WO2013076372A1 - Composites à base de nanocellulose - Google Patents

Composites à base de nanocellulose Download PDF

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Publication number
WO2013076372A1
WO2013076372A1 PCT/FI2012/051159 FI2012051159W WO2013076372A1 WO 2013076372 A1 WO2013076372 A1 WO 2013076372A1 FI 2012051159 W FI2012051159 W FI 2012051159W WO 2013076372 A1 WO2013076372 A1 WO 2013076372A1
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Prior art keywords
cellulose
graphene
graphite
mixture
nanocellulose
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PCT/FI2012/051159
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English (en)
Inventor
Päivi LAAKSONEN
Markus Linder
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Teknologian Tutkimuskeskus Vtt
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Publication of WO2013076372A1 publication Critical patent/WO2013076372A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H11/00—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only
    • D21H11/16—Pulp or paper, comprising cellulose or lignocellulose fibres of natural origin only modified by a particular after-treatment
    • D21H11/18—Highly hydrated, swollen or fibrillatable fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/08—Flakes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
    • D21H21/52—Additives of definite length or shape

Definitions

  • the present invention relates to cellulose based composite materials and their manufacture and use.
  • Dry-strength additives teaches that dry strength is a structural property of the paper web, which is mainly derived from the formation of bonds between fibers as the fiber network forms and dries. The strength of the actual paper depends on the strength of the individual fibers and of the bonds between fibers, on the number of bonds, and on the distribution of the bonds and fibers. Substances called dry- strength additives enhance one or more of these features but not, however, the strength of individual fibers.
  • the strength of the fiber network can also be increased mechanically by more beating or refining, in which case the larger amount of micro-fibrils promotes the formation of bonds between fibers.
  • the strength of paper can be enhanced by altering the fiber composition, for instance, by raising the proportion of long-fiber chemical pulp, by reducing the filler content, or by adding dry-strength additives. Process changes can also boost the strength, for example, by improving the formation, raising the pH, or adding wet pressing. Nevertheless, more refining and beating probably remains the most common way of increasing strength. However, when the negative effects of beating and refining are to be avoided, dry- strength additives remain the practical option.
  • Dry-strength additives are generally water-soluble, hydrophilic polymers, either natural or synthetic.
  • the most prominent commercial products are: starch, vegetable gums, carboxymethyl cellulose and synthetic polymers.
  • WO 2011/059398 Al discloses a nanopaper that has a structure where micro fibrillated cellulose (MFC) and clay form a layered structure arranged substantially parallel to the surface of the paper.
  • the clay particles, or platelets are in the nanometer range and the length of the nanofibres of the MFC is in the micrometer range. Further the clay particles, or platelets, are preferably substantially isolated from each other.
  • the length of the micro fibrillated cellulose nanofibres can be in the range of 5-20 ⁇ and, according to an embodiment, the amount of microfibrillated cellulose is more than 10wt% and also the amount of clay is more than 10wt%.
  • the nanopaper further comprises a water soluble cross-linker, the amount of which is more than 5wt%, based on the total weight of the nanopaper.
  • the cross-linker is either chitosan or hyaluronic acid.
  • a method for preparing the clay-microfibrillated cellulose nano fibre nanopaper comprises:
  • the object of the invention is achieved by preparing the composite material from a mixture containing water and cellulose, and graphite and/or graphene as an additive.
  • the resultant composite material comprises cellulose fibers and/or fibrils and particles of graphite and/or graphene dispersed in the material such that at least a portion of the cellulose fibers and/or fibrils are attached to each other by means of said particles of graphite and/or graphene acting as binder.
  • the use of graphite/graphene particles as binder or strength additive improves adhesion between the cellulose fibers and/or fibrils and therefore also the strength of the composite material.
  • the cellulose fibers themselves are, of course, one of the determining factors as to the strength of the composite, and therefore different fibers compositions give different "basic strength" to the composite.
  • the cellulose used is native cellulose.
