conductivity, as long as they can be dispersed in the polymer matrix. We have observed that the low-layer graphite platelet materials of the present invention do in fact also offer satisfactory transparency, so that they can be used in this very important technical area, for example, as suitable for ITO.
[0068] Independently, there is a general value in being able to incorporate nanoscale particles (particles having at least a dimension of less than 100 nm) of any type, for example, CNTs such as SWCNTs or MWCNTs, nanobuses (not -ococci), in-sheets or nano-platelets such as graphitic platelets, effectively within a matrix material such as a matrix polymer. These are desirably carbon or carbon based. To achieve effective dispersion it is necessary that the nanoscale particles are sufficiently de-agglomerated or not cohesive so that they can be initially dispersed in the matrix, and also that the chemical nature or compatibility of the nanoparticle surfaces with respect to the matrix material is such that they remain stable dispersed, for example, as a substantially discontinuous and / or substantially uniformly dispersed phase, and desirably without significant agglomeration or reaglomeration of the particulate in the composite. Again, this may require controllable functionalization of the particle surfaces.
[0069] The treated particles have a wide range of uses. In a preferred embodiment, the particles, treated or produced by the present methods, are incorporated into a polymeric matrix. Said polymeric matrix can be, or can form the basis of a specialized functional component such as a conductive plastic component, or an electro-functional organic component or material, such as a photovoltaic element or layer, or a structural component in which the nanoparticles dispersed materials such as graphical platelets and / or CNTs provide additional strength.
[0070] Other applications for particles that have been processed according to the present method are in paints, paints, coatings or laminar materials. A masterbatch of a corresponding liquid containing the particles can be prepared, for example, in the treatment vessel containing the activated particles.
[0071] A liquid introduced into the container for the dispersion of the particles can be a curable polymer composition, or component or precursor thereof.
[0072] Since the particles tend to carry the same electrical charge, they naturally tend to self-disperse in a fluid or matrix, transport or liquid vehicle.
[0073] An alternative for the use of liquid is to store the particles at low temperature, for example, under liquid nitrogen, to minimize the chemical reaction with the activated particles. This can be done in the same container.
[0074] Features of Plasma Treatment
[0075] In WO 2010/142953 particular methods of treating low pressure plasma (luminescence) were proposed as a means of providing chemical activity of CNTs and other small particles and dispersing them. Certain general methods and apparatus from WO 2010/142953 are applicable here, for example, as follows.
[0076] Particles are placed in the container, the container is closed and the particles are subjected to plasma treatment when generating plasma inside the container. Plasma treatment involves positioning the electrodes in opposite positions relative to an interior space in the container, and generating plasma between the electrodes in a region within the container.
[0077] In a preferred embodiment, an electrode extends within an interior space of the container to be surrounded by the space, for example, as a central or axial electrode, and the other electrode is an external or surrounding electrode. The outer wall of the container is desirably cylindrical, or circular in cross-section. It can be or can comprise the counter electrode. The container is desirably in the form of a drum.
[0078] In a preferred embodiment an interior, for example, the axial trode is, or comprises, or is positioned in the recessed portion or socket formation of the container wall. For example, the recessed portion of the container wall can extend axially, like a hollow formation, through the middle of the container space. It can be (or comprise) the dielectric wall of the container portion, or the conductive wall of the container portion. To generate plasma, a central electrode connected to an electric actuator can be connected to or inserted into said central recessed electrode or electrode cover of the container. A counter electrode is positioned around, outside or surrounding the container wall. The application of an electric field between the electrodes generates plasma in the container.
[0079] It is preferred that the plasma treatment is by means of low pressure plasma of the "luminescence discharge" type, generally using DC or low frequency RF (less than 100 kHz). [Alternatively microwaves can be used, in which case the specified electrode structure may not be necessary]. The pressure in the treatment vessel is desirably less than 1000 Pa, more preferably less than 500 Pa, less than 300 Pa and even more preferably less than 200 Pa or less than 100 Pa. For the treatment of CNTs and graphitic particles especially, pressures in the range of 0.05 - 5 mbar (5 - 500 Pa) are generally suitable, more preferably 0.1 - 2 mbar (10 -200 Pa).
[0080] In order to generate low pressure or luminescent plasma, the inner container needs to be evacuated. An evacuation port can be provided for this purpose, and in the present method it is connected to an evacuation medium via a suitable filter to retain the particles. The filter must be selected with respect to its pore size to retain the particles in question, and with respect to its material to resist processing conditions and to avoid unwanted chemical or physical contamination of the product, depending on its intended use. For particle retention, HEPA, ceramic, glass or sintered filters may be suitable depending on the size of the particles. The evacuation door can be on a main wall of the container or on a lid or cover.
