WO2014130687A1 - Procédé de modification du nitrure de bore, et utilisation du nitrure de bore modifié - Google Patents

Procédé de modification du nitrure de bore, et utilisation du nitrure de bore modifié Download PDF

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WO2014130687A1
WO2014130687A1 PCT/US2014/017420 US2014017420W WO2014130687A1 WO 2014130687 A1 WO2014130687 A1 WO 2014130687A1 US 2014017420 W US2014017420 W US 2014017420W WO 2014130687 A1 WO2014130687 A1 WO 2014130687A1
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boron nitride
nitride material
hbn
sheets
present disclosure
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Douglas H. Adamson
Zhenhua Cui
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University Of Connecticut
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0648—After-treatment, e.g. grinding, purification
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    • 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
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    • C08K3/38—Boron-containing compounds
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/77—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by unit-cell parameters, atom positions or structure diagrams
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
    • C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
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    • C01P2006/37—Stability against thermal decomposition
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron

Definitions

  • the present disclosure relates to systems and methods of functionalizing and exfoliating boron nitride (BN) and using same and, more particularly, to methods for functionalizing and exfoliating hexagonal boron nitride (hBN) and using same in filler materials (e.g., polymer-based filler materials).
  • BN boron nitride
  • hBN hexagonal boron nitride
  • filler materials e.g., polymer-based filler materials
  • Hexagonal boron nitride is a thermally stable material with uses ranging from cosmetics to high temperature lubricants. BN does not occur naturally, but is manufactured industrially at high temperatures from boron sources such as boron oxide or boric acid and nitrogen sources such as melamine, urea, or ammonia. In some ways hBN resembles graphite; both consist of stacked sheets with the component atoms arranged in a honeycomb pattern, the boron/nitrogen pair of atoms is isoelectric to a pair of atoms in graphite, and both are good thermal conductors.
  • the cubic form of boron nitride (cBN) is analogous to diamond, both in structure and hardness, with the hardness of cBN second only to diamond.
  • hBN is an electrical insulator with a band gap of about 5.2 eV. It also has a much higher thermal stability than graphite, with a melting temperature near 3,000°C. In addition, hBN has been shown to be a superior substrate to silicon for graphene- based electrical devices. Despite these advantageous properties, the number of reports of hBN composites is small compared to graphite. Recent reviews of the field describe examples of solvent based sonication techniques, successful for graphite exfoliation, capable of generating partially exfoliated hBN at mg/ml concentrations.
  • the present disclosure provides advantageous systems and methods of modifying (e.g., functionalizing and exfoliating) boron nitride, and improved methods/systems for using the same. More particularly, the present disclosure provides improved systems and methods for modifying hexagonal boron nitride and using same in filler materials (e.g., polymer-based filler materials). In general, the present disclosure is directed to the preparation and use of boron nitride materials. In certain embodiments, the present disclosure provides for the preparation and/or use of boron nitride based polymer fillers.
  • the present disclosure provides systems and methods for exfoliating hexagonal boron nitride (hBN) for use as a filler (e.g., as a nanofiller) in polymer composites.
  • hBN hexagonal boron nitride
  • This non-flammable, transparent, high surface area material of the present disclosure can advantageously be utilized as a flame retardant.
  • the improved boron nitride materials (e.g., polymer composites including hexagonal boron nitride) of the present disclosure can be utilized for a range of applications, as discussed further below.
  • the present disclosure provides for the functionalization of BN for application as a composite component.
  • Hexagonal BN has similar structural properties of graphite, a known lubricant.
  • BN is an electrical insulator and is also an excellent thermal conductor. BN is useful in making flame retardant polymer composites and coatings. In general, a range of other fillers have been used for flame protection in plastics. These can include, for example, inorganic salts, fluoropolymers, and halogenated hydrocarbons.
  • the boron nitride filler disclosed herein provide unique and useful properties.
  • the high aspect ratio of the atomically thin sheets provides for very efficient use of the filler in a polymer.
  • the material is non-toxic.
  • the disclosed material is transparent and so can be used in applications such as, for example, aircraft windows.
  • the material has a temperature stability that is nearly double that of other known fillers.
  • Disclosed herein is a unique and highly advantageous process/method that successfully produces functionalized and exfoliated boron nitride.
  • the method includes a controlled thermal treatment step to partially oxidize the boron nitride material.
  • a subsequent step includes water washing of the material, as discussed further below in connection with the thermal gravimetric analysis data for the partial decomposition of BN in air, nitrogen and argon.