  • Native cellulose refers to chemically unmodified cellulose and/or non-oxidized and non- functionalized cellulose.
  • Figures 1A, IB and 1C present nanocellulose films with a graphene/graphite content of 1 wt-%, 5 wt-% and 29 wt-%, respectively;
  • Figure 2 presents a TEM image of a graphene flake embedded in a MFC suspension
  • Figures 3A and 3B present respectively an optical microscope image and a Raman spectrum of a composite surface
  • Figures 4A, 4B, 4C, 4D and 4E present different mechanical properties of composites containing different amounts of graphene
  • FIG. 5 depicts results of measurements in one comparative example
  • Fig. 6A, Fig. 6B and Fig. 6C describe results of another experiment
  • Fig. 7A and Fig. 7B are respective a TEM image and a hexagonal electron diffraction (ED) pattern in a further experiment.
  • ED hexagonal electron diffraction
  • All embodiments include a mixture of cellulose and graphite and/or graphene in some form, and therefore it is useful first to discuss these materials.
  • Graphene is an allotrope of carbon shaped into one-atom-thick planar sheets of carbon atoms bound together into a "chicken wire" -type ring structure.
  • graphene sheets when several graphene sheets are stacked together, they form the crystalline or "flake" form with an interplanar spacing between the graphene sheets of 0.335 nm.
  • graphene is basically one layer of atoms
  • the term graphene is also used to refer to particles that have two or several layers of atoms but still exhibit properties clearly deviating from those of graphite in the application in question.
  • the material when there are several layers of atoms and the relevant properties change, the material is called graphite.
  • Graphene can be produced, for example, by abrasion of graphite, by sonication of graphite, by cutting from nanotubes, or by epitaxial growth on various substrates or by growth from carbon-containing melts.
  • a further alternative that can be utilized is exfoliation, which is easily carried out in large scale. High yields of graphene can also be obtained by burning magnesium metal in dry ice. However, the exfoliation is a simpler alternative for bringing graphene to solution environment.
  • the graphene can also be produced during the present methods from graphite by means of exfoliation, for instance.
  • U.S. Patent Application Publication No. US 2008/0279756 Al discloses a method of exfoliating a layered material (e.g., graphite and graphite oxide) to produce nano-scaled platelets.
  • the method comprises dispersing graphite or graphite oxide particles in a liquid medium containing therein a surfactant or dispersing agent to obtain a suspension or slurry, and exposing the suspension or slurry to ultrasonic waves (ultrasonication) to produce the separated nano-scaled platelets.
  • WO 2010/097517 A2 discloses another method of exfoliating graphene platelets from graphite.
  • the method comprises facilitating exfoliation by treatment with proteins.
  • the proteins adhere to the surface of graphene and then the produced platelets may contain a graphene layer and a protein layer on the surface of the graphene layer.
  • Graphite is naturally found in three types, which are crystalline flake graphite, amorphous graphite, and lump graphite.
  • the preferred type is crystalline flake graphite, due to its particular capability of exfoliating into graphene layers.
  • the cellulose used in the embodiments is intended to include regular cellulose or nanocellulose, or a mixture thereof.
  • cellulose includes all cellulosic materials containing cellulose or nanocellulose, or mixtures thereof, obtained from any cellulose-containing source material, such as wood-based materials, including pulp from softwood or hardwood trees, or plant materials, including agricultural sources, grasses or other non-wood plant materials.
  • the cellulose is generally isolated from these source materials by chemical, mechanical or thermo -mechanical pulping to provide cellulose fibers of a diameter of 15 - 30 um.
  • the cellulose can include other components, such as lignin and hemicelluloses, particularly when the cellulose has been prepared from wood pulp. However, these are present in a total content of less than 50 % by weight of the cellulose or cellulose mixture.
  • the used cellulose has undergone at least one treatment stage to remove such other components. Chemical reactions affecting the other components such as removal of hemicellulose or lignin may be carried out. However, any treatment stages are preferably selected from those leaving the surface of the cellulose unmodified, i.e. leaving the functional groups on said surface intact. The resulting cellulose is referred to as chemically unmodified cellulose.