[0081] During plasma treatment, the container is desirably shaken or rotated to cause the relative movement of the particles within. This can include the movement of particles falling through the space of the container, through the plasma zone. The treatment vessel (defining the treatment chamber) can be rotated about an axis, for example, an electrode axis that protrudes internally as mentioned above.
[0082] In a low pressure plasma treatment system, the application of vacuum is desirably combined with a gas supply for the formation of plasma, so that the treatment atmosphere can be controlled and, if necessary, gas contaminated or spent on treatment removed during the process. Again, said gas supply can be through a particle retention filter built into the container wall. A suitable location for the gas supply filter is on a recessed electrode or electrode cover portion portion as mentioned above.
[0083] The above-mentioned internally projecting electrode portion, or electrode cover portion into which an external electrode is inserted, can itself be detachably inserted into the body of the container. This can be by means of a screw thread, grounding gasket, plug fitting or other suitable sealed union. The joint must be able to prevent the escape of particles. Said electrode portion or electrode cover portion may in general be tubular. It can be cantilevered, or it can be a connection between opposite walls. When swinging, a gas inlet filter can be positioned at the distal end of the filter.
[0084] The container may be provided with a removable or removable sealable lid or cover, for example, to cover a main opening through which the particles can be loaded into and / or discharged from the inner container. The container wall, for example the lid, can incorporate a door for the application of vacuum, for example, including a filter as mentioned above. The container wall, for example, the lid can incorporate a port for the injection of reagent or gas for chemical treatment.
[0085] An electrode or electrical supply of the plasma treatment apparatus can be inserted into or connected to a recessed electrode or electrode cover formation of the container. If the reentrant formation is conductive in itself, then it constitutes an electrode when the electrode of the system is connected to it. If the recessed formation of the container comprises or constitutes an electrode cover of dielectric material, for example, glass, then the electrode of the inserted system, needs to fit tightly inside it to avoid the generation of unwanted plasma in the spaces between said components. The electrode of the system in the form of a rod or tube is then desirably fit into an elongated tubular cover.
[0086] An external or counter electrode can be an external conductor drum or housing. It can be or be incorporated in an external wall of the treatment container itself, for example, the wall of the drum. Or, it can be a separate rotating treatment drum for plasma devices, within which the treatment container containing the particles can be supported to rotate with the drum.
[0087] The wall of the treatment container or drum may have elevation formations, such as shovels, vanes, deflectors, recesses, dents or the like that are formed and sized so that, as it is rotating at a predetermined operational speed , with the mass of particles for treatment contained in the treatment chamber, the particles are lifted by the drum wall formations from a lower region of the chamber and released to fall, for example, selectively along a path that passes through the plasma zone adjacent to the axial electrode. Said formations can be integral with or fixed to the container wall. They can be made of conductive material or non-conductive material (dielectric). However, when contact bodies or contact formations are used they may be unnecessary, as the contact bodies / formations may have their own plasma "halos", and with heavy or dense bodies falling it may be undesirable. The gentle agitation of the mass of the bodies in contact with the particles for treatment, for example, at the bottom of a rotating, oscillating, alternating or vibrating drum or container, provides good results.
[0088] By experimentation it has been observed however that with the alternative adjustment, in which plasma in a rotating drum is located along a generally axial region, and the wall of the drum is formed and the drum rotated in such a way that the particles fall preferably through that region, together with the use of a low pressure discharge plasma, a useful particle treatment can be achieved especially for activation or functionalization, or for moderate disintegration, even without contact bodies where, for example, exfoliation does not it is a necessity. This is reflected in improved performance of the resulting particle population.
[0089] The size of the particle charge in the drum is not fundamental. Typically it occupies less than 25% and preferably less than 15% of the volume available in the treatment chamber (evaluated with the particles in a loose bed, for example, immediately after loading or after the rotation ceases).
[0090] An additional proposal refers to the way of supplying gas to the treatment chamber for the formation of low pressure discharge plasma adjacent to the elongated electrode. It is desired to provide conditions in which the treatment chamber is subjected to progressive, and preferably continuous, gas evacuation, for example, to a vacuum pump via a filter suitable to retain particles in the chamber and protect the pump. This can have the important function of progressively cleaning the chemical degradation and volatilization products from the treatment chamber, which would otherwise tend to accumulate in the product or in the components of the device. A clean gas supply is necessary to compensate for the gas evacuated in the said rinsing operation. For many purposes, including activating the surface of the particles, the specific nature of the gas is not critical as long as it can support the plasma. Gases containing oxygen and especially air are suitable and economical.
