• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    in situ exfoliation method for making a graphene-reinforced polymer matrix compound - a method for forming a graphene-reinforced polymer matrix compound by distributing graphite microparticles in a molten thermoplastic polymer phase, comprising one or more fused thermoplastic polymers, and applying a succession of shear deformation events to the molten polymer phase so that the molten polymer phase exfoliates graphene successively with each event, until the breakdown of the exfoliated multilayer sheets of graphene occurs and produces reactive edges on the multilayer sheets that react and bind one or more thermoplastic polymers by crosslinking, where one or more thermoplastic polymers are selected from thermoplastic polymers subject to UV degradation.
    公开号:BR112015026355B1
    申请号:R112015026355-0
    申请日:2014-04-18
    公开日:2021-03-30
    发明作者:Nosker Thomas；Lynch Jennifer；Kear Bernard；Hendrix Justin；Chiu Gordon
    申请人:Rutgers, The State University Of New Jersey；
    IPC主号:
    专利说明:

    Cross-Reference to Related Orders
    001. The present request claims the benefit of priority according to 35 U.S.C. § 119 (e) of the provisional U.S.C. Order number 61/813 / 813.621 filed on April 18, 2013, the entire description of which is incorporated herein by reference. Technical area
    002. The present invention relates to highly efficient mixing methods for transforming a polymeric compound containing well-crystallized graphite particles, into single or multi-layered nanodispersed graphene particles, having various commercial applications. The present invention also relates to methods for activating graphite and graphene using mechanical exfoliation in situ. Background of the Invention
    003. Polymeric compositions are increasingly being used in a wide range of areas that have traditionally employed the use of other materials, such as metals. Polymers have several desirable physical properties, are lightweight and economical. In addition, many polymeric materials can take different shapes, show significant flexibility in the shapes they take and can be used as coatings, dispersions, extrusion and molding resins, pastes, powders and the like.
    004. There are several applications for which the use of polymeric compositions that require materials with electrical conductivity would be desirable. However, a significant number of polymeric materials are not sufficiently electro- or thermo-conductive for many of these applications.
    005. Graphene is a substance composed of pure carbon in which the atoms are positioned in a hexagonal pattern on a sheet the thickness of an atom, densely compacted. This structure is the basis for understanding the properties of many carbon-based materials, including graphite, large fullerenes, nano-tubes and the like (for example: carbon nano-tubes are generally thought of as graphene sheets rolled up in size cylinders. nanometric). Graphene is a simple flat sheet of sp2-linked carbon atoms. Graphene is not an allotrope of carbon because the sheet is of limited size and other elements can be attached to the edge in non-fading stoichiometric reasons.
    006. When used to reinforce polymers, graphene in any form increases the strength of the polymer, inhibiting the spread of cracks. Graphene can also be added to polymers and other compositions to provide electrical and thermal conductivity. Graphene's thermal conductivity makes it an ideal additive for thermal management (eg flat heat dissipation) for electronic devices and lasers. Some commercial applications of carbon fiber reinforced polymer matrix compounds (CF-PMCs) include aeronautical and aerospace systems, automotive systems and vehicles, electronics, government defense / security products, pressurized ships and reactor chambers, among others.
    007. Progress in the development of low-cost methods to effectively produce graphene-reinforced polymer matrix compounds (G-PMCs) remains very slow. Currently some of the challenges affecting the development of viable G-PMCs for use in real-world applications include the cost of materials and the impracticality of the chemical and / or mechanical manipulations used at present for large-scale commercial production. Thus, a low-cost method for producing a G-PMC suitable for large-scale commercial production that offers many advantageous properties, including specific hardness and strength, greater electro / thermal conductivity and retention of optical transparency, would be desirable. Summary of the Invention
    008. The present description provides methods for processing polymers to manufacture a graphene-reinforced polymer matrix compound (G-PMC) by elongational flow and folding of well crystallized graphite particles dispersed in a molten polymer matrix.
    009. In one aspect, a method is provided herein to form a graphene-reinforced polymer matrix compound, including: distribution of graphite micro particles in a melt thermoplastic polymer phase and application of a succession of shear deformation events to the molten polymeric phase so that the molten polymeric phase exfoliates the graphite successively with each event until at least 50% of the graphite is exfoliated to form a distribution, in the molten polymer phase, of nano single and multilayer graphene particles of less thickness than 50 nanometers along a c-axis direction.
    0010. In certain embodiments, graphite particles can be prepared by crushing and crushing a graphite-containing mineral in millimeter dimensions.
    0011. In certain embodiments, millimeter particles can be reduced to micron dimensions using any known method, such as ball milling or friction milling.
    0012. In certain embodiments, the graphite particles are extracted from mixtures of micronic dimensions, preferably by a flotation method.
    0013. In certain embodiments, the extracted graphite particles can be incorporated into a polymeric matrix using a single screw extruder with axial striated extension elements for mixing or spiral striated extension elements for mixing.
    0014. In certain incorporations, the polymer matrix containing graphite is subjected to repeated extrusion to induce exfoliation of the graphitic material, thus forming a uniform dispersion of graphene nanoparticles in the polymer matrix.
    0015. In certain embodiments, the thermoplastic polymer is an aromatic polymer. The aromatic polymer preferably comprises phenyl groups, optionally substituted, either as part of the backbone or as substituents on the backbone. In certain embodiments, the optionally substituted phenyl groups are contained within the polymer backbone as optionally substituted phenylene groups. In certain other embodiments, the optionally substituted phenyl groups are substituents on the polymer. In specific embodiments, the thermoplastic polymer is selected from polyetheretherketones, polyetheretherketones, polyphenylene sulfides, polyethylene sulfides, polyetherimides, polyvinylidene fluorides, polysulfones, polycarbonates, polyphenylene ethers or oxides, polyamides such as nailons, polyesters, arsenic, arsenic, thermoplastics. thermoplastics, liquid crystal polymers, thermoplastic elastomers, polyethylenes, polypropylenes, polystyrenes, acrylics such as: polymethylmethacrylate, polyacrylonitrile, acrylonitrile, butadiene, styrene, and the like; ultra-high molecular weight polyethylene, polytetrafluoroethylene, polyoxymethylene plastic, polyarylethylketones, polyvinylchloride, and mixtures thereof.
    0016. In certain incorporations, in combination with other incorporations, the succession of shear deformation events can be applied until at least 50% of the graphite is exfoliated to form a distribution, in the melted polymer phase, of simple graphene nanoparticles multilayer with thickness below 25 nanometers along the direction of the "c" axis.
    0017. In certain incorporations, in combination with other incorporations, the succession of shear deformation events can be applied until at least 50% of the graphite is exfoliated to form a distribution, in the melted polymer phase, of single and multilayer graphene nanoparticles less than 10 nanometers thick along the direction of the "c" axis.
    0018. In certain incorporations, in combination with other incorporations, the succession of shear deformation events can be applied until at least 90% of the graphite is exfoliated, to form a distribution in the melted polymer phase, of simple and multilayer graphene nanoparticles less than 10 nanometers thick along the direction of the "c" axis.
    0019. In certain incorporations, in combination with other incorporations, the succession of shear deformation events can be applied until at least 80% of the graphite is exfoliated, to form a distribution in the melted polymer phase, of simple and multilayer graphene nanoparticles less than 10 nanometers thick along the direction of the "c" axis.
    0020. In certain incorporations, in combination with other incorporations, the succession of shear deformation events can be applied until at least 75% of the graphite is exfoliated, to form a distribution in the melted polymer phase, of simple and multilayered graphene nanoparticles with thickness less than 10 nanometers along the direction of the "c" axis.
    0021. In certain incorporations, in combination with other incorporations, the succession of shear deformation events can be applied until at least 70% of the graphite is exfoliated, to form a distribution in the melted polymer phase, of simple and multilayered graphene nanoparticles with thickness less than 10 nanometers along the direction of the "c" axis.
    0022. In certain incorporations, in combination with other incorporations, the succession of shear deformation events can be applied until at least 60% of the graphite is exfoliated, to form a distribution in the melted polymer phase, of simple and multilayer graphene nanoparticles with thickness less than 10 nanometers along the direction of the "c" axis.
    0023. In certain incorporations, in combination with other incorporations, graphite can be doped with other elements to modify the surface chemistry of exfoliated graphene nanoparticles.
    0024. In certain embodiments, in combination with other incorporations, graphite is expanded graphite.
    0025. In certain embodiments, in combination with other embodiments, the surface chemistry or nanostructure of the dispersed graphite can be modified to increase the bond strength with the polymer matrix, thereby increasing the strength and stiffness of the graphene compound.
    0026. In certain incorporations, in combination with other incorporations, the directional alignment of graphene nanoparticles is used to obtain uni-, bi-, or three-dimensional reinforcement of the polymer matrix phase.
    0027. In another aspect of the described invention, the present provides a method for forming a cross-linked G-PMC, including: distributing graphite microparticles in a molten thermoplastic polymer phase comprising one or more molten thermoplastic polymers; and applying a succession of shear events to said melted polymer phase, in such a way that said melted polymer phase exfoliates graphene with each event until the exfoliated graphene multilayer sheets break, producing reactive edges on said sheets multilayers that react and cross-connect with said thermoplastic polymer.
    0028. In another aspect of the described invention, a method is provided for forming a high-strength cross-linked G-PMC, including: distribution of graphite microparticles in a melted thermoplastic polymer phase, comprising one or more fused thermoplastic polymers; application of a succession of shear deformation events to the melted polymer phase, so that said melted polymer phase exfoliates the graphene successively with each event until the rupture of exfoliated multilayer graphene sheets occurs and produces reactive edges on said sheets multi-layers that react and cross-link with said thermoplastic polymers, to form a polymer matrix compound, reinforced by graphene with another non-cross-linked thermoplastic polymer.