  • no oxidation of the cellulose is carried out, and no reactive functional groups are added to the surface of the cellulose.
  • the resulting cellulose is referred to as non-oxidized and non-functionalized cellulose. This is due to the fact that no additional reactivity is required, since the method according the embodiments will function well based on pure hydrophobic interactions.
  • native cellulose refers to cellulose that fulfils both of the above requirements, i.e. that the cellulose is chemically unmodified, non-oxidized and non-functionalized. However, native cellulose does not preclude other treatments such as fibrillation and pulping. Thus, native cellulose can also nanofibrillated cellulose (NFC) or micro fibrillated cellulose (MFC).
  • NFC nanofibrillated cellulose
  • MFC micro fibrillated cellulose
  • nanocellulose is intended to mean fine cellulose fibers, nanofibrillated cellulose (NFC) or microfibrillated cellulose (MFC), and refers to any cellulose fibers with an average diameter of ⁇ 10 ⁇ , preferably 5 nm - 1 ⁇ , which consist of, fibrils 5 - 200 nm in diameter.
  • NFC nanofibrillated cellulose
  • MFC microfibrillated cellulose
  • cellulose fibers with an average diameter of ⁇ 10 ⁇ , preferably 5 nm - 1 ⁇ , which consist of, fibrils 5 - 200 nm in diameter.
  • the use of the separated fibrils is preferred.
  • partial flocculation generally occurs, providing also a portion of larger bundles.
  • Common to such cellulose fibers is that they have a high specific surface area, resulting in a high contact area between the fibrils in the product, such as the mixture of cellulose and nanocellulose.
  • the specific area of the nanocellulose used according to an embodiment is preferably at least 15
  • nanocellulose is prepared by isolating the nano- or micro-sized fibrils from cellulose fibers using homogenizers, such as refiners or fibrillators.
  • the raw-material can be bleached or unbleached cellulose, preferably unbleached cellulose obtained by chemical pulping.
  • nanocellulose produced partly or entirely by bacterial processes can be used (bacterial cellulose).
  • nanocellulose is cellulose that is native cellulose as defined above. Therefore, according to an embodiment, the cellulose, or at least a portion of the cellulose, is native nanocellulose.
  • WO 2011/059398 Al One method that can be used to prepare nanocellulose is described in WO 2011/059398 Al that has already been discussed above. Other processes for the manufacture of nanocellulose are disclosed in US 2007/0207692, WO 2007/91942 and US 7381294.
  • the method of preparing a composite material comprises preparing a mixture that contains water, cellulose and additives.
  • the additives contain at least graphite and/or graphene as an additive that strengthens adhesion between the cellulose fibrils. Also other additives can be used but are not required according to the embodiments. After the preparation of the mixture, a sufficient amount of water is removed so that a solid composite material is formed.
  • the formed mixture can contain, for example (wt% of the dry matter): cellulose 50-99.995 wt%, such as 75-99.5 wt%; graphene and graphite (in total) 0.005-50 wt%, for example 0.005-10 wt%, such as 0.1-5 wt%,; other dry-matter constituents 0-49,995 wt%, such as 0.1-20 wt%; and sufficient amount of water.
  • cellulose 50-99.995 wt% such as 75-99.5 wt%
  • other dry-matter constituents 0-49,995 wt% such as 0.1-20 wt%
  • sufficient amount of water for example (wt% of the dry matter): cellulose 50-99.995 wt%, such as 75-99.5 wt%; graphene and graphite (in
  • the mixture is homogenized, for example by a pressure homogenizer, fluidizer or rotor-stator mixer. Also sonication can be used.
  • at least a portion of the cellulose comprises nanocellulose.
  • the portion of the nanosellulose can be 0-100 wt%, such as 10-100 wt% (of the total weight of the cellulose).