[0091] Fresh gas can be injected into the chamber through a gas injection structure or distributor, for example, in or adjacent to an electrode inside, for example, along an axis of the chamber.
[0092] It is desirably arranged that the axial electrode is removable, for example, detachable from an opening in an end wall of the treatment drum, to facilitate cleaning and processing.
[0093] The size of the treatment drum is not particularly limited. It is predicted that it can be anything from 1 liter to more.
[0094] Although a central electrode is preferred, and several of the proposals above refer to said arrangement, it is also possible to carry out the plasma treatment in a rotating drum of the type described but creating the region of central or axial plasma by other means, for example, by a magnet and waveguide.
[0095] The treatment time is not particularly limited, and can be readily determined and optimized by testing according to the materials involved, such as plasma conditions and intended end use. For activation or brief functionalization, a treatment time (that is, for the operation of the drum with the active plasma and the particles moving in it) from 30 to 500 seconds is often effective. However, for the disaggregation and especially exfoliation of graphic particles, and / or more vigorous institutionalization, more time is needed and in general the longer the better: in general at least 10, at least 20 or at least 30 minutes and possibly an hour or more. CONTACT BODIES / CONTACT FORMATIONS
[0096] As mentioned, it is strongly preferred to use the following process characteristics which have been found to be remarkably effective in the breakdown of particles, for example, particles containing CNT, and in the exfoliation of graphene or graphical sheets of few layers from graphitic particles, for example, particles as produced by the known "volume" method such as vapor deposition on the catalyst and arc discharge, or (for graphene) particles of natural graphite, or graphite fibers.
[0097] In this aspect the particles defined above to be treated ("the particles") are subjected to plasma treatment under agitation, for example, as described above, in the treatment chamber having a plasma area where plasma is formed in use . The treatment chamber contains or comprises multiple solid contact bodies or solid contact formations. These are electrically conductive, or have electrically conductive surfaces, and come into contact with the particles as they are agitated.
[0098] In preferred procedures the contact bodies are mobile or mobile, preferably freely mobile, in the chamber and are agitated together with the particles. This can be rotation agitation and / or drumming in a treatment drum as proposed above. Or it can be an agitation not completely rotating, for example, alternating agitation. The contact bodies can pick up electrical charge on their surfaces by contact with an electrode comprised in the treatment chamber, for example, in an external container or drum wall, or assume its voltage in relation to the other electrode, and / or the pass through the plasma zone.
[0099] The contact bodies can be of any suitable format. Spheres are preferred because the symmetry of the surface provides a uniform distribution of the phenomenon related to the electric field. Other shapes with circular symmetry, cuboid or polyhedron can also be used. The size is not fundamental, but preferably they are larger than the particles being treated. In general they are at least 1 mm, at least 2 mm or at least 5 mm in maximum dimension (for example, diameter). In general, the maximum dimension (for example, diameter) is not more than 100 mm, or not more than 60 mm, or not more than 40 mm or 30 mm. With smaller bodies the intensity field can be larger.
[00100] The material of the bodies is not fundamental. For the electrical conductivity of the surface, a conductive coating such as a metal coating on an insulating body will do. However, this accumulates less load, so the adjacent field is less in use. Bodies produced entirely of conductive material in general provide a larger field. They can be metal or a conductive compound such as metal carbide or metalloid. Simple steel balls are very effective, although they are susceptible to corrosion in air after being exposed to plasma. Use of more chemically inert conductive materials, such as non-ferrous carbides can reduce this item. Conductive ceramics are an additional possibility.
[00101] The material of the contact bodies must be selected so as not to be substantially destroyed or disintegrated by the treatment environment. Similarly, materials are preferably avoided which contain substantial levels of components that can vaporize from the surface of the bodies under treatment conditions and deposit in or otherwise contaminate the released particles of the product, unless this is intended for some special reason.