    0029. In certain embodiments, graphite particles can be prepared by crushing and crushing a mineral containing graphite in millimeter dimensions, followed by reduction to micron sized particles by grinding.
    0030. In certain embodiments, the graphite particles are extracted from the mixture of particles of micronic dimensions, preferably by a flotation method, to obtain Separate Mineral Graphite ("SNG").
    0031. In certain embodiments, the molten thermoplastic polymer phase comprises two molten thermoplastic polymers.
    0032. In certain embodiments, thermoplastic polymers are selected from polyether etherketone (PEEK), polyethercetone (PEK), polyphenylene sulfide (PPS), polyethylene sulfide (PES), polyetherimide (PEI), polyvinylidene fluoride (PVDF), polycarbonate (PC ), polyphenylene ether, aromatic thermoplastic polyesters, thermoplastic polyimides, liquid crystal polymers, thermoplastic elastomers, polyethylene, polypropylene, polystyrene (OS), acrylics, such as polymethylmethacrylate (PMMA), polyacrylonitrile (PAN), acrylonitrile (butadiene) and acrylonitrile (butadiene) similar, ultra high molecular weight polyethylene (UHMWPE), polytetrafluoroethylene (PTFE / Teflon®, polyamides (PA) such as polyphenylene oxide (PPO), polyoxymethylene plastic (POM / Acetal), polyarylethylketones, polyvinyl chloride (PVC) and mixtures thereof) . Brief Description of Drawings
    0033. Figure 1 illustrates the morphological analysis of 2% polysulfone exfoliated graphite with mixing times of 3 minutes, 30 minutes and 90 minutes, according to an in situ exfoliation method in this description.
    0034. Figure 2 illustrates 90G-PMC micrographs at various scales and magnification levels according to an in situ exfoliation method in this description.
    0035. Figure 3 illustrates the morphology of SMG-PEEK_90 in (a) 10 pm and 1,000 X scale, (b) 10 μm and 5,000 X scale, (c) 1 μm and 10,000 X scale, and (d) 1 μm scale and 50,000 X. Detailed Description of the Invention
    0036. This description is not limited to the specific systems, methodologies, or protocols described, as these may vary. The terminology used in this description is intended to describe specific versions or incorporations, and is not intended to limit the scope.
    0037. When used in this document, the singular forms "a" "an" and "o" include references in the plural, unless the dispute clearly indicates otherwise. Unless otherwise stated, all technical and scientific terms used in the present have the same meanings, commonly understood by a professional experienced in the art. All publications mentioned in this document are incorporated by reference. All sizes mentioned in this document are for example purposes only, and the invention is not limited to structures that have the specific sizes or dimensions mentioned below. Nothing in this document should be construed as an admission that the embodiments described in this document do not have the right to predate that description by virtue of a previous invention. When used herein the term "comprising" means "including, without limitation".
    0038. The following term (s) will, for the purposes of this order, have the respective meanings set forth below.
    0039. The term "graphene" refers to the name given to a simple layer of carbon atoms densely packed in a fused benzene ring structure. Graphene, when used alone, can refer to multilayer graphene, graphene flakes, graphene platelets, and low-layer or single-layer graphene in a pure, uncontaminated form.
    0040. The present invention provides a high-efficiency mixing method for transforming a polymeric compound, which contains well-crystallized graphite particles, into single-layer or multilayer nanodisperse graphene particles. The method involves in-situ exfoliation of the graphite layers by composition in a batch mixer or extruder that transmits high shear deformation rates. In both processes, longer mixing times result in marked exfoliation of graphite in graphene nanoparticles, inside the polymeric matrix compound (BMC). In addition, additives can be used to promote the graphene / polymer bond, thereby producing a low density graphene-reinforced polymer matrix compound (G-PMC). The method is inexpensive to produce a G-PMC that offers numerous advantageous properties, including greater specific stiffness and strength, marked electro / thermal conductivity and retention of optical transparency. Furthermore, these properties can be fine-tuned by modifying the process. See below.
    0041. The repeated composition during a batch mixing process or single screw extrusion, is used to progressively transform the dispersion of initial graphite particles into uniform nanodispersion of discrete graphene particles. In some cases, an inert gas or vacuum may be used during processing. The method is described in the present as "mechanical" exfoliation, to differentiate it from the "chemical" exfoliation that is the main objective of most of the current research. An advantage of the mechanical method is that contamination-free graphene-polymer interfaces are formed during high shear mixing, thus ensuring good adhesion or bonding at the interfaces. Other advantages of in-situ exfoliation are that it avoids making and handling graphene flakes, as well as avoiding the need to disperse them evenly in the polymeric matrix phase. The superior mixing produces finer composite structures and very good particle distribution.
    0042. Depending on the number of shear deformation events, the method provides multilayer graphene, graphene flakes, graphene platelets, low-layer graphene or single-layer graphene in a pure, uncontaminated form. Platelets have diamond-like stiffness and are used for polymeric reinforcement. Graphene, in any form, increases the stiffness of the polymer by inhibiting the spread of cracks as a polymeric reinforcement. Graphene can be used as an additive to polymers and other compositions to provide conductivity, both electrical and thermal. The thermal conductivity of graphene makes it a desirable additive for thermal management by electronic devices and lasers.
    0043. Graphite, the starting material from which graphene is formed, is composed of a layered planar structure in which the carbon atoms in each layer are arranged as a hexagonal lattice. Planar layers are defined as having an "a" and "b" axis, with a "c" axis perpendicular to the plane defined by the "a" axis and the "b" axis. Graphene particles produced by the inventive method have an aspect ratio defined by the distance from the "a" or "b" axis, divided by the distance from the "c" axis. The aspect ratio values for the inventive nanoparticles exceed 25: 1 and are typically in the range between 50: 1 and 1000: 1.
    0044. It is understood that, essentially, any polymer inert to graphite and capable of transmitting sufficient shear deformation to exfoliate graphene from graphite can be used in the method of the present invention. Examples of such polymers include, without limitation, polyetheretherketones (PEEK) polyetherketones (PEK), polyphenylene sulfides (PPS), polyethylene sulfide (PES), polyetherimides (PEI), polyvinylidene fluoride (PVDF), polysulfone (PSU), polycarbonates (PC) , polyphenylene ethers, polyesters, thermoplastics, aromatics, aromatic polysulfones, thermoplastic polyimides, liquid crystal polymers, thermoplastic elastomers, polyethylene, polypropylene, polystyrene (PS), acrylics such as polymethylmethacrylate (PMMA) polyacrylene (Nitrile) acrylonitrile (PAN) ABS), and the like, ultra high molecular weight polyethylene (UHMWPE), polytetrafluoroethylene (PTFE / Teflon ®), polyamides (PA) such as nailons, polyphenylene oxide (PPO), plastic polyoxymethylene (POM / Acetal), polyarylether ketones, polyvinylchloride (PVC), mixtures thereof, and the like. Polymers capable of wetting the graphite surface can be used, as well as amorphous polymers with a high melting point, according to the method of the present invention. In certain embodiments, the thermoplastic polymer of the polymer matrix reinforced by graphene is an aromatic polymer, as defined in this document.
    0045. Graphene can be produced as a graphene-polymer mixture suitable for immediate use as a G-PMC which can be pelletized by conventional means, for subsequent manufacturing processing. Alternatively, higher concentrations of graphite can be used at the beginning to provide a master batch of graphene-polymer in a concentrated form, which can also be pelletized and then used to add graphene to polymeric compositions as a reinforcing agent. As an additional alternative, graphene can be separated from the polymer, for example, by combustion or selective dissolution to provide essentially pure graphene particles.
    0046. The graphene-reinforced polymers according to the present invention typically contain between about 0.1 and about 30% of the weight of graphene, more typically the polymers contain between about 1.0 and about 10% of the weight of graphene. Master batches of polymers typically contain between about 5 and about 50% of the weight of graphene and more typically between about 10 and about 30% of the weight of graphene.
    0047. The availability of mineral deposits rich in graphite, containing relatively high concentrations (for example, about 20%) of well-crystallized graphite is responsible for a low cost and a virtually inexhaustible source of raw material. As explained below, the extraction of graphite particles from mining material can be carried out economically. Synthetic graphite of high purity and exceptional crystallinity (for example, pyrolytic graphite) can also be used for the same purpose. However, in this case the batch mixing or extrusion, or exfoliation process induced by extrusion or mixing composition creates a laminated compound in which the graphene nanoparticles are oriented over a relatively wide area. Said laminated compounds may be preferred for specific applications.
    0048. Mechanical exfoliation of graphite within a polymeric matrix can be performed by a polymer processing technique that transmits repetitive, high shear deformation events to mechanically exfoliate graphite microparticles in multilayer or single layers of graphene nanoparticles within the matrix polymeric.
    0049. For the purposes of the present invention, graphite microparticles are defined as graphite in which at least 50% of the graphite consists of multilayer graphite crystals in the thickness between 1.0 and 1000 microns along the c-axis of the structure trellis. Typically 75% of the graphite consists of crystals in the range between 100 and 750 microns in thickness. Expanded graphite can also be used.
    0050. The expanded graphite is made by separating, by force, the planes of the crystal lattice in graphite from natural flakes, thus expanding the graphite, for example: dipping the graphite flakes in a bath of chromic acid, and then in acid concentrated sulfuric. Expanded graphite suitable for use in the present invention includes: expanded graphite with open edges at a bilayer level, such as mesograph.