  • the weight of the graphite and graphene is 0.005-10 %, such as 0.1-5 %, for example 0.2-4 %, of the weight of the cellulose.
  • the weight of the graphite and graphene refers here to the total combined weight of these ingredients i.e. the sum of the weights of graphite and graphene.
  • the graphene/graphite is originally added into the mixture in the form of graphite powder. Then, the relative portions of the graphite can be very high in the beginning but decrease during the manufacture as part of the graphite disintegrates as graphene. In the final product, the relative portion of the graphene can thus be higher. In other words, the relative portions of the graphite and graphene can vary during the manufacture, at least in embodiments that apply sonication or promote exfoliation in the mixture itself.
  • the relative weight portion of graphene/graphite in the final product is for example 5/95 - 95/5, particularly 20/80 - 80/20.
  • the graphene/graphite mostly, or at least partly, in the form of small platelets, such as platelets having thicknesses in the order of nanometres, or at the most few micrometers.
  • the portion of platelets having their thickness less than 100 nm can be, for example at least 5 %, such as at least 15 % or at least 50 % of the total weight of the graphene/graphite.
  • the thickness of less than 100 nm referred to above is replaced by a thickness of less than 10 nm.
  • the method comprises first preparing the mixture containing water, cellulose and graphite powder and then sonicating the mixture to effect exfoliation of graphene from surfaces of particles of graphite powder.
  • the method comprises applying the mixture on a surface and allowing to dry, wherein the composite forms a coating on the surface. Drying may also be facilitated by filtration, hot-pressing or warming the film otherwise.
  • the method comprises forming the mixture into a pulp and removing the water in a paper-making process, wherein the composite is a wood- based fiber product.
  • a composite material is formed that comprises cellulose fibers and particles of graphite and/or graphene dispersed in the material.
  • a special characteristic of the material is that at least a portion of the cellulose fibers are attached to each other such that said particles of graphite and/or graphene are used as binder.
  • the particles of graphite and/or graphene makes the adhesion between the cellulose fibers stronger and therefore the resultant composite material is stronger and stiffer than without the graphite/graphene binder.
  • At least a portion of the cellulose fibers in the composite material are nanocellulose fibrils.
  • the portion of the nanocellulose fibers from the cellulose fibers in the composite material is between 0.1-100 %, such as 1-100%, for example 5- 100 % in weight.
  • the weight of the graphite and graphene is 0.005-10 %, such as 0.1-5 %, for example 0.2-4 %, of the weight of the cellulose in the composite material.
  • the composite material is used in the form of a coating.
  • a new kind of a coating can be provided that has the properties described above.
  • the composite material is used to make a package. Then, the package is made of, or comprises as a part thereof, the composite material that has the properties described above.
  • the composite material is used in construction elements.
  • the construction element is made of, or comprises as a part thereof, the composite material that has the properties described above.
  • a paper product that is made of, or comprises as a part thereof, the composite material that has the properties described above.
  • the products according to the embodiments are applicable not only as separate composite structures and products but also as coatings on surfaces and reinforcing layers or parts in different kinds of products that also comprise other materials. Therefore, also the mixture itself has individual utility. Therefore, according to an embodiment, there is provided a mixture for making a composite material or a coating.
  • the mixture comprises water, cellulose and particles of graphite and/or graphene such that the weight of the graphite and graphene is 0.005-10 %, such as 0.1-5 %, for example 0.2-4 %, of the weight of the cellulose.
  • At least a portion of the cellulose in the mixture comprises nanocellulose.
  • the portion of the nanocellulose fibrils from the cellulose fibers is between 0.1-100 %, such as 1-100%, for example 5- 100 % in weight.
  • the graphene/graphite in the mixture is in the form of substantially planar flakes, sometimes called also as platelets.
  • the planar graphene/graphite flakes or platelets have thicknesses less than 1 ⁇ , preferably less than 100 nm, such as less than 10 nm.
  • the portion of such platelets having their thickness separately within each of the above ranges can be, for example at least 5 %, such as at least 15 % or at least 50 % of the total weight of the graphene/graphite.