[00102] The agitation of particles with contact bodies seems at first sight analogous to crushing with ball or beads, which was previously considered as a means of breaking up the aggregated particles. However, ball or bead crushing is in fact found to be essentially ineffective for this with particles of the type described. In fact, when our experiments were repeated (described later) with the contact spheres but without the activated plasma, a negligible effect was observed. In contrast to mere plasma flushing, although effective, it is far less effective for disintegration and exfoliation than the combination with contact bodies. The present method using plasma and agitated moving bodies in combination achieves remarkably good results.
[00103] However, the coagitation of the contact bodies provides mixing, promoting the contact of substantially all particles in the charge with the active charged surfaces of the bodies during the treatment period.
[00104] The number of bodies depends on how much is expected of their size, material, the treatment time, the amount of material to be treated etc. Desirably they form a bed - at least when static and preferably also when agitated - sufficiently deep to incorporate the charge of particles being treated, at least at the beginning of the treatment (graphite particles and agglomerated CNT particles, for example, if they expand very greatly during treatment as they are disaggregated or exfoliated and can rise above the contact bodies after having been previously lost between them).
[00105] In an alternative mode the contact of the agitated particles is with the contact formations connected to the treatment container or mounted in a fixed position in it, for example, a structure of projections of fingers facing inwards from the wall of the same through which the particles drum, or a grid or lattice or other fine structure in which the particles can mix and move under agitation, and which are connected in order to be electrostatically charged, or to assume the relative voltage of the adjacent wall of the electrode container or component, desirable luminescent plasma forms on the surfaces of contact bodies or contact formations and this treats the particles.
[00106] The first aspect above requires conductive bodies. However, the combination of shredding with beads or beads with plasma treatment in the same chamber is also new and more effective than any of the measures adopted in isolation, and thus it is an aspect of our proposals even if non-conductive contact bodies are used.
[00107] It has been observed that the use of plasma treatment is effective to remove some contaminants, and in particular amorphous carbon and post-production residual contaminants such as catalysts, more gently than by the known methods of acid washing, that is, with less damage to regular particle structure.
[00108] After the treatment the disaggregated particulate product was observed to exhibit several advantageous properties. An important property is specific surface area, which can be determined by the BET standard or MR methods. Conventional treatments applied to aggregate CNT particles strive to achieve BET-specific surface areas better than 50m2 / g in the product material, due to the great tendency to maintain aggregation. It has been observed that CNT granules treated by these methods can provide materials with specific surface areas for BET of at least 300, at least 500, at least 800 or at least 1000 m2g. Such materials are believed to be new in themselves in the context of volume production methods, and they are an aspect of the present invention. Methods comprising the synthesis of CNTs or graphitic particles and then applying the present methods for disintegrating or exfoliating the particle product are an additional aspect of the present invention. Methods in which disintegration or exfoliation treatment is followed by dispersing the material in a liquid carrier or matrix material (or precursor of matrix material) is an additional aspect of the present invention. Said dispersion may involve the use of one or more dispersants such as surfactants, or polymeric materials whose molecules associate themselves with the individual dispersed component particles, for example, separate CNTs or graphene sheets, to inhibit their re-aggregation in the liquid . BRIEF DESCRIPTION OF THE DRAWINGS
[00109] The present proposals are now explained further with reference to the attached drawings, in which:
[00110] Fig. 1 is a perspective view of a treatment container;
[00111] Fig. 2 is a schematic view of a central electrode formation in one version;
[00112] Fig. 3 is a schematic view of a central electrode formation in another version;
[00113] Fig. 4 is a schematic end view of the treatment vessel operating in the plasma generating apparatus;
[00114] Fig. 5 is a side view of the same thing;
[00115] Fig. 6 is a perspective view of an additional treatment drum modality, and,
[00116] Fig. 7 is an axial cross section of the same.
[00117] Figs. 8 to 16 show details of current carbon materials before and after treatment according to the new proposals:
[00118] Figs. 8 and 9 are SEM images of a MWCNT material before treatment;
[00119] Figs. 10 and 11 are SEM images of the same MWCNT material after treatment;
[00120] Figs. 12 (a) and 12 (b) are particle size data for the MWCNT material before and after treatment;
[00121] Figs. 13 and 14 are SEM images of disordered graphical material or graphene produced by arc discharge, before and after treatment;
[00122] Figs. 15 and 16 are SEM images of a natural graphite material before and after treatment.