  • the method produces atomically thin sheets of BN with lateral dimensions of several hundred
  • the present disclosure provides for a method for modifying boron nitride including: a) providing a boron nitride material; b) thermally treating the boron nitride material under controlled conditions to partially oxidize the boron nitride material; c) water washing the partially oxidized boron nitride material; and d) allowing the boron nitride material to dry.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), the boron nitride material includes boron nitride oxide.
  • the present disclosure also provides for a method for modifying boron nitride wherein step b) includes thermally treating the boron nitride material at about 950°C to about 1000°C in air for a predetermined period of time.
  • the present disclosure also provides for a method for modifying boron nitride wherein step a) includes providing a hexagonal boron nitride material.
  • step a) includes providing a hexagonal boron nitride material.
  • step d includes providing a hexagonal boron nitride material.
  • step d includes thermally treating the boron nitride material at about 950°C to about 1000°C in air and holding at that temperature for about one hour.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), the boron nitride material includes a plurality of single sheets of boron nitride material, and one or more sheets extend about 150 nm in their lateral dimension.
  • the present disclosure also provides for a method for modifying boron nitride wherein the plurality of single sheets of the boron nitride material are water dispersible.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), the dried boron nitride material is reacted with phenyl isocyanate.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), the boron nitride material is incorporated covalently into a polymer composite material.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), the boron nitride material is utilized as a filler in a polymer composite material.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), the boron nitride material is utilized in combination with graphene sheets to form a substrate material.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), the boron nitride material is utilized as a flame retardant in a polymer composite material.
  • the present disclosure also provides for a method for modifying boron nitride wherein the polymer composite material includes polycarbonate.
  • the present disclosure also provides for a method for modifying boron nitride wherein after step d), a polymer is grafted or attached to the boron nitride material.
  • the present disclosure also provides for a method for modifying boron nitride wherein the polymer is poly(methyl methacrylate) or polyurethane.
  • the present disclosure also provides for a method for modifying boron nitride wherein the polymer composite material includes a material selected from the group consisting of poly(methyl methacrylate), polyurethane, polycarbonate and nylon.
  • the present disclosure also provides for a method for modifying boron nitride wherein one or more sheets have a sheet thickness of about 0.69 nm.
  • the present disclosure also provides for a method for modifying boron nitride wherein step d) includes spray-drying the boron nitride material.
  • the present disclosure also provides for a method for fabricating a filler material for a composite including: a) providing a hexagonal boron nitride material; b) thermally treating the hexagonal boron nitride material at about 900°C to about 1000°C in air for a
  • the present disclosure also provides for a method for fabricating a filler material for a composite including: a) providing a boron nitride material; b) thermally treating the boron nitride material under controlled conditions in air for a predetermined period of time; c) water washing the thermally treated boron nitride material; d) allowing the boron nitride material to dry; e) reacting the dried boron nitride material with phenyl isocyanate; and f) utilizing the boron nitride material as a filler in a polymer composite material.
  • Figure 2 shows FTIR spectra of BN after different treatments.
  • the top line is pristine BN with no heat treatment.
  • the other lines are BN heated to about 1000°C in air and held at that temperature for increasing amounts of time.
  • the second line from the top is BN held for less than about one minute.
  • the third line from the top is BN held at temperature for about one hour.
  • the fourth line from the top is BN held for about 3 hours 10 minutes.
  • the fifth line from the top (the bottom line) is BN held for about six hours.
  • the formation of B-0 bonds are observed as peaks arising at about 640 cm "1 .
  • the peaks occurring at about 3200 cm "1 arise from O-H stretching;
  • Figure 3 shows TGA traces of BN heated at different temperatures in air.
  • FIGS. 4A and 4B are AFM images of BN exfoliated flakes. These flakes were imaged by spin coating a suspension of BN in the water used to wash the flakes after heat treatment.
  • FIG. 4A is a 5 ⁇ by 5 ⁇ image
  • FIG. 4B is a 2 ⁇ by 2 ⁇ image.
  • the sheets are shown to be single sheets approximately 150 nm in lateral dimension;
  • FIGS. 5A-F show FESEM images of BN at different stages of the exfoliation process. After heat and water treatment, the material imaged is a minority component.
  • FIG. 5A is the pristine hexagonal BN.
  • FIGS. 5B and 5C show the oxidized BN before washing.
  • FIG. 5D is the BN after washing, and
  • FIGS. 5E and 5F is the BN suspended in the aqueous wash.
  • the scale bars in each frame denote a length of 1 micron;
  • FIGS. 6A-D are FESEM images of oxidized BN before and after reaction with an isocyanate.