  • the cellulose used in the above methods, products and mixtures is chemically unmodified cellulose.
  • the cellulose used in the above methods, products and mixtures is non-oxidized and non-functionalized cellulose. According to a further embodiment, the cellulose used in the above methods, products and mixtures is chemically unmodified nanocellulose.
  • the cellulose used in the above methods, products and mixtures is non-oxidized and non-functionalized nanocellulose. According to an embodiment, at least 50 wt-% of the cellulose used in the above methods, products and mixtures is chemically unmodified cellulose.
  • At least 50 wt-% of the cellulose the cellulose used in the above methods, products and mixtures is non-oxidized and non-functionalized cellulose.
  • At least 50 wt-% of the cellulose used in the above methods, products and mixtures is chemically unmodified nanocellulose.
  • At least 50 wt-% of the cellulose used in the above methods, products and mixtures is non-oxidized and non-functionalized nanocellulose.
  • Nanocellulose in this example microfibrillated cellulose (MFC), was obtained from UPM-Kymmene Corporation as a dilute hydrogel (solids content 1.9 %).
  • the sample was prepared by mechanical disintegration of bleached birch pulp by ten passes through a M7115 Fluidizer (Micro fluidics M. Paakko, M. Ankerfors, H. Kosonen, A. Nykanen, S. Ahola, M. Osterberg, J. Ruokolainen, J. Laine, P. T. Larsson, O. Ikkala, T. Lindstrom, Biomacromolecules 2007 8, 1934-1941 Corp.) according to previous reports.
  • Composite preparation Micro fluidics M. Paakko, M. Ankerfors, H. Kosonen, A. Nykanen, S. Ahola, M. Osterberg, J. Ruokolainen, J. Laine, P. T. Larsson, O. Ikkala, T. Lindstrom, Biomacromolecule
  • Fig. 1A shows a MFC/graphene film containing 1 wt-% of graphene/graphite
  • Fig. IB shows a corresponding film with 5 wt- % graphene/graphite content
  • Fig. 1C the graphene/graphite content is 29 wt-%.
  • TEM Transmission electron microscopy
  • Fig. 3 A is an optical microscope image from a composite surface. The size of the red rectangle is 10 ⁇ x 10 ⁇ .
  • Fig. 3B is a Raman spectrum showing the characteristic bands of a few layered graphene flake, deviating from those of bulk graphite, measured at the indicated spot.
  • Fig. 4A shows Young's moduli of the specimens with different graphene/graphite contents.
  • the graphene/graphite contents of the specimens are expressed as the ratio of the weight of graphene/graphite to the weight of the cellulose.
  • the measured Young's moduli are shown at contents of 0.00 %, 0.63 %, 1.25 %, 2.50 %, 5 %, 25 % and 50 %. Based on this example, it appears that best improvements in Young's modulus can be attained at graphene/graphite contents between approximately 0.7-3 %, more particularly between 0.8-2 % and especially at about or exactly 1.25 %, when using nanocellulose and graphene/graphite as prepared above.
  • Fig. 4A shows Young's moduli of the specimens with different graphene/graphite contents.
  • the graphene/graphite contents of the specimens are expressed as the ratio of the weight of graphene/graphite to the weight of the cellulose.
  • FIG. 4B shows ultimate tensile strengths of the specimens with different graphene/graphite contents corresponding to those of Fig. 4A. Based on this example, it appears that best improvements in the ultimate tensile strength can be attained at graphene/graphite contents between approximately 1-2 %, and especially at about or exactly 1.25 %, when using nanocellulose and graphene/graphite as prepared above.
  • Fig. 4C shows ultimate strains of the specimens with different graphene/graphite contents corresponding to those of Fig. 4A. This example indicates that, even though the strength increased, the ultimate strain did not substantially decrease when using nanocellulose and graphene/graphite as prepared above.