[00123] Figs. 17 and 18 are SEM images of a disordered graphical material or graphene produced by arc discharge, before and after treatment;
[00124] Figs. 19 and 20 are SEM images of a natural graphite material before and after treatment;
[00125] Figs. 21 and 22 are front views and an edge view of the product obtained in Example 6;
[00126] Fig. 23 shows a selected nanoplate material obtained in Example 7;
[00127] Fig. 24 shows an additional version of the treatment drum (3rd device modality);
[00128] Figs. 25 and 26 are ESCA results (XPS) showing the analysis of the elemental surface of the CNTs functionalized by the present treatment methods. DETAILED DESCRIPTION
[00129] With reference to Fig. 1 a generally cylindrical glass container or drum 4 has a rear end wall of integral glass 43 and a front opening 41. Quartz or borosilicate glass is suitable. Axially extending rib formations 44 are distributed circumferentially and project inwardly from the inner surfaces of the drum wall 42. They can be formed integrally with the wall glass, or be bonded plastic components.
[00130] The rear wall 43 has a central recessed portion or socket 431 forming an insulating location support for an electrode formation that extends forward axially through the inner drum. Said formation can be a device and insertion of fixed metal electrode, as exemplified in Fig. 2. The embodiment of Fig. 2 is a tubular electrode with a gas supply port via a fine filter disc 32 closing its end front (free), for example, secured by a threaded ring cap 33. Its open rear end is sealable, or more preferably sealably connected, but removable (for example, by a thread or tapered plug as shown), in a central opening of glass socket 431.
[00131] Alternatively the interior electrode formation can be or comprise a dielectric electrode cover, for example, an integral tubular front extension 3 'of the glass wall itself as shown in Fig. 3, having a fine particle filter 32' for example, sintered glass or ceramics at its front end. An alternative has a separate tubular dielectric electrode cover element attached or connected, like the electrode in Fig. 2.
[00132] An advantage of the removable electrodes / electrode cover is the ease of cleaning, replacement or replacement with different ones, for example, of different size, material, type of filter etc.
[00133] A plastic sealing cap 5 is provided for the open front end of the glass treatment vessel. Said cover has a peripheral sealing skirt portion 53 to fit snugly into the opening of the drum 41, a filter port 52 incorporating a HEPA filter element, for pressure equalization with a vacuum system, and an injection port for fluid 51 having a sealing cover for the introduction of liquid.
[00134] In use, a load of particles is placed in container 4. The lid 5 is sealed. The HEPA 52 filter is thin enough that particles cannot escape, and can in any case be covered with a seal as a precaution against damage. The particle-loaded container is sent for plasma treatment using plasma generation apparatus having a vacuum generating treatment chamber, plasma-forming gas supply, means for rotating the container and actuation of the system electrode to generate a suitable electric field for the generation of plasma, for example, RF energy.
[00135] In the case of Fig. 2 where the electrode 3 is integrated, it is necessary to connect it by a suitable connector, for example, a threaded element 6 with a gas supply duct 70, for the electric drive. Of course, said connector can alternatively extend inward or fully along the inside of the tubular electrode 3. However, the connector is in any case connected in a removable or releasable way.
[00136] In the case of Fig. 3 where the drum comprises a 3 'dielectric electrode cover, an elongated electrode 7 of the plasma generation devices is inserted, fitting tightly to avoid intermediate space (the slight space in the drawings being only to indicate the distinct parts).
[00137] A central gas supply channel 70 can be provided inside connector 6 or electrode 7, for supplying gas to the inner container through the filter 32.32 'at the front end of the electrode.
[00138] Figs. 4 and 5 show a plasma treatment apparatus schematically: a support container 8 is pivotally mounted in a fixed sealable housing 9. Any of them or part of them can comprise the counter electrode. The counter electrode must be formed and positioned in relation to the axial electrode to allow stable luminescent plasma to form substantially along the entire axial electrode within the treatment chamber. The particle treatment container 4 is loaded into the support container 8 through a front door 81, and held axially in position by padding of location 82, and by connection of the axial electrode at its rear end. The housing 9 is evacuated via an evacuation port V, and the vacuum is applied through the system via a vacuum port on the container 83 and the front filter port 52 on the treatment container. The gas is fed axially through the 32.32 'filter in the electrode formation. The application of RF or other suitable energy according to the known principles creates plasma in the container 4, especially in the region adjacent to the axial formation of electrode 3. As the drum rotates (Fig. 4) the internal vanes 44 displace the nanoparticles upwards and drop them down selectively through said plasma-rich zone.
[00139] The treatment atmosphere can be chosen freely as long as it supports the plasma. An oxygen-containing atmosphere is an example, and is effective for producing functional groups containing oxygen in the particles, thereby activating them.