    0051. A succession of shear deformation events is defined by subjecting the molten polymer to an alternating series of upper and lower shear deformation rates, essentially over the same time intervals, so that a pulsating series of shear forces Upper and lower shear, associated with the rate of shear deformation, are applied to the graphite particles in the molten polymer. The upper and lower shear strain rates are defined as a first, the upper shear strain rate, which is at least twice the magnitude of a lower shear strain rate. The first shear strain rate is expected to range between 100 and 10,000 see-1. At least 1,000 to over 10,000,000 alternating pulses of upper and lower shear strain are applied to the molten polymer to form the exfoliated graphene nanoparticles. The number of alternating pulses required to exfoliate graphite particles into graphene particles may depend on the dimensions of the original graphite particle at the beginning of this process, that is, smaller original graphite particles may need fewer alternating pulses than the larger particles. of original graphite. This can be readily determined by a professional experienced in the art, guided by the present specification, without undue experimentation.
    0052. After high shear mixing, the graphene flakes are uniformly dispersed in the molten polymer, are randomly oriented and have a high aspect ratio. Graphene orientation can be achieved by many different methods. Conventional methods of drawing, winding and extrusion can be used to directionally align the graphene within the fiber, filament, tape, sheet, DPMC, or any other long aspect format. The method for making and characterizing a G-PMC comprises four main steps, namely: I. Extraction of crystalline graphite particles from a mineral source; II. Incorporation of the graphite particles extracted in a polymeric matrix phase and conversion of the polymer containing graphite into a graphene-reinforced polymeric matrix compound (G-PMC) by a high efficiency mixing / exfoliation process; III. Morphological analysis to determine the extent of mechanical exfoliation and distribution of multilayer graphene and graphene nanoparticles; and IV. X-ray diffraction analysis to determine multilayer graphene or graphene crystal size as a function of mechanical exfoliation.
    0053. Highly crystalline graphite can be extracted from graphite ore by a multi-stage process, as described below. I. Crushing: a graphite ore drilling bar from the mine can be placed in a "vice" and crushed. II. Crushing: the crushed graphite ore can then be crushed in a pestle. III. Size reduction: crushed graphite ore can be placed in a small millimeter mesh sieve. Larger pieces that do not pass through the screen can be crushed by pestle and then reduced in size by passing through the millimeter mesh again. Eventually all material passed through the millimeter mesh to obtain graphite ore powder. IV. Density separation by water: the millimeter-sized powder can be placed in a column filled with water and stirred until a clear separation is formed between the denser portions of the solids and the less dense portions. Graphite is close to the density of water (1 g / cm3), while silicone is much more dense (2.33 g / cm3). The taller materials are siphoned with water and then dried. The dry powder graphite is called Separate Mineral Graphite (SMG).
    0054. In commercial practice, very large machines are available for crushing and crushing, to produce tons of mixed powders, from which the graphite component can be separated by standard flotation methods.
    0055. An incorporation is intended for an in-situ exfoliation method to manufacture a G-PMC. In this method, a polymer uniformly mixed with micron particles of crystalline graphite undergoes repeated processing of the composition element during batch mixing or extrusion at a temperature at which the polymer adheres to the graphite particles. Typical polymers have a heat viscosity (without graphite) greater than 100 cps at the composition temperature. The composition temperature will vary with the polymer and can range from room temperature (for polymers that are melted at room temperature) to 600 ° C. The temperatures of typical compositions vary between 180 ° C and 400 ° C.
    0056. In one embodiment, the composition elements of the extrusion are as described in United States Patent No. 6,962,431, the description of which is incorporated herein by reference, with composition sections, known as axial striated extendable elements for mixing or elements spiral striated extensions for mixing. The composition sections act to elongate the flow of the polymer and graphite, followed by repeated folds and elongation of the material. This results in superior distributive mixing, which in turn causes progressive exfoliation of the graphite particles in discrete graphene nanoparticles. Batch mixers can also be equipped with equivalent mixing elements. In another embodiment, a standardized injection molding machine is modified to replace the standard screw with a composition screw, in order to compose materials as the composition is molded by injection. Such a device is described in US 2013/0072627, the entire description of which is incorporated herein by reference.
    0057. Thus, the effect of each composition step is the shearing of graphene layers, one after the other, so that the original graphite particles are gradually transformed into a very large number of graphene nanoparticles. After an adequate number of these passes, the end result is a uniform dispersion of discrete graphene nanoparticles in the polymeric matrix phase. Longer mixing times or a higher number of passages through the composition elements provide smaller sizes of graphite crystals and marked exfoliation of graphite on graphene nanoparticles within the polymeric matrix; however, shear events should not have a duration that would degrade the polymer.
    0058. As. the content of graphene nanoparticles increases during the extrusion of multi-layers, the viscosity of the polymer matrix increases due to the influence of the increasing number of polymer / graphene interfaces. To ensure continued refinement of the compound's structure, the extrusion parameters are adjusted to compensate for the higher viscosity of the compound.
    0059. There are automatic extrusion systems to subject a composite material to as many steps as desired, with mixing elements as described in United States Patent No. 6,962,431, and equipped with a recirculating current to direct a flow back to the extruder inlet. As the processing of the graphene-reinforced PMC is straightforward and does not involve any handling of the graphene particles, the manufacturing costs are low.
    0060. To mechanically exfoliate graphite in multilayer graphene and / or single-layer graphene, the shear deformation rate generated in the polymer during processing must cause a shear deformation in the graphite particles greater than the critical deformation required to separate two layers of graphite, or interlayer shear strength (ISS). The shear strain rate within the polymer is controlled by the type of polymer and the processing parameters, including the geometry of the mixer, the processing temperature, and speed in revolutions per minute (RPM).
    0061. The temperature and processing speed (RPM) required for a particular polymer can be determined from the polymer rheology data, since, at a constant temperature, the shear strain rate) is linearly dependent on the RPM, as shown in equation 1. The geometry of the mixer appears as the rotor radius, r, and the space between the rotor and drum, Δr:

    0062. The polymer rheology data collected for a particular polymer at three different temperatures provides a graph of shear stress versus shear strain rate. The graphite ISS is between 0.2 MPa and 7 GPa, but a new method quantified the ISS at 0.14 GPa. Thus, to mechanically exfoliate the graphite in a polymeric matrix during processing, the required processing temperature, the rate shear strain, and the RPM can be determined for a particular polymer from a graph of shear stress versus shear strain rate, collected for a polymer at a constant temperature, so that the shear stress within of the polymer is equal to or greater than the ISS of the graphite. Under typical processing conditions, polymers have sufficient surface energy to behave like the sticky side of an adhesive tape and are thus able to share the shear stress between the molten polymer and the graphite particles.
    0063. In an embodiment, a method for forming a G-PMC includes distributing graphite microparticles within a melted thermoplastic polymer phase. A succession of shear deformation events is then applied to the molten polymer phase so that the molten polymer phase exfoliates the graphite successively at each event until at least 50% of the graphite is exfoliated to form a distribution in the molten polymer phase. of graphene nanoparticles of single and multilayer layers with thickness below 50 nanometers along the direction of a "c" axis.
    0064. In another embodiment, a method for forming a crosslinked G-PMC includes distributing graphite microparticles within a melted thermoplastic polymer phase comprising one or more thermoplastic polymers. A succession of shear deformation events, as illustrated in the examples, are then applied to the molten polymer phase in such a way that the molten polymer phase exfoliates the graphene successively with each event to a lower level of graphene layer thickness. be achieved, after which the breaking of exfoliated multilayer graphene sheets occurs and produces reactive edges on the multilayer sheets, which react with the thermoplastic polymer with which they are cross-linked.
    0065. In another embodiment, the crosslinked G-PMC can be ground into particles and mixed with host polymers without crosslinking to serve as hardening agents for the host polymer. The non-crosslinked polymer acquires the properties of the crosslinked polymer because of the chain entanglement between the two polymer species. The present invention, therefore, also includes the cross-linked polymers of the present invention in particulate form that can be mixed with other polymers to form a high strength compound. In one embodiment, cross-linked polystyrene and polymethyl methacrylate (PMMA) particles of the present invention can be used as hardening agents for host polymers. The compositions according to the present invention include host thermoplastic polymers hardened to between about 1 and about 75% by weight of the crosslinked polymer particles of the present invention. In an embodiment, the host polymers are hardened to between about 10 and about 50% of the weight of the crosslinked polymer particles.