  • FIGS. 6A and 6B are oxidized BN after reaction with isocyanate,
  • FIGS. 6C and 6D are after sonication and dispersion in THF;
  • Figure 7 shows XRD traces of BN.
  • the upper trace at 0.3 is pristine BN, the other lines are after oxidation.
  • the insert shows a zoom- in view of two lower lines: the rounded peak is oxidized BN after reaction with the isocyanate;
  • Figure 8 shows a top row that is PC control sample with no BNO. From left to right (top row) is immediately after lighting, 3 seconds after lighting, and 8 seconds after lighting. The bottom row is PC containing about 1% BNO. From left to right (bottom row) is immediately after lighting, 3 seconds after lighting, and 8 seconds after lighting.
  • the images are frame captures from video;
  • Figure 9 is a schematic diagram of a procedure of exfoliation and functionalization of BNNS, and using them as fillers;
  • Figure 10 displays an exemplary mechanism of oxidation of hBN
  • Figure 11 displays a structure of boric acid and hydroxide groups on fBNNS
  • Figure 12 shows an exemplary functionalization of BNO by phenyl isocyanate
  • Figure 13 displays FTIR of pBN (second line from bottom at 3400), BNO (top line at 3400), hot water washed BNO (second line from top at 3400), and isocyanate fBNO (bottom line at 3400);
  • Figure 14 is an image showing filtration samples
  • Figures 15A-C are images showing: A) Unfunctionalized hBN in water, B) functionalized and exfoliated hBN in water, and C) AFM image of oxidized and exfoliated hBN sheets;
  • Figures 16A-D show an analysis of hydroxylated hBN: A) FTIR traces of hBN at different stages of preparation: a. pristine hBN before heating, b. hBN after heating but before being placed in water, c. BNO after washing with water, and d.
  • BNO that has been washed by water and reacted with phenyl isocyanate
  • Figures 17A-D show FESEM images of hBN: A) pristine hBN, B) BNO precipitate after washing with water, C) image of BNO nanosheets from water suspension, and D) BNO precipitate after reaction with phenylisocyanate with the curling of the edges consistent with the XRD data in FIG. 16C;
  • Figure 18 shows an exemplary structure of hydroxylated hexagonal boron nitride
  • Figure 19 shows a height histogram of FIG. 15C
  • Figures 20A-D show TEM images of: (a) BNO sheets from water suspension, (b) lower magnification of BNO sheets, (c) BNO precipitate after addition of thermally treated sample to water with voids on the surface (marked by arrows), and (d) selected area
  • Figure 21 shows Raman spectra of pristine hBN and hydroxylated BNO nanosheets
  • Figure 22 shows DLS result of hydroxylated BNO nanosheets water suspension
  • Figure 23 shows FTIR of oxidation product (BNO without any treatment) of different reaction times.
  • Figure 24 shows TGA traces of oxidation at 800°C, 900°C, 1000°C.
  • exemplary embodiments disclosed herein are illustrative of advantageous boron nitride materials, and systems of the present disclosure and methods/techniques thereof. It should be understood, however, that the disclosed embodiments are merely exemplary of the present disclosure, which may be embodied in various forms. Therefore, details disclosed herein with reference to exemplary boron nitride materials/fabrication methods and associated processes/techniques of assembly and use are not to be interpreted as limiting, but merely as the basis for teaching one skilled in the art how to make and use the advantageous boron nitride materials/systems and/or alternative materials of the present disclosure.
  • the present disclosure is directed to the preparation and use of boron nitride materials.
  • the present disclosure provides improved systems and methods of modifying (e.g., functionalizing and/or exfoliating) boron nitride, and related
  • the present disclosure provides advantageous systems and methods for modifying hexagonal boron nitride, and using the same in filler materials (e.g., polymer-based filler materials).
  • filler materials e.g., polymer-based filler materials
  • the present disclosure provides systems and methods for exfoliating hexagonal boron nitride for use as a filler (e.g., nanofiller) in polymer composites. It has been found that this non-flammable, transparent, high surface area material of the present disclosure can advantageously be utilized as a flame retardant. Moreover, the improved boron nitride materials (e.g., polymer composites including hexagonal boron nitride) of the present disclosure can be utilized for a wide range of applications. In certain embodiments, the present disclosure provides for the functionalization of boron nitride (e.g., for use as a composite component).
  • a filler e.g., nanofiller
  • the disclosed method is scalable for production of the BN sheets. Also disclosed are methods of compounding BN sheets with various selected polymers to produce BN-polymer composites having desirable properties (e.g., with respect to dispersion and flame retardancy).