[00140] Thus, the treatment container 4 can be connected to the plasma devices and operated to activate the particles to plasma without ever having to be opened. After treatment, the liquid introduction port 51 can be used to inject a suitable liquid to disperse and / or carry the particles. It can be, for example, a solvent vehicle, water or polymeric material.
[00141] For process gas injection, the treatment chamber can be provided with more than one gas injection point (for example, different points in the housing or drum and / or different options for injecting gas into or along the electrode central). The appropriate point can then be selected to produce effective treatment according to the material to be treated.
[00142] The rotation speed of the treatment drum is adjustable so that the particles can be caused to fall selectively through the region of luminescent plasma.
[00143] The drum can be formed in several ways. One possibility is a conductive wall of the drum itself forming the counter electrode for the formation of plasma. Front and rear end plates can be dielectric. An additional possibility is a total dielectric drum, with a separate counter electrode structure or other plasma energizing structure. Said structure can be an external housing.
[00144] Glass is a suitable and dielectric material readily available for the formation of any of the vanes, drum end plates and drum wall. Plastic or ceramic materials can also be used. Second Device Mode
[00145] Figs. 6 and 7 show an additional treatment drum suitable for treating particles comprising CNTs, or graphitic granules. It has a 2004 cylindrical metal drum wall, for example, steel or aluminum to act as the counter electrode. It must be mounted for rotation in a vacuum chamber, for example, on support rollers.
[00146] The end walls are insulating. The rear end wall is glass or inert plastic, for example, PTFE and comprises inner and outer layers 2432, 2431 between which a filter layer (not shown) is attached. Said end-wall filter module has a large window 2111 that occupies more than half of its area so that the speed of gas flow through the filter is low. It was observed that this improved the stability of the plasma, that is, it inhibited the arching. The center of the rear end wall has a support for the axial electrode, not shown. The electrode is a tubular metal electrode along which process gas is fed in use. It can be housed in a sheath.
[00147] A set of eight non-conductive (plastic) lift vanes 244 is mounted around the inside of the metal drum. The front end wall has a simple insulating sealing wall or cover held in place by a tight collar that can optionally - as can the module at the rear end - be screwed onto the metal end of the drum. Device Third Mode
[00148] Fig. 24 shows a third modality of the treatment drum, in a little more detail. Said is a large drum, volume of about 60 liters and without internal vanes or elevators, that is, so that the bed of contact bodies, for example, steel balls resided in the bottom during the treatment. The central tubular electrode is used for gas supply, through a sintered brass plug at the front end (not shown). The front wall is formed in a cone with a limited opening (having a window plug, not shown) to facilitate the emptying of the product after treatment. The rear wall is a filter, as before. Mechanical drive elements, vacuum communication and gas supply are also shown, to assist those skilled in the art. The gas flow through the large volume of the system is relatively slow, and it has been observed that there is no tendency for the very fine particulate product to escape through the filter, that is, the product is not "transported" by the gas flow. EXAMPLES Devices and Conditions
[00149] In an experimental work a steel treatment drum was used substantially as shown in Figs. 6 and 7 and also as shown in Fig. 24, without any internal lift vanes. Internal volume of about 12 liters, 400 mm diameter, central electrode diameter of 3 mm, central steel electrode and with an observation window on the front wall. As the contact bodies common steel bearings were used: size 10 mm, weight 12 grams, number of about 500. Each load of starting material (aggregates or initial carbon particles to be treated) weighing about 100 grams was put in the drum with the steel balls and the lid closed. For the treatment, the conditions in the drum were, for example, as follows: Gas atmosphere supply Oxygen Gas flow coefficient 1000cm3 per minute Pressure 50 torr Drum rotation speed 60 rpm Applied voltage (plasma) 100 volts 30 mins treatment
[00150] The best results were observed at speeds at which the mass of the particles being treated, mixed with the moving bodies (steel balls), resides at the bottom of the drum in the average that it rotates. At 60 rpm the ball bed and particles are gently agitated but remain at the bottom of the drum.
[00151] Carbon sample materials used in Examples 1 to 3 were as follows. WCNT material produced by Bayer's CVD process; widely graphical material produced by an arc unloading process, by Rosseter (Cyprus); natural graphite powder.
[00152] During the treatments, plasma-like halos of light were observed around the steel spheres, especially those at the top of the bed closest to the central electrode, as they drummed in the drum with the carbon particles.