    0066. In certain embodiments, the thermoplastic polymer is an aromatic polymer. As defined herein, the term "aromatic polymer" refers to a polymer comprising aromatic moieties, either as part of the polymer's backbone or as substituents attached to the polymer's backbone, optionally by means of a binder. Linkers include straight or branched alkylene groups, such as methylene, ethylene and propylene,} straight or branched heteroalkylene groups such as —OCH2—, - CH2O—, -OCH2CH2-, -CH2CH2O-, - OCH2CH2CH2-, -CH2OCH2-, -CHCH (CH3) -, -SCH2-, -CH2S-, -NRCH2-, -CH2NR-, and the like, in which the heteroatom is selected from the groups consisting of oxygen, nitrogen and sulfur and R is selected from hydrogen and lower alkyl. The ligands can also be heteroatomic, such as O—, —NR— and —S—. When the binders contain sulfur, the sulfur atom is optionally oxidized. The aromatic moieties are selected from monocyclics, for example, phenyl, and polycyclic moieties, for example naphthyl, indole, anthracene, etc., and are optionally substituted with amino, NHR, NR2, halogen, nitro, cyano, alkylthio, alkoxy, alkyl , haloalkyl, CO2R where R is defined as sign, and combinations of two or more of the same. The aromatic moieties can also be heteroaryl, comprising one to three heteroatoms selected from the group consisting of oxygen, nitrogen and sulfur, and optionally substituted as described above. The aromatic polymer preferably comprises phenyl groups, optionally substituted as described above, either as part of the polymer backbone or as substituents on the backbone, the latter optionally by means of a binder as described above. In certain embodiments, the optionally substituted phenyl groups are contained within the polymer backbone as optionally substituted phenylene groups. In certain other embodiments, the optionally substituted phenyl groups are substituents on the polymer backbone, optionally connected through a linker, as described above. *
    0067. Examples of host thermoplastic polymers include, without limitation, polyetheretherketone (PEEK), polyetherketone (PEK), polyphenylene sulfide (PPS), polyethylene sulfide (PES), polyetherimide (PEI), polyvinylidene fluoride (PVDF), polysulfone (PSU), polycarbonate (PC), polyphenylene ether, aromatic thermoplastic polyesters, aromatic polysulfones, thermoplastic polyimides, liquid crystal polymers, thermoplastic elastomers, polyethylene, polypropylene, polystyrene (PS), acrylics such as polymethylmethacrylate (PMMA), polyacryl-nitrile (PAN) acrylonitrile butadiene styrene (ABS), and the like, ultra-high molecular weight polyethylene (UHMWPE), polytetrafluoroethylene (PTFE / Teflon®), polyamides (PA) such as nylon, polyphenylene oxide (PPO), polyoxymethylene plastic (POM / Acetal) , polyimides, polyarylethylketones, polyvinylchloride (PVC), acrylics, mixtures thereof and the like. When the thermoplastic host polymer and the crosslinked polymer are of the same polymer species, the crosslinked polymer particles are essentially a concentrated master batch of the degree of the desired crosslinked species to be introduced into the polymer formulation.
    0068. Therefore, another aspect of the present invention provides a method for forming a polymer matrix compound reinforced by high strength graphene, distributing graphite microparticles in a molten thermoplastic polymer phase, comprising one or more fused thermoplastic polymers. A succession of shear deformation events, as shown in the examples, is then applied to the molten polymer phase so that the molten polymer phase exfoliates the graphene, successively with each event until the exfoliated multilayer sheets of graphene break and produce reactive edges on said multilayer sheets that react and cross-connect the thermoplastic polymer. A thermoplastic polymer of graphene cross-linked and then ground into particles that are distributed in another non-cross-linked polymer.
    0069. Thus, activated graphene is formed like graphene fractures, through the basal plane and offers potential sites for cross-linking the matrix or attaching other chemically unstable groups for functionalization. Therefore, cross-linking is performed under exclusion of oxygen, preferably under an inert atmosphere or a vacuum, so that the reactive edges do not oxidize or on the contrary become non-reactive. The formation of covalent bonds between graphene and the matrix significantly increases the strength of the compound. Polymers that cross-link when subjected to the method of the present invention include polymers subject to degradation by ultraviolet (UV) light. This includes polymers and contains aromatic rings, for example, benzene rings, such as polystyrene, polymers containing tertiary carbons such as polypropylene and the like, polymers containing backbone oxygen, such as poly (alkylene oxides), and the like.
    0070. In certain embodiments, graphite particles can be prepared by crushing and crushing a graphite-containing mineral in millimeter dimensions. Millimeter-sized particles can be reduced to micronic dimensions using ball milling and friction milling.
    0071. In certain embodiments, the graphite particles can be extracted from the mixture of micronic particles, preferably by a flotation method. The extracted graphite particles can be incorporated into a polymeric matrix using a single screw extruder with extensional mixing elements axially spiral striated. The polymeric matrix containing graphite undergoes repeated extrusion, as described in the present to induce exfoliation of the graphitic material thus forming a uniform dispersion of graphene nanoparticles in the polymeric matrix.
    0072. In other embodiments, the succession of shear deformity events can be applied until at least 50% of the graphite is exfoliated to form a distribution in the melted polymer phase of simple nanoparticle and multilayer graphene with a thickness below 10 nanometers to the along the direction of the c-axis.
    0073. In other embodiments, the succession of shear deformity events can be applied until at least 90% of the graphite is exfoliated to form a distribution in the melted polymer phase of single and multilayer graphene nanoparticles with a thickness below 10 nanometers at a time. along the direction of the c-axis.
    0074. In other embodiments, the succession of shear deformity events can be applied until At least 80% of the graphite is exfoliated to form a distribution in the melted polymer phase of simple and multilayer graphene nanoparticles with a thickness below 10 nanometers along the direction of the c-axis.
    0075. In other embodiments, the succession of shear deformation events can be applied until at least 75% of the graphite is exfoliated to form a distribution in the melted polymer phase of simple and multilayer graphene nanoparticles with a thickness below 10 nanometers at a time. along the direction of the c-axis.
    0076. In other embodiments, the succession of shear deformity events can be applied until at least 70% of the graphite is exfoliated to form a distribution in the melted polymer phase of simple and multilayer graphene nanoparticles with a thickness below 10 nanometers at a time. along the direction of the c-axis.
    0077. In other embodiments, the succession of shear deformity events can be applied until at least 60% of the graphite is exfoliated to form a distribution in the melted polymer phase of simple and multilayer graphene nanoparticles with a thickness below 10 nanometers at a time. along the direction of the c-axis.
    0078. In other incorporations, graphite can be doped with other elements to modify the surface chemistry of exfoliated graphene nanoparticles. Graphite is expanded graphite.
    0079. In other embodiments the surface chemistry or nanostructure of the dispersed graphite can be modified to increase the bond strength with the polymer matrix to increase the strength and stiffness of the graphene compound.
    0080. In other incorporations, the directional alignment of graphene nanoparticles is used to obtain uni-, bi-, or three-dimensional reinforcement of the polymeric matrix phase.
    0081. In another embodiment, a graphene-reinforced polymer matrix compound is formed according to the methods described herein. Provides thermoplastic polymer compounds in which polymeric chains are cross-linked inter-molecularly by single and multi-layered torn graphene sheets by means of covalent bonding sites exposed at the edges of the torn graphene sheet.
    0082. In certain embodiments, the thermoplastic polymer of the graphene-reinforced polymer matrix compound is an aromatic polymer, as defined above.
    0083. In other embodiments, the graphene-reinforced polymer matrix compound consists of cross-linked graphite with polymers selected from the group consisting of polyetheretherketone (PEEK), polyetherketone (PEK), polyphenylene sulfide (PPS), polyethylene sulfide (PES), polyetherimide (PEI), polyvinylidene fluoride (PVDF), polycarbonate (PC), polyphenylene ether, aromatic thermoplastic polyesters, thermoplastic polyimides, liquid crystal polymers, thermoplastic elastomers, polyethylene, polypropylene, polystyrene (PS), acrylics such as polymethyl AMP , polyacrylonitrile (PAN), acrylonitrile butadiene styrene (ABS), and the like, ultra high molecular weight polyethylene (UHMWPE), polytetrafluoroethylene (PTFE / Teflon®), polyamides (PA) phials such as nylon, oxide polyphenylene (PPO), plastic polyoxymethylene (POM / Acetal), polyimides, polyarylethylketones, polyvinylchloride (PVC), mixtures thereof and the like.
    0084. In other embodiments, the graphene-reinforced polymer matrix compound consists of graphite and cross-linked with polyetheretherketone (PEEK). Sulphonated PEEK can also be cross-linked. PEEK that is cross-linked in this way will have very high specific properties and is suitable for automotive, aeronautical and aerospace uses. Therefore, the present invention also includes automotive, aeronautical and aerospace parts formed of cross-linked PEEK of the present invention, which can replace heavier metal parts without loss of mechanical properties or high temperatures. For example, cross-linked PEEK can be used in engine components such as pistons, valves, crankshafts, turbochargers and the like because of their high melting point and slip resistance. The formation of the rotating portions of the turbine parts and a cross-linked PEEK turbo-compressor of the present invention will reduce the turbo-compressor delay because of the resulting weight reduction. Other advantages are obtained by forming the rotating portions of the jet engine turbine and compressor formed with the cross-linked PEEK of the present invention. Example
    0085. The present invention is further illustrated by the following examples, which should in no way be construed as limitations. At the same time that some incorporations have been illustrated and described, it should be understood that changes and modifications can be made, according to experience in the art, without departing from the invention and its broader aspects, as defined in the following claims.