  • Fig. 4D shows works of fracture of the specimens with different graphene/graphite contents corresponding to those of Fig. 4A. Based on this example, it appears that best improvements in the work of fracture can be attained at graphene/graphite contents between approximately 1-2 %, and especially at about or exactly 1.25 %, when using nanocellulose and graphene/graphite as prepared above.
  • Fig. 4C shows ultimate strains of the specimens with different graphene/graphite contents corresponding to those of Fig. 4A. This example indicates that, even though the strength increased, the ultimate strain did not substantially decrease when using nanocellulose and graphene/graphite as prepared above.
  • Fig. 4D shows works of fracture of the specimens with different graph
  • FIG. 4E shows yield strengths of the specimens with different graphene/graphite contents corresponding to those of Fig. 4A. Based on this example, it appears that best improvements in the yield strength can be attained at graphene/graphite contents between approximately 1-2 %, and especially at about or exactly 1.25 %, when using nanocellulose and graphene/graphite as prepared above.
  • Fig. 5 depicts measurements of a nanocellulose film without graphene and a film containing 2.5 w-% of graphene.
  • Fig. 5 shows reinforcement of nanocellulose film (grey) by addition of graphene (black). Stiffness and strength of the material increases significantly by the addition of graphene.
  • the particularly preferred graphene/graphite contents are those between 1-2 %, more specifically between 1.0-2.0
  • the optimal range is related to the several factors, such as size and shape of the graphene/graphite flakes and the quality of the cellulose.
  • the weight of the graphite and graphene can be 0.005-10 %, such as 0.1-5 %, for example 0.2-4 %, of the weight of the cellulose.
  • the ranges 1.0-2.0 %, 1.0-1.5 % and 1.1-1.3 % can be used at least as starting points.
  • Fig. 6A, Fig. 6B and Fig. 6C describe results of another experiment.
  • exfoliation of graphene was observed as appearance of brown colour to the nanocellulose/graphene dispersions after exfoliation. This was followed by measuring transmission of light by the solutions.
  • the results are shown in Fig. 6A.
  • the energy used in the sonication varied from 1.65 to 33 kJ (from top to bottom curve).
  • NFC concentration was 2mg/ml and initial amount of graphite 0.4 mg/ml.
  • the solutions were diluted ten times before measurement.
  • Fig. 6B shows the corresponding transmission values at 660 nm as a function of the exfoliation energy.
  • Fig. 6C is a picture of the graphene/NFC solution after 33 kJ exfoliation. The solution was diluted ten times.
  • Fig. 7A is a TEM image of the solution containing graphene flakes in the nanocellulose matrix.
  • Fig. 7B shows a hexagonal electron diffraction (ED) pattern measured from the graphene flake. The pattern indicates to a crystalline few-layer graphene flake.
  • ED hexagonal electron diffraction

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des matériaux composites qui comprennent des fibres de cellulose. Le raccordement des fibres de cellulose entre elles est renforcé au moyen de particules de graphite et/ou de graphène agissant comme liant. Le matériau composite est préparé à partir d'un mélange contenant de l'eau et de la cellulose, et de graphite et/ou de graphène comme additif.