[00153] Particle sizes were measured in water dispersion (using the standard laser diffraction method) by a MasterSizer 2000 machine (Malvern Instruments, UK). (Those skilled in the art will note that this provides only relative measurements, due to the high aspect ratio of the product). SEM images are from the Hitachi S-4800. Example 1
[00154] The MWCNT material as supplied, that is, as manufactured, is seen in the SEM images of Figs. 8 and 9 and their particle size distribution is in Fig. 12 (a). These are large, tightly aggregated granules approaching 1 mm (1000 pm) in size. The treated material is seen in the SEM images of Figs. 10 and 11 and their particle size distribution is in Fig. 12 (b). It can be readily seen that the particle size has been drastically reduced to a range between 1 and 10 μπi, that is, there has been substantial disaggregation, and also that the treated material has a substantial proportion of released and distinct CNTs, visible in SEM images. Example 2
[00155] The starting material, consisting mainly of disordered lumps, stacked graphite and platelets with small fullerenes (Fig. 13), was subjected to the same treatment as described above. Portions of the treated material are seen in Fig. 1. It can be readily seen that there was substantial thinning of the platelets, exfoliation of some graphene and reduction in size.
[00156] BET methods were used to measure the specific surface area, with 2 hr degassing at 300 ° C: treated = 92 m2 / g untreated = 62 m2 / g Increase = 48% Example 3
[00157] The starting material was powdered natural graphite. Fig. 15 shows the typical particle: a graphite plate with multiple layers that will not show the special properties of graphene. Fig. 16 shows the material after the treatment. There was substantial exfoliation, producing a large number of single graphene flakes. The referred ones can be functionalized in its borders, as it is known. Example 4
[00158] The starting material, consisting mainly of lumps and disorderly platelets of graphite stacked with a few small fullerenes (Fig. 17), was subjected to the same treatment as described above. Portions of the treated material are seen in Fig. 18. It can be readily seen that there was substantial thinning of the plates, exfoliation of some graphene and reduction in size.
[00159] BET methods were used to measure the specific surface area, with 2 hr degassing at 300 ° C: treated = 92 m2 / g untreated = 62 m2 / g Increase = 48% Example 5
[00160] The starting material was powdered natural graphite. Fig. 19 shows the typical particle: the graphite plate with multiple layers that will not show the special properties of graphene. Fig. 20 shows the material after treatment. There was substantial exfoliation, producing a large number of single graphene flakes. The referred ones can be functionalized in its borders, as it is known. Example 6
[00161] The starting material was natural graphite powder of Chinese origin. Fig. 21 is a representative view of the treated product, with platelets completely separated. No measured platelet was thicker than 57 nm. Most were less than 25 nm thick. The thinnest was 2.7 nm.
[00162] The referred material, which carries the oxygen-containing functionalities from the plasma treatment, was promptly dispersed at 2% by weight of molten polyethylene which was then stretched on a wire. In a qualitative laboratory comparison, the loaded wire showed much higher resistance to tension than a wire of corresponding unloaded material. Example 7
[00163] Exfoliated graphite obtained as in Example 6 was subjected to classification by dispersion in water and ultrasonication, whereby only the finer particles remained on top of the jar. The said ones were physically separated and recovered. Fig. 23 shows that they are remarkably small and uniformly very thin platelets; a very high value material obtained by a simple and economical process. Functionalization
[00164] Figs. 25 and 26 show XPS surface analysis (ES-CA) for treated carbon nanotubes (Baytubes ™). The untreated tubes showed 96% carbon, 4% oxygen.
[00165] After thirty minutes of treatment of a 25 g sample in a plasma containing ammonia (ammonia diluted in Ar), using the steel balls as above, the analysis showed 97.2% carbon, 0.9% oxygen, 1.9% nitrogen: see Fig. 25. The unwanted has been reduced and the NH functions have been introduced.
[00166] Fig. 26 shows the corresponding results after the same treatment, but in a CF4 containing plasma. After treatment, carbon was 83.3%, oxygen 2.6% and fluorine 14.1%. This represents a high level of fluoride functionalization on the surface.

权利要求:
Claims (15)
[0001]
1. Particle treatment method in which particles for treatment are subjected to plasma treatment in a treatment chamber to break down, de-agglomerate, exfoliate, clean or functionalize the particles, the particles being agitated in contact with the plasma in the characterized treatment chamber by the fact that the treatment chamber comprises multiple electrically conductive solid contact bodies that are mobile in it, the particles being agitated with said contact bodies in the treatment chamber.