    0086. In one embodiment, a small-scale extension mixer with a capacity of 10 grams was used to compose 2% SNG with Udel P-1700 Polysulfone (PSU) 332 ° C (630 ° F) and under vacuum for 3, 30 , and 90 minutes. The method is described below. The samples collected for characterization after each period of time are called 3G-PMC, 30G-PMC, 90G-PMC. 1. 9.8 grams DPSU was loaded into the mixer and allowed to melt. 2. 0.2 grams of SMG were added to the melted PSU and mixed. 3. After 3 minutes of mixing time, 3 grams of GPMC were extruded out of the mixer and collected for characterization. 4. 3 grams of 2% SMG in PSU were loaded into the mixer and mixed. 5. After 30 minutes of mixing, 3 grams of the GPMC were extruded out of the mixer and collected for characterization. 6. 3 grams of 2% SMG in PSU were added to the mixer and mixed. 7. After 90 minutes of mixing time, 3 grams of the GPMC were extruded out of the mixer and collected for characterization. Morphological Analysis
    0087. A Zeiss Sigma Field Emission Scanning Electron Microscope (FESEM) with EDS Oxford was used to determine the degree of mechanical exfoliation of graphite in multilayer graphene or graphene nanoparticles and the thickness of these particles. An acceleration voltage of 3 kV and an operating distance of approximately 8.5 mm were used during visualization. Prior to visualization, specimens from each sample of 3G-PMC, 30G-PMC and 90G-PMC were notched and cryogenically fractured to produce a flat fracture surface, placed under vacuum for at least 24 hours, coated with gold and stored under vacuum. X-Ray Diffraction Analysis (XRD)
    0088. The XRD analysis in each sample of 3G-PMC, 30G-PMC and 90G-PMC, includes 4 steps: (1) sample preparation, (2) acquisition of the diffraction pattern, (3) profile adjustment and ( 4) calculation of crystallite sizes, according to the Debye-Scherrer equation. 1. The samples for XRD analysis were prepared by pressing thin films from each sample 3G-PMC, 30G-PMC and 90G-PMC at 230 ° C. and 5, 500 PSI over a two minute time period. Each sample was placed between aluminum foils before being pressed, using a uniaxial press press with heated presses. 2. Diffraction patterns of the pressed films were acquired, using a Phillips Xpert Pownder Diffractometer with 40 kV and 45 mA sample changer (Xpert) with an incident 0.3 mm gap thickness of 4 ° - 70 ° 2θ and a step size of 0.02 ° 20. 3. Diffraction patterns were loaded into the powder diffraction graph tool WinPLOTR, without background correction or profile adjustments prior to peak adjustment. Simple peak adjustment was applied over a range of 20 26 ° - 27.5 °, using a pseudo Voigt function and taking into account a global eta FWHM, (Lorentz ratio) and linear antecedents. The simple peak adjustment of the profile provides the complete width at half the maximum (FWHM) of the relevant peak.
    0089. The average crystallite size outside the plane (D) (sometimes cited as along the c axis, and proportional to the number of graphene layers that are stacked) is calculated using the Debye-Scherrer Equation and the FWHM values (002), whereby À is the X-ray wavelength, coefficient K = 0.89, β is the FWHM in radians, and 0 is the diffraction angle. The d-spacing is also calculated.
    Morphological Results
    0090. The morphology of each sample 3G-PMC, 30G-PMC, and 90G-PMC, in three different scales, (magnification) is shown in Figure 1. In (ac) a 20 μm scale and a magnification of 1,000X , shows good distribution of multilayer graphene or graphene within the PSU matrix at each mixing time. In (d-f) on a 1 μm scale and 10,000X magnification and (g- i) a 1 μm scale and 50.00X magnification shows mechanically exfoliated graphite within the PSU matrix. (d-i), multilayer graphene micro-fold or graphene is evident, as well as the good connection between the graphene nanoparticles and the polymeric matrix.
    0091. The 90G-PMC sample, which has been mixed for longer and exposed to more repetitive shear, exhibits superior mechanical exfoliation and the smallest crystal size. As shown in Figure 2, mechanical exfoliation reduced the thickness of the graphene nanoparticle in the 90G-PMC sample to 8.29nm. X-Ray Diffraction Results
    0092. The Debye-Scherrer equation was applied to the results of FWHM and d-spacing obtained from the X-ray diffraction patterns for 3G-PMC, 30G-PMC and 90G-PMC to provide the crystal thickness (D) of the multilayer graphene or graphene nanoparticles. The results of XRD and crystal thickness are shown in Table 1. For samples 3G-PMC, 30G-PMC and 90G-PMC, the crystal thickness is 40nm, 31nm, and 23nm; FWHM is 0.202 °, 0.257 ° and 0.353 °; and the d-spacing is 3,361nm, 3,353nm and 3,387nm, respectively. FWHM increases with the mixing time, and the thickness of the crystal decreases with the mixing time, which indicates that the mechanical exfoliation of graphite to multilayer graphene or graphene is occurring and increases over longer mixing times. Decreasing the size of the crystal is a function of FWHM. Table 1 The Debye-Scherrer Equation applied to the average XRD results of each 2% of Exfoliated Graphite in a PSU sample mixed for 3min, 30min and 90min
    Graphene Modification
    0093. The mechanical exfoliation of graphite in multilayer graphene, or graphene as a result of the repetitive shear deformation action on the polymer processing equipment, generates outstanding primary and secondary bonds that provide the opportunity for various chemical reactions to occur, which can be used to increase the properties of G-PMC. This represents an improvement over conventional methods of the prior art, forming graphene oxides, in which the pendant primary and secondary bonds bond covalently with oxygen that typically remains in these positions even after the graphene oxide is reduced.
    0094. For example, chemical reactions that covalently attach these pending bonds, from multilayer graphene or graphene nanoparticles to the polymeric matrix, would provide superior mechanical properties of the GPMC. Alternatively, electrical conductivity can be enhanced by chemically bonding appropriate broadband materials to the edges of graphene nanoparticles or coordinating with conductive metals, such as gold, silver, copper, and the like. The graphene-reinforced polymer can then be added to polymers or other compositions to provide or increase electrical conductivity. The bonds can also be coordinated with metals, such as platinum and palladium, to provide a catalyst with the graphene-reinforced polymer, serving as a support for the catalyst. Other forms of functionalized graphene are described in US Patent No. 8,096,353, the description of which is hereby incorporated by reference.
    0095. The method of the present invention is particularly advantageous because the in situ functionalization reactions can be carried out during the exfoliation process, via reactive one-pot composition.
    0096. Graphene-reinforced polymers can be used as electrodes for lightweight batteries. Other uses include hulls of composite ships, aircraft, aerospace systems, transport vehicles, lightweight bodies, pressurized ships, reactor chambers, spray coatings, polymeric powders for 3-D printing, transparent electrodes for electronic device touch screens , and the like. The addition of 1-2% of the weight of graphene to a polymeric matrix transmits electrical conductivity, while maintaining optical transparency, thus allowing applications in solar panels, flat panel displays and for statistics and discharge control in hospitals.
    0097. Mechanical exfoliation successfully converted 2% of molten graphite and mixed with PSU and a G-PMC, using a repetitive shearing action on the small scale extention mixer, manufactured by Randcastle Extrusion Systems, Inc ("Randcastle"). The results can be improved by modifying the machine to increase shear; for example using a larger diameter mixing element to increase the rotational speed and / or minimizing the spacing between the mixing element and the cylinder wall. Modified Randcastle Extrusion System's Small Scale Extent ion Mixer:
    0098. The design of the existing small batch mixer and can be modified to provide a higher shear rate, which in turn provides superior mechanical exfoliation of graphite within the polymer matrix. The shear rate /, is calculated according to equation 1, where r is the tool radius and Δr is the release to compose. Machine modifications are listed in table 2, together with the maximum attainable shear rate. The new designed mixer has a maximum shear rate 22 times that of the current mixer which will provide greater mechanical exfoliation of the graphite within a polymeric matrix in shorter periods of time. In other words, the size of the crystal, D, can be reduced to smaller dimensions in a more efficient period of time. Table 2 Modifications to the Randcastle Extrusion System's Small Scale Extension Mixer to provide greater mechanical exfoliation
    Modified single screw extrusion:
    0099. Randcastle made modifications to the extruder screw that will allow better mechanical exfoliation of graphite in multilayer graphene or graphene in a polymeric matrix to manufacture a G-PMC. Materials
    00100. Crude graphite was extracted from the earth, crushed to a powder and separated by flotation to obtain Separated Mineral Graphite ("SMG").
    00101. PEEK has a specific gravity of 1.3, a melt flow of 3g / 10min (400 ° C., 2.16kg), a glass transition temperature of 150 ° C and a melting point of 340 ° C. The elasticity and resistance modules are 3.5 GPa and 95 MPa, respectively. Prior to the creation of xG-PMC in this example, SMG and PEEK were dried for approximately 12 hours at 100 ° C and 150 ° C, respectively. In this example SMG was mixed with PEEK, using a Randcastl microlot mixer with a 10-gram capacity at 360 ° C (680 ° F) and without RPM under a nitrogen blanket according to the following steps: PEEK_3 - to create a control sample, 10 grams of PEEK were added to the mixer, after 3 minutes of mixing time, the door was opened to allow PEEK to flow out as extruded and 2.6 grams were extruded and removed until no more material could Flow. SMG-PEEK3 - to create a composition ratio by weight 2-98% SMG-PEEK, 2.4g PEEK and 0.2g SMG were added to the mixer, after 3 minutes of mixing time the door was opened to allow G-PMC flowed out as extruded and 96g were extruded out until no additional material could flow. SMG-PEEK_30 - to maintain the composition ratio of 298% by weight, 1.92 g of PEEK and 0.04 g of SMG were added to the mixer. After 30 minutes of mixing time the door was opened to allow G-PMC to flow out as extruded and 0.94g was extruded out until no more material could flow. SMG-PEEK_90 - to maintain the composition ratio of 298% by weight, 0.92g of PEEK and 0.02g of SMG, were added to the mixer. After 90 minutes of mixing time the door was opened to allow G-PMC to flow out as extruded; however, no more material could flow.
    00102. The experiment ended and the mixer was opened. Upon visual observation, the GPMC did not appear as a standard fused polymer, but was in a fibrous, rubbery shape.