PCT/FI2012/051159 2011-11-24 2012-11-23 Composites à base de nanocellulose WO2013076372A1 (fr)

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CN109896522A (zh) * 2017-12-11 2019-06-18 山东省圣泉生物质石墨烯研究院 一种石墨烯复合纳米纤维素、制备方法和用途
WO2019157301A1 (fr) * 2018-02-09 2019-08-15 University Of Maryland, College Park Matériaux en graphite et leurs procédés de fabrication et d'utilisation
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US10729988B2 (en) 2016-08-02 2020-08-04 Washington University Bilayered structures for solar steam generation
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EP3872172A1 (fr) * 2020-02-28 2021-09-01 CIC nanoGUNE - Asociación Centro de Investigación Cooperativa en Nanociencias Matériaux composites de cellulose conductrice et leurs utilisations
EP3872173A1 (fr) * 2020-02-28 2021-09-01 CIC nanoGUNE - Asociación Centro de Investigación Cooperativa en Nanociencias Procédé de production de nanocellulose cristalline
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CN104910398A (zh) * 2014-03-12 2015-09-16 中国科学院金属研究所 以纳米纤维素辅助制备高含量石墨烯柔性导电复合膜方法
CN105218841A (zh) * 2014-07-02 2016-01-06 中国科学院金属研究所 一种由石墨到复合石墨烯纸的简易制备方法
CN105218841B (zh) * 2014-07-02 2019-03-01 中国科学院金属研究所 一种由石墨到复合石墨烯纸的简易制备方法
US10396328B2 (en) 2014-11-06 2019-08-27 Teknologian Tutkimuskeskus Vtt Oy Cellulose based functional composites, energy storage devices and manufacturing methods thereof
CN104477878A (zh) * 2014-12-04 2015-04-01 中国科学院山西煤炭化学研究所 一种石墨烯基多级孔炭材料及制法和应用
KR101751349B1 (ko) 2015-03-03 2017-06-27 한국원자력연구원 방향족 화합물을 포함하는 나노셀룰로오스 제조 및 이를 통한 유무기 복합체 제조방법
WO2017092778A1 (fr) * 2015-11-30 2017-06-08 Knauf Gips Kg Produits de construction comprenant du graphène ou de l'oxyde de graphène dans le matériau en vrac et procédé de production de tels produits de construction
JP2019502619A (ja) * 2015-11-30 2019-01-31 クナーフ ギプス カーゲーＫｎａｕｆ Ｇｉｐｓ Ｋｇ バルク材料にグラフェン又は酸化グラフェンを含む建材製品、及び、このような建材製品の製造方法
US10836679B2 (en) 2015-11-30 2020-11-17 Knauf Gips Kg Building products comprising graphene or graphene oxide in the bulk material and method for producing such building products
US10729988B2 (en) 2016-08-02 2020-08-04 Washington University Bilayered structures for solar steam generation
US10744461B2 (en) 2016-08-02 2020-08-18 Washington University Ultrafiltration membrane based on bacterial nanocellulose and graphene oxide
CN109896522A (zh) * 2017-12-11 2019-06-18 山东省圣泉生物质石墨烯研究院 一种石墨烯复合纳米纤维素、制备方法和用途
WO2019157301A1 (fr) * 2018-02-09 2019-08-15 University Of Maryland, College Park Matériaux en graphite et leurs procédés de fabrication et d'utilisation
US20210078864A1 (en) * 2018-02-09 2021-03-18 University Of Maryland, College Park Graphite materials, and methods for fabricating and use thereof
US12060274B2 (en) 2018-02-09 2024-08-13 University Of Maryland, College Park Graphite materials, and methods for fabricating and use thereof
EP3872172A1 (fr) * 2020-02-28 2021-09-01 CIC nanoGUNE - Asociación Centro de Investigación Cooperativa en Nanociencias Matériaux composites de cellulose conductrice et leurs utilisations
EP3872173A1 (fr) * 2020-02-28 2021-09-01 CIC nanoGUNE - Asociación Centro de Investigación Cooperativa en Nanociencias Procédé de production de nanocellulose cristalline
WO2021170789A1 (fr) * 2020-02-28 2021-09-02 Asociación Centro De Investigación Cooperativa En Nanociencias “Cic Nanogune” Procédé de production de nanocellulose cristalline
WO2021170770A1 (fr) * 2020-02-28 2021-09-02 Asociación Centro De Investigación Cooperativa En Nanociencias “Cic Nanogune” Matériaux composites à base de cellulose conductrice et leurs utilisations
WO2021255068A1 (fr) 2020-06-17 2021-12-23 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. Procédé de production d'un matériau composite contenant de la cellulose
CN114181413A (zh) * 2021-12-20 2022-03-15 上海交通大学 一种纳米纤维素/膨胀石墨复合薄膜及其制备方法

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