  • Exfoliated BN nanosheets produced by the disclosed process have a higher aspect ratio than is achievable by other methods.
  • the process produces a signature on the material through the OH groups on the perimeter of the nanosheets.
  • BN nanosheets with their high aspect ratio have advantages over the lower aspect ratio BN produced by other methods.
  • the present disclosure provides for improved systems and methods for modifying (e.g., functionalizing and/or exfoliating) boron nitride that includes the steps of heating in air, followed by exfoliation in water, thereby providing a significant commercial, manufacturing and/or operational advantage as a result.
  • modifying e.g., functionalizing and/or exfoliating
  • boron nitride that includes the steps of heating in air, followed by exfoliation in water, thereby providing a significant commercial, manufacturing and/or operational advantage as a result.
  • hexagonal boron nitride sheets were placed in a quartz tube in a tube furnace. The furnace was then heated to 1000°C, held at that temperature for half an hour in air, then the furnace was turned off and the tube was allowed to cool. The thermally treated boron nitride was then washed with water and dried. The reaction that occurred upon heating the boron nitride, followed by treatment with water, resulted in functionalized sheets of BN.
  • thermogravimetric analysis it has been shown that there was a weight gain of boron nitride when it was heated in air, in contrast to a weight loss when it was heated in nitrogen. There was no change in weight when BN was heated in argon.
  • FIG. 1 shows the TGA traces.
  • FIG. 2 shows the results. What can be seen is that the BN stayed largely intact, but there was an additional peak.
  • the top line of FIG. 2 is BN as received, e.g., before heat treatment.
  • the other lines of FIG. 2 are BN after being heated for increasing amounts of time in air.
  • the oxidation of the BN was shown to result in the formation of B-0 and O-H bonds that increase in density with increasing oxidation time, leveling off after several hours.
  • FIG. 3 shows the results. Heating at 800°C or less produced no observable oxidation. Heating at 900°C showed some oxidation, with heating at 1000°C being needed for extensive oxidation. For comparison, also included in FIG. 3 is a trace of BN heated at 1000°C in nitrogen, where substantially no oxidation occurs.
  • FIG. 5 shows field emission scanning electron microscopy (FESEM) images of this residue. Holes can be seen in these larger sheets that correlate with sizes of the exfoliated BN seen by AFM. It is also possible to see that the initially smooth edges of the BN have become rough.
  • FESEM field emission scanning electron microscopy
  • the oxygen functional groups react to form B-O-H groups at the edges of the BN. This leads to the larger BN flakes being reduced in size.
  • the smaller BN sheets are water dispersible leading to exfoliation of the sheets as the introduced hydroxyl groups interfere with stacking.
  • the oxidized BN is reacted with phenyl isocyanate.
  • the larger oxidized BN samples were collected by filtration and reacted with phenyl isocyanate.
  • FIG. 6 shows the change in morphology caused by this functionalization.
  • FIG. 7 shows the effect the reaction has on the stacking of the oxidized BN.
  • X-ray diffraction (XRD) indicates that BN stacking is affected by the reaction with the isocyanate.
  • BN prepared by the method disclosed herein is novel in that it can be functionalized with organic molecules. The method disclosed herein provides material having properties such that the BN sheets may be incorporated covalently into polymer composites.
  • exfoliated BN produced by the process disclosed herein, flame resistance has been demonstrated in an exemplary BN polymer composite.
  • a polycarbonate (PC) sample was blended with 1% of oxidized boron nitride (BNO). As illustrated in FIG. 8, when ignited, a control sample of PC burns until entirely consumed. Due to the relatively small amounts of BNO sample, tests were run using small test samples. These small samples are demanding in flame retardant tests as their large surface areas make the samples extremely flammable. Nevertheless, a sample of the same size as a control sample, but which comprised 1% BNO, extinguished quickly upon lighting and would not relight. The above-described tests were conducted with five commercial samples of BN purchased from Saint-Gobain Advanced Ceramics.
  • BN nanosheets The exfoliated hexagonal BN produced by the method disclosed herein, also referred to as BN nanosheets (BNNS), is highly functionalized and chemically reactive. By using such nanosheets as fillers, hybrid composites are prepared that have excellent mechanical, thermal and surface properties.
  • BN resembles graphite: the hexagonal BN (hBN) consists of stacked sheets similar to graphite.
  • hBN hexagonal BN
  • hBN that is an analog of graphite oxide (GO).
  • GO graphite oxide
  • the availability of large quantities of exfoliated, functionalized hBN allows the incorporation of hBN into composites and coatings to create materials with previously unattainable properties.
  • hBN nanosheets prepared by the methods disclosed herein.