    00103. In this next example SMG and PEEK were processed in a Randcastle micro-batch mixer with a capacity of 100g to 360GC (680 ° F) and 30 RPM over a nitrogen blanket, according to the following steps: PEEK90 - to create a Control sample 100g PEEK was added to the mixer. After 90 minutes of mixing time, the door was opened to allow PEEk to flow out as extruded and 28.5g was extruded out until no additional material could flow. SMG-PEEK_25 - to create a weight composition ratio of 2-98% SMG-PEEK, 98g PEEK and 2g SMG were added to the mixer. After 25 minutes of mixing time the door was opened to allow G-PMC to flow out as extruded and 5.1 g was extruded out until no more material could flow. Description
    00104. The samples used for characterization appear in Table 3, as follows: Table 3 Samples used for characterization
    Morphology
    00105. The morphology of the xG-PMC was examined using a Zeiss Sigma Field Emission Scanning Electron Microscope ("FESEM") with Oxford EDS. An acceleration voltage of 3kV and an operating distance of approximately 8.5 mm was used during visualization . Before visualization, specimens were carved cryogenically fractured to produce a flat fracture surface, positioned under vacuum for at least 24 hours coated with gold and stored under vacuum. As shown in Figure 3, the SMG-PEEK_90 morphology is shown in (a) 10 μm scale and magnification by 1,000, (b) 10 μm scale and 5,000 magnification, (c) 1 μm scale and magnification by 10,000 and (d) 1 μm scale and 50,000 magnification. Thermal analysis
    00106. The thermal properties of the samples were characterized using a TA Instruments Q1000 Differential Scanning Calorimeter (DSC). Each sample underwent a 0-400 ° C heat / cold / heat cycle at 1 10 C / min at glass transition temperature (Tg) and melting temperature (Tm) for the initial hot scan is shown in figure 3. The TG increases from 152 ° C for PEEK_3 to 154 for SMG-PEEK90; however, this increase is not significant. The Tm is consistent for samples PEEK_3, SMG-PEEK_3 and SMG-PEEK_30 at almost 338 ° C, but decreases significantly to 331.7 ° C for SMG-PEEK — 90. Delta H is similar for samples PEEK_3, SMG — 3 and SMG-PEEK_30, and varies between initial, cold and reheated scans, and varies between 116 and 140 J / g. However, delta H for SMG-PEEK_90 is much lower and consistent at around 100 J / g, for initial, cold, and reheated scans. The observable difference in PEEK fusion heat for the SMG-PEEK_90 sample, when compared to other samples, indicates an important difference in morphology. Furthermore, the constant heat of fusion between the initial, cold and reheated scans of the SMG-PEEK_90 sample supports the existence of cross-links between the graphene and the PEEK matrix. Parallel Plate Rheology
    00107. A frequency scan of 100 to 0.01 Hz at 1.0% strain was performed at a temperature of 360 ° C, using a TA InstrumentsAR 2000 in parallel plate mode. The SMG-PEEK30, SMG-PEEK_3, and PEEK3 samples were tested. G'e G "and delta" tan ", for samples SMG-PEEK_30, SMG-PEEK_3 and PEEK_3, have been recorded. The delta" tan "is equal to G" /G'.These rheology data provide information regarding the sample morphology, according to table 4, as shown in the table below. The transition point of sol / gel, or "gel point" of a fixed term resin, occurs when delta "tan" is = 1, or even when G '= G ". For samples SMG-PEEK_3 and PEEK_3, the G" is greater than G ', indicating a behavior similar to that of the liquid.
    00108. In contrast, for the SMG-PEEK_30 sample, G'is greater than G ", indicating a behavior more similar to that of elastic or solid. Furthermore," tan "delta is less than 1 and remains almost constant , across the entire frequency range for SMG-PEEK_30, indicating that SMG-PEEK — 30 has undergone some degree of cross-linking. Table 4 Rheology Data and the Sol-Gel Transition Point
    Dissolution
    00109. Thermosetting resins slightly gelled when placed in solvents swell through absorption to a degree that depends on the solvent and the structure of the polymer. The original shape is preserved and the swollen gel exhibits elastic properties rather than plastic. Cross-linking in thermoplastic polymers is commonly performed by 1} peroxides, 2) a silane grafting process of cross-linking by water, 3) electron radiation, 4) UV light.
    00110. In this example, cross-linking was induced between SMG and PEEK during a mechanical exfoliation process due to the splitting of graphene flakes which results in pending free radicals. To confirm the presence of cross-linking in the SMG-PEEK XG-PMC, a dissolution method was used, placing pure samples of PEEK, PEEK_3, PEEK_90, SMG-PEEK_3, SMG-PEEK_30, and SMG-PEEK_90 in sulfuric acid, according to the following steps: A 10 mg specimen of each sample was prepared. Each specimen was placed in a 20 mL test tube, from 95 to 98% by weight of sulfuric acid ((A300S500 Fisher Scientific). The solution was shaken for 5 minutes; Each test tube was capped with Teflon® tape to keep hermetically sealed, photographs of each sample were taken at 0, 24, 48, and 72 hours.
    00111. By visual observation the PEEK samples dissolve within the sulfuric acid before 24 hours and the SMG-PEEK_90 sample is the only one that remains in the sulfuric acid after 72 hours. The SMG-PEEK_90 sample was cross linked and swelled when placed in the solvent similar to a thermoset resin. The SMG-PEEK_30 sample remained in sulfuric acid after 24 hours, but dissolved before 48 hours. SMG-PEEK_30 required additional testing to determine whether cross-linking was induced, as the other data suggests that SMG-PEEK_30, was cross-linked. }
    00112. The examples and description above of the preferred embodiments are to be considered illustrative and not as limitations of the present invention, as defined by the claims. As will be readily understood, numerous variations and combinations of the characteristics stipulated above can be used without departing from the present invention, as described in the claims. Said variations are not considered to be a divergence in the spirit and scope of the invention and all such variations are intended to be included in the scope of the following claims.
    权利要求:
    Claims (16)
    [0001]
    1. Method for forming a graphene-reinforced polymer matrix composite, characterized by the fact that it comprises: (a) distributing graphite microparticles in a melted thermoplastic polymeric phase consisting essentially of one or more melted thermoplastic polymers to form a thermoplastic polymeric phase graphite cast, in which at least 50% of the graphite in the graphite microparticles consists of multilayer graphite crystals between 1.0 and 1000 microns thick along the direction of the c-axis; and (b) applying a succession of shear stress events to the thermoplastic polymer phase fused with graphite while providing elongated flow, so that the shear stress within said molten polymer phase exceeds the interim shear strength (ISS) of said microparticles. of graphite and said melted polymer phase exfoliates the graphite microparticles successively with each event until said graphite microparticles are at least partially exfoliated to form a distribution in the melted polymer phase of single-layer or multilayer graphene nanoparticles, or both , less than 10 nm thick in the direction of the c-axis and continuing further the shear stress events until the fracture of said exfoliated graphene sheets of one or several layers occurs through the basal plane and produces binding sites of graphene carbon of reactive free radicals at the fractured edges of the referred sheets graphene of one or more layers which react with said one or more polymer fused thermoplastics to provide a compound where the polymer thermoplastic chains are covalently bonded directly to, and intermolecularly cross-linked by said one or more layer graphene sheets; in which the succession of shear stress events that provide the composite where the chains of thermoplastic polymers are directly covalently linked and cross-linked by the said single- or multi-layer graphene sheets, is a series of at least 1,000 to more than 10,000,000 alternating pulses of a first shear strain rate and a second shear strain rate, where the first shear strain rate is between 100 and 10,000 sec-1 and is at least twice the magnitude of the second rate deformation.
    [0002]
    Method according to claim 1, characterized by the fact that at least one of said one or more fused thermoplastic polymers is an aromatic polymer.
    [0003]
    Method according to claim 2, characterized in that said aromatic polymer comprises phenyl groups, optionally substituted, in the spine or as substituents.
    [0004]
    Method according to claim 3, characterized in that the optionally substituted phenyl groups are (i) contained in the polymer backbone as optionally substituted phenylene groups; or (ii) substituents on the polymer.
    [0005]
    Method according to any one of claims 1, characterized in that said one or more fused thermoplastic polymers are selected from the group consisting of polyetheretherketone (PEEK), polyetherketone (PEK), polyphenylene sulfide (PPS), polyethylene sulfide (PES), polyetherimide (PEI), polyvinylidene fluoride (PVDF), polycarbonate (PC), aromatic thermoplastic polyesters, thermoplastic polyimides, liquid crystal polymers, thermoplastic elastomers, polyethylene, polypropylene, polystyrene (PS), polymethylmethyl (polyacrylate) PMMA), polyacrylonitrile (PAN) - high molecular weight polyethylene (UHMWPE), polytetrafluoroethylene (PTFE), acrylonitrile-butadiene-styrene (ABS), polyamides (PA), polyphenylene oxide (PPO), polyoxymethylene plastic (POM / Acetal ), polyarletherketones, polyvinyl chloride (PVC), acrylics and their mixtures.
    [0006]
    6. Method for forming a polymer matrix composite reinforced with high strength graphene, characterized in that it comprises: (a) forming the composite of any one of claims 1 to 5 in crosslinked polymer particles; and (b) distributing the polymer particles to another polymer in the thermoplastic matrix of the non-crosslinked fused host.
    [0007]
    Method according to any one of claims 1 to 6, characterized in that said molten thermoplastic polymer phase comprises two or more molten thermoplastic polymers.
    [0008]
    8. Method according to any one of claims 1 to 7, characterized in that the graphite microparticles are prepared by grinding and grinding a mineral containing graphite in millimeter dimensions, followed by grinding into a mixture of micron-sized particles, optionally in which graphite microparticles are extracted from the micron-sized particle mixture by a flotation method.
    [0009]
    Method according to claim 1 or claim 8, characterized in that said one or more fused thermoplastic polymers is polyetheretherketone (PEEK).
    [0010]
    Method according to any one of claims 1 to 9, characterized in that the graphite is expanded graphite.
    [0011]
    11. Thermoplastic polymer composite formed by the method defined in claim 1, characterized by the fact that it comprises chains of thermoplastic polymers that are directly covalently linked and intermolecularly interconnected by graphical carbon binding sites of reactive free radicals at the fractured edges of a single sheet of graphene and / or multilayers.