[0002]
2. Particle treatment method, according to claim 1, characterized by the fact that the particles to be treated consist of carbon nanotubes (CNTs) or other nanoparticles.
[0003]
Particle treatment method according to claim 1 or 2, characterized in that the treatment chamber is a drum, preferably a rotating drum, in which the plurality of contact bodies are drummed with the particles to be treated.
[0004]
4. Particle treatment method according to any one of the preceding claims, characterized in that the wall of the treatment vessel is conductive and forms a counter electrode to an electrode that extends into an interior space of the treatment chamber .
[0005]
5. Particle treatment method according to any of the preceding claims, characterized by the fact that luminescent plasma forms on the surfaces of the contact bodies.
[0006]
6. Particle treatment method according to any one of the preceding claims, characterized by the fact that the contact bodies are metal spheres or metal coated spheres.
[0007]
7. Particle treatment method according to any of the preceding claims, characterized by the fact that the contact bodies have a diameter, and the diameter is at least 1 mm and no more than 60 mm.
[0008]
8. Particle treatment method according to any of the preceding claims, characterized by the fact that the pressure in the treatment vessel is less than 500 Pa.
[0009]
Particle treatment method according to any of the preceding claims, characterized by the fact that during treatment, gas is fed into the treatment chamber and gas is removed from the treatment chamber through a filter.
[0010]
10. Particle treatment method according to any one of the preceding claims, characterized by the fact that the treated material, that is, the particles or components disintegrated, de-agglomerated or exfoliated from them resulting from the treatment, are chemically functionalized components of the gas plasma forming, forming, for example, carbonoxy, carbonyl, OH, amine, amide or halogen functionalities on their surfaces, and / or where the plasma forming gas in the treatment chamber is or comprises any of oxygen, water , hydrogen peroxide, alcohol, nitrogen, ammonia, amine-sustaining organic compound, halogen such as fluorine, halohydrocarbon such as CF4 and noble gas.
[0011]
11. Particle treatment method according to any one of the preceding claims, characterized in that the particles consist of or comprise graphitic carbon, such as mined graphite, which is exfoliated by treatment, and after treatment the treated material comprises or consists of distinct graphene or graphitic platelets having a platelet thickness of less than 100 nm and a larger dimension perpendicular to the thickness which is at least 10 times the thickness.
[0012]
Particle treatment method according to claim 11, characterized in that said treatment is continued for at least 30 minutes and / or until the treated carbon material comprises at least 90% of the platelets by weight less than 100 nm in thickness and where the largest dimension is at least 10 times the thickness, preferably at least 100 times the thickness, or until the treated carbon material comprises by weight at least 80%, preferably at least 90%, of the platelets less than 30 nm in thickness, preferably less than 20 nm in thickness, and where the largest dimension is at least 10 times the thickness, preferably at least 100 times the thickness.
[0013]
13. Method of preparing a particle dispersion or a composite material, characterized in that it comprises (a) treating particles by a particle treatment method as defined in any of claims 1 to 12, and, (b) dispersing the material treated in a liquid vehicle or matrix material.
[0014]
Method according to claim 13, characterized in that the particles are dispersed in a matrix material that is polymeric, for example, epoxy resin, polyolefin, polyurethane, polyester, polyamide or poly (meth) acrylic material or mixture or copolymer of said types of polymer, or is a precursor, for example, oligomer or monomer, of said polymer.
[0015]
15. Method for making an article or device characterized by the fact that it comprises an electrically conductive layer or element, such as a photovoltaic device, field emission device, hydrogen storage device, battery or battery electrode, the method comprising obtaining a composite material by the method as defined in claim 13 or 14, and forming the electrically conductive layer or element comprising or consisting of said composite material.

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法律状态:
2018-01-23| B25D| Requested change of name of applicant approved|Owner name: HAYDALE GRAPHENE INDUSTRIES LIMITED (GB) |

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2018-03-06| B25D| Requested change of name of applicant approved|Owner name: HAYDALE GRAPHENE INDUSTRIES PLC (GB) |

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2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C01B 32/225 (2017.01), B01J 19/08 (2006.01), B82Y |

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2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2018-05-15| B15K| Others concerning applications: alteration of classification|Ipc: C09C 1/44 (2006.01), B01J 19/08 (2006.01), H01J 9/ |

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2019-07-02| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|

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2020-05-05| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2020-10-06| B09A| Decision: intention to grant|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 08/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GB1020836.1|2010-12-08|

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