    [0012]
    12. Graphene crosslinked polymer particles, characterized in that they are formed from the compound of Claim 11.
    [0013]
    Polymer composition characterized in that it comprises a host thermoplastic polymer and the graphene crosslinked polymer particles of Claim 12 dispersed therein.
    [0014]
    14. Thermoplastic polymer composite according to claim 11 or polymer composition according to claim 13, characterized in that said host thermoplastic polymer is selected from the group consisting of polyetheretherketone (PEEK), polyether- ketone (PEK), polysulfones (PS), polyphenylene sulfide (PPS), polyethylene sulfide (PES), polyetherimide (PEI), polyvinylidene fluoride (PVDF), polycarbonate (PC), aromatic thermoplastic polyesters, thermoplastic polyimides, polymers of liquid crystal, thermoplastic elastomers, polyethylene, polypropylene, polystyrene (PS), polymethylmethacrylate (PMMA), polyacrylonitrile (PAN), high molecular weight polyethylene (UHMWPE), polytetrafluoroethylene (PTFE), acrylonitrile-butadiene-styrene (ABS ), polyamides (PA), polyphenylene oxide (PPO), polyoxymethylene plastic (POM / Acetal), polyarletyl ketones, polyvinyl chloride (PVC), acrylics and mixtures thereof.
    [0015]
    Automotive, aircraft or aerospace part, characterized in that it is formed from the polymeric composite of Claim 11 or the polymeric composition of Claim 13, optionally wherein said part is an engine part.
    [0016]
    16. Method according to any one of claims 1 to 10, characterized in that said succession of shear stress events is applied while imparting elongated flow using a single screw extruder, in which the screw composition sections of the extruder are characterized by extensional mixing elements with axial channels or extensional mixing elements with spiral pleats.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112015026355B1|2021-03-30|IN SITU SKINING METHOD FOR MANUFACTURING A POLYMERIC MATRIX COMPOSITION REINFORCED BY GRAPHENE
    US11225558B2|2022-01-18|Graphene-reinforced polymer matrix composites
    JP6633676B2|2020-01-22|In situ exfoliation method for producing graphene reinforced polymer matrix composite
    BR112015008949B1|2021-11-30|METHOD FOR FORMING A GRAPHENE-REINFORCED POLYMER MATRIX COMPOUND
    US20200048425A1|2020-02-13|Covalent Conjugates of Graphene Nanoparticles and Polymer Chains and Composite Materials Formed Therefrom
    US20210363321A1|2021-11-25|In Situ Exfoliation Method to Fabricate a Graphene-Reinforced Polymer Matrix Composite
    TW202115166A|2021-04-16|Covalent conjugates of graphene nanoparticles and polymer chains and composite materials formed therefrom
    同族专利:
    公开号 | 公开日
    HK1221440A1|2017-06-02|
    WO2014172619A1|2014-10-23|
    MX2015014631A|2016-09-29|
    JP6633703B2|2020-01-22|
    JP2019002021A|2019-01-10|
    US20190233611A1|2019-08-01|
    BR112015026355A2|2017-09-26|
    KR20160003719A|2016-01-11|
    CN105324241B|2017-06-13|
    US10253154B2|2019-04-09|
    EP2994308A1|2016-03-16|
    KR102292918B1|2021-08-24|
    JP2016519191A|2016-06-30|
    CA2909715A1|2014-10-23|
    SG11201508599PA|2015-11-27|
    US11174366B2|2021-11-16|
    JP2020063447A|2020-04-23|
    US20160083552A1|2016-03-24|
    JP6393743B2|2018-09-19|
    CN105324241A|2016-02-10|
    EP2994308A4|2016-11-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5298214A|1990-10-30|1994-03-29|Rutgers, The State University|Method of deriving polystyrene and polyolefin plastics composite from recycled plastics|
    CA2135322C|1993-11-10|2001-02-06|Hiroshi Sugahara|Method for producing a fiber-reinforced thermoplastic resin foamed product|
    JP3419093B2|1994-08-11|2003-06-23|三菱化学株式会社|Thermoplastic resin composition, method for producing the same, and electromagnetic wave shield molded product comprising the composition|
    US5789477A|1996-08-30|1998-08-04|Rutgers, The State University|Composite building materials from recyclable waste|
    JP5770962B2|1999-12-07|2015-08-26|ウィリアム・マーシュ・ライス・ユニバーシティ|Oriented nanofibers embedded in a polymer matrix|
    US6660241B2|2000-05-01|2003-12-09|Saint-Gobain Ceramics & Plastics, Inc.|Highly delaminated hexagonal boron nitride powders, process for making, and uses thereof|
    US6962431B1|2000-11-08|2005-11-08|Randcastle Extrusion System, Inc.|Extruder mixer|
    JP2002234773A|2001-02-02|2002-08-23|Mitsubishi Gas Chem Co Inc|Method for producing porous carbon material|
    JP3958137B2|2001-08-20|2007-08-15|大塚化学ホールディングス株式会社|Resin composition|
    US20050070658A1|2003-09-30|2005-03-31|Soumyadeb Ghosh|Electrically conductive compositions, methods of manufacture thereof and articles derived from such compositions|
    US20050186378A1|2004-02-23|2005-08-25|Bhatt Sanjiv M.|Compositions comprising carbon nanotubes and articles formed therefrom|
    JP4245514B2|2004-05-24|2009-03-25|日信工業株式会社|Carbon fiber composite material and method for producing the same, method for producing carbon fiber composite metal material, method for producing carbon fiber composite non-metal material|
    US8048940B2|2004-07-09|2011-11-01|Vanderbilt University|Reactive graphitic carbon nanofiber reinforced polymeric composites showing enhanced flexural strength|
    US20070099792A1|2005-04-27|2007-05-03|William Marsh Rice University|Carbon nanotube reinforced thermoplastic polymer composites achieved through benzoyl peroxide initiated interfacial bonding to polymer matrices|
    US20110223405A1|2005-11-18|2011-09-15|Northwestern University|Composite polymer film with graphene nanosheets as highly effective barrier property enhancers|
    WO2007145918A2|2006-06-05|2007-12-21|University Of Akron|Ultrasound assisted continuous process for dispersion of nanofibers and nanotubes in polymers|
    MX2009000042A|2006-07-05|2009-03-04|Owens Corning Intellectual Cap|Polymer foams containing multi-functional layered nano-graphite.|
    US7745528B2|2006-10-06|2010-06-29|The Trustees Of Princeton University|Functional graphene-rubber nanocomposites|
    JP5207351B2|2007-03-23|2013-06-12|独立行政法人産業技術総合研究所|Melt-kneaded product, resin molded product and method for producing the same|
    US7824651B2|2007-05-08|2010-11-02|Nanotek Instruments, Inc.|Method of producing exfoliated graphite, flexible graphite, and nano-scaled graphene platelets|
    EP2176163B1|2007-08-01|2017-10-25|Dow Global Technologies LLC|Highly efficient process for manufacture of exfoliated graphene|
    WO2009029984A1|2007-09-03|2009-03-12|Newsouth Innovations Pty Limited|Graphene|
    DE102007049439A1|2007-09-27|2009-04-02|Electrovac Ag|Plastic composite material and method for its production|
    US7906053B1|2008-02-21|2011-03-15|Northwestern University|Polymer-graphite nanocomposites via solid-state shear pulverization|
    CN102015529B|2008-02-28|2014-04-30|巴斯夫欧洲公司|Graphite nanoplatelets and compositions|
    CN101998971A|2008-03-18|2011-03-30|拉特格斯,新泽西州立大学|Methods for increasing toughness of immiscible polymer blends|
    WO2009126592A2|2008-04-07|2009-10-15|Vorbeck Materials Corp.|Fuel system components|
    WO2009143405A2|2008-05-22|2009-11-26|The University Of North Carolina At Chapel Hill|Synthesis of graphene sheets and nanoparticle composites comprising same|
    JPWO2010007763A1|2008-07-15|2012-01-05|パナソニック株式会社|Radio receiver and method for measurement of out-unit band reference signal|
    TW201012749A|2008-08-19|2010-04-01|Univ Rice William M|Methods for preparation of graphene nanoribbons from carbon nanotubes and compositions, thin films and devices derived therefrom|
    KR101074027B1|2009-03-03|2011-10-17|한국과학기술연구원|Graphene composite nanofiber and the preparation method thereof|
    EP2408954A4|2009-03-16|2012-09-05|Ilhan A Aksay|Reinforced polymeric articles|
    CN102612490B|2009-04-03|2016-05-18|沃尔贝克材料有限公司|The polymer composition that contains graphene film and graphite|
    US20110133134A1|2009-06-09|2011-06-09|Vorbeck Materials Corp.|Crosslinkable and Crosslinked Compositions of Olefin Polymers and Graphene Sheets|
    US8652362B2|2009-07-23|2014-02-18|Nanotek Instruments, Inc.|Nano graphene-modified curing agents for thermoset resins|
    KR101090517B1|2009-08-17|2011-12-08|성균관대학교산학협력단|Nanocarbon-polymer composites and method for preparing the same|
    US8299159B2|2009-08-17|2012-10-30|Laird Technologies, Inc.|Highly thermally-conductive moldable thermoplastic composites and compositions|
    IT1396193B1|2009-10-07|2012-11-16|Polimeri Europa Spa|EXPANDABLE THERMOPLASTIC NANOCOMPOSITE POLYMER COMPOSITIONS WITH IMPROVED THERMAL INSULATION CAPACITY.|
    IT1396918B1|2009-11-03|2012-12-20|Polimeri Europa Spa|PROCEDURE FOR THE PREPARATION OF GRAPHENIC NANOPIASTRINES WITH HIGH LEVELABILITY IN LOW POLARITY POLYMER MATRICES AND THEIR POLYMERIC COMPOSITIONS|
    EP2550332B1|2010-03-23|2018-05-16|Solvay SA|Polymer compositions comprising semi-aromatic polyamides and graphene materials|
    US8420042B2|2010-09-21|2013-04-16|High Temperature Physics, Llc|Process for the production of carbon graphenes and other nanomaterials|
    FR2959231B1|2010-04-22|2012-04-20|Arkema France|THERMOPLASTIC AND / OR ELASTOMERIC COMPOSITE MATERIAL BASED ON CARBON NANOTUBES AND GRAPHICS|
    CN101817516A|2010-05-21|2010-09-01|哈尔滨工业大学|Method for preparing graphene or graphene oxide by using high-efficiency and low-cost mechanical stripping|
    KR20120009978A|2010-07-23|2012-02-02|현대자동차주식회사|Manufacturing Method of Polymer Nanocomposite article by using Aligned Carbonnanotube|
    DE102010032885A1|2010-07-30|2012-02-02|Daimler Ag|Fastening device for a fiber-reinforced plastic profile|
    US9187612B2|2010-08-11|2015-11-17|Imerys Graphite & Carbon Switzerland Sa|Ground expanded graphite agglomerates, methods of making, and applications of the same|
    US10377838B2|2010-09-03|2019-08-13|Sekisui Chemical Co., Ltd.|Resin composite material and method for producing resin composite material|
    TW201219447A|2010-10-12|2012-05-16|Solvay|Polymer compositions comprising polys and graphene materials|
    WO2012133303A1|2011-03-30|2012-10-04|積水化学工業株式会社|Resin composite material and process for producing same|
    CN102225759A|2011-04-14|2011-10-26|温州医学院|Low-temperature preparation method of hydroxy-functionalized graphene|
    US8167190B1|2011-05-06|2012-05-01|Lockheed Martin Corporation|Electrically conductive polymer compositions containing metal particles and a graphene and methods for production and use thereof|
    JP5953014B2|2011-07-08|2016-07-13|積水化学工業株式会社|Flame retardant resin composition, flame retardant resin sheet and flame retardant multilayer sheet|
    KR101245815B1|2011-07-14|2013-03-21|국립대학법인 울산과학기술대학교 산학협력단|Edge-functionalized graphite via mechanic-chemical process and Manufacture of Its|
    JP6047569B2|2011-07-21|2016-12-21|インテグリス・インコーポレーテッド|Nanotube and finely pulverized carbon fiber polymer composite composition and production method|
    EP2770013A4|2011-10-18|2015-04-01|Sekisui Chemical Co Ltd|Method for producing resin composite material, and resin composite material|
    JP2013233790A|2012-04-11|2013-11-21|Sekisui Chem Co Ltd|Method for manufacturing resin molded article, and resin molded article|
    CA2885330C|2012-09-28|2020-12-22|Applied Nanostructured Solutions, Llc|Composite materials formed by shear mixing of carbon nanostructures and related methods|
    EP2909028B1|2012-10-19|2019-09-25|Rutgers, the State University of New Jersey|In situ exfoliation method to fabricate a graphene-reinforced polymer matrix composite|
    US10060019B2|2012-11-16|2018-08-28|The Boeing Company|Thermal spray coated reinforced polymer composites|
    GB201304770D0|2013-03-15|2013-05-01|Provost Fellows Foundation Scholars And The Other Members Of Board Of|A scalable process for producing exfoliated defect-free, non-oxidised 2-dimens ional materials in large quantities|
    EP2994308A4|2013-04-18|2016-11-23|Univ Rutgers|In situ exfoliation method to fabricate a graphene-reninf-orced polymer matrix composite|
    ES2534575B1|2013-09-24|2016-01-14|Consejo Superior De Investigaciones Científicas |GRAPHITE EXFOLIATION WITH DEEP EUTETIC SOLVENTS|
    JP7001472B2|2014-07-30|2022-01-19|ラトガース，ザ ステート ユニバーシティ オブ ニュー ジャージー|Graphene reinforced polymer matrix complex|
    CN107250236A|2014-12-22|2017-10-13|瑞来斯实业公司|Graphite in resin is peeled off|
    CN104945659A|2015-06-29|2015-09-30|殷明|Novel CNT surface treatment method and application thereof in preparing polymer/CNT nano composite material|
    US10685763B2|2016-01-19|2020-06-16|Xerox Corporation|Conductive polymer composite|EP2909028B1|2012-10-19|2019-09-25|Rutgers, the State University of New Jersey|In situ exfoliation method to fabricate a graphene-reinforced polymer matrix composite|
    EP2994308A4|2013-04-18|2016-11-23|Univ Rutgers|In situ exfoliation method to fabricate a graphene-reninf-orced polymer matrix composite|
    JP7001472B2|2014-07-30|2022-01-19|ラトガース，ザ ステート ユニバーシティ オブ ニュー ジャージー|Graphene reinforced polymer matrix complex|
    US9518160B2|2015-01-05|2016-12-13|The Boeing Company|Graphene-augmented composite materials|
    US9421739B2|2015-01-05|2016-08-23|The Boeing Company|Graphene aerospace composites|
    US10266677B2|2015-01-05|2019-04-23|The Boeing Company|Graphene-augmented composite materials|
    US10875986B2|2015-01-05|2020-12-29|The Boeing Company|Graphene fiber for aerospace composites|
    US9434826B2|2015-01-05|2016-09-06|The Boeing Company|Graphene-augmented carbon fiber for aerospace composites|
    JP6499450B2|2015-01-07|2019-04-10|株式会社日本触媒|Graphene oxide composite composition|
    WO2016157151A1|2015-04-03|2016-10-06|Milazzo Giovanni|Composite material comprising at least one thermoplastic resin and granular shive from hemp and / or flax|
    US9926427B2|2015-12-10|2018-03-27|Nanotek Instruments, Inc.|Chemical-free production of graphene-reinforced polymer matrix composites|
    KR20190034581A|2016-07-22|2019-04-02|럿거스, 더 스테이트 유니버시티 오브 뉴 저지|In situ bonding to polymers of carbon fibers and nanotubes|
    CN106496712B|2016-09-30|2018-01-23|北京化工大学|A kind of reaction in-situ peels off the method that expanded graphite prepares rubber nano composite material|
    CN106564175B|2016-10-21|2018-11-30|成都新柯力化工科技有限公司|A kind of graphene conductive masterbatch and preparation method thereof|
    KR20190122780A|2017-03-07|2019-10-30|가부시키가이샤 가네카|Styrene-based resin extruded foam and its manufacturing method|
    CN106928448B|2017-04-06|2017-12-15|常州恒利宝纳米新材料科技有限公司|The continuous production equipment and preparation method of a kind of graphene composite material|
    WO2018189670A1|2017-04-11|2018-10-18|Reliance Industries Limited|Process for preparing polymer-graphene composites|
    CN109082048A|2017-06-13|2018-12-25|沙冰娟|A kind of preparation method of the high-heat-conductive composite material based on graphene|
    KR102284847B1|2017-06-26|2021-08-03|항저우 고우시 테크놀로지 컴퍼니 리미티드|Graphene composite material and its manufacturing method|
    CN107501845B|2017-08-25|2020-01-31|天津大学|Preparation of graphene/ABS nano composite material by master batch-ball milling-hot pressing method|
    CN108659390A|2018-05-14|2018-10-16|诸城市福日机械有限公司|A kind of vehicle rear-axle housing plastic rubber material|
    US11136480B2|2018-08-01|2021-10-05|The Boeing Company|Thermal spray plastic coating for edge sealing and fillet sealing|
    CN109021454A|2018-08-17|2018-12-18|于浩淼|A kind of preparation method of bed computer desk high strength panel material|
    CN109233196A|2018-08-20|2019-01-18|苏州宏久航空防热材料科技有限公司|A kind of preparation method of flexible flame retardant foamed material|
    CN109705488A|2018-11-23|2019-05-03|苏州鼎烯聚材纳米科技有限公司|A kind of preparation method of graphene/PVC concentration masterbatch|
    CN109486155B|2018-12-06|2020-10-23|上海长伟锦磁工程塑料有限公司|Graphene modified halogen-free flame-retardant PC/ABS material and preparation method thereof|
    CN110343347B|2019-07-19|2021-09-14|广州特种承压设备检测研究院|Polyvinylidene fluoride SiO2Modified graphene composite material and preparation method thereof|
    WO2021128257A1|2019-12-27|2021-07-01|桐乡市小老板特种塑料制品有限公司|Cured product containing single-layer graphene, single-layer graphene, preparation method therefor, and article containing single-layer graphene|
    WO2021154903A1|2020-01-28|2021-08-05|Rutgers, The State University Of New Jersey|Elastomers enhanced with in situ formation of 2d nanoparticles from layered materials for multifunctional sensors|
    EP3875429A1|2020-03-03|2021-09-08|Avanzare Innovacion Tencologica S.L.|Procedure to produce graphene and graphenic materials|
    CN111393823B|2020-04-22|2021-05-18|福州大学|Gn-PET/PC alloy with excellent mechanical property and preparation method thereof|
    CN113121838A|2021-03-31|2021-07-16|海南大学|Method for preparing MOF/carbon composite material with assistance of atomic layer deposition, obtained product and application|
    法律状态:
    2020-02-04| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-01-19| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/04/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201361813621P| true| 2013-04-18|2013-04-18|
    US61/813,621|2013-04-18|
    PCT/US2014/034624|WO2014172619A1|2013-04-18|2014-04-18|In situ exfoliation method to fabricate a graphene-reninf-orced polymer matrix composite|
    [返回顶部]