  • EXAMPLE 3 A versatile strategy for chemical peeling and functionalization of hBN
  • BNNS boron nitride nanosheets
  • compatibility and dispersibility of nanosheets are of importance.
  • the problems of physical exfoliation such as low yield and low functionality limit the use of this material in composites. Therefore, a chemical method may possess advantages, such as efficient, effective, highly reactive and better processibility, over other methods, which can significantly improve the interaction between BNNS and organic molecules.
  • the oxidation of boron nitride has been proven to be effective for exfoliation. Obtained boron nitride oxide is suitable for further functionalization reactions and better properties of composites.
  • Boron nitride is an inorganic compound with chemical formula BN.
  • the hexagonal form corresponding to graphite, hexagonal boron nitride (hBN) is a used material with desirable properties.
  • the lattice structure of hBN appears very similar to that of graphite in which alternating B and N atoms substitute for C atoms to form 2-dimensional layer structures.
  • Nanosheets of graphite, graphene, the isoelectric analogue of hBN has become one of the most exciting topics of research in the last several years. Presumably, hBN can also be exfoliated to form unique 2D crystal structures.
  • fabrication of BNNS has been attempted by mechanical exfoliation, nanotube unwrapping, liquid phase sonication, reacting boric acid with urea, and chemical vapor deposition. Several techniques were attempted for the preparation of minute quantities of BNNS.
  • BNNS The unique properties of BNNS are primarily valuable as novel nanofillers in highly thermoconductive and electrically insulating polymeric composites, or as functional materials in electronic devices working in hazardous or high-temperature environments.
  • most investigations in the literature were focused on BNNS in the solid state, because these nanosheets, like graphene, are generally insoluble in common organic and aqueous media.
  • the research efforts on their functionalization have stimulated and enabled the exploitation of the properties and applications that are not accessible in the solid state, such as the dispersion of graphene in polymeric nano-composites.
  • effects on the research of BNNS may be expected from the introduction of BNNS into solution or suspension.
  • thermoplastic polyurethane films with 5% of BNNS as fillers show improved modulus, stress at low strain and ultimate tensile strength.
  • Authors of both papers attribute the properties increases to efficient matrix interactions with the embedded BNNSs, which indicates that increasing interaction may result in better properties.
  • BN nanoflakes are also reported to improve the thermally conductive of a photosensitive polyimide by up to three times when weight fraction equals to 30%. Their exfoliation process is based on a surfactant modified BN and the yield is not mentioned, which might not be higher than other similar methods. More important, matrix- filler interactions can be increased by introducing covalent bond instead of surfactants.
  • TGA data The oxidation reaction of hBN was studied by thermogravimetric analysis (TGA) in air atmosphere, as shown in FIG. 3.
  • TGA thermogravimetric analysis
  • the weight loss-temperature dependence curve revealed that the rate of oxidation increases from 900°C to 1000°C.
  • FIG. 1 shows hBN's behavior in nitrogen and in argon atmosphere for comparison. A slight mass loss is observed in nitrogen atmosphere, which can be attributed to the formation of boron lattice vacancies.
  • FTIR Fourier transform infrared spectroscopy
  • B-0 bonds Due to the formation of B-0 bonds, further oxidation may occur from defects or edges and finally cut large flakes into smaller ones. But this process is controlled by diffusion of oxygen. So TGA shows the rate of increasing slows down. When size of tiny sheets is small enough, they will able to be washed away and filtered out by hot water, because they are soluble in it and small enough. B-0 bonds not only decrease Van der Waal force between layers but also increase interactions with polar solvent like water, so having relatively higher functionality smaller sheets are peeled and dispersed in solvent. It was found that, compared with BNO, washed BNO has lower intensity of B-0 bonds. When all edges and defects are reacted, the very inner sheets still cannot be oxidized because of isolation of air by the outer layers.
  • BNO is not as unctuous as as-purchased hBN but the color of BNO is still pure white.
  • the filtration that contains BNO sheets in it is cloudy.
  • AFM AFM- AFM measurement in FIGS. 4 A and 4B was performed on hot water washed BNO. The sample was dispersed in water at about 0.1 mg/mL with a tip sonicator for about 30 mins. Tapping mode AFM shows very small ( ⁇ 100 nm diam.) single-layer sheets. Sheet heights are on average 0.77 nm. 5 x 5 ⁇ scan using tapping mode AFM with a sharp tip yields small, uniform particles less than 100 nm in diameter. 2 x 2 ⁇ scan using tapping mode AFM with a sharp tip shows more detailed view of sheets. Origin of these nanosheets has been explained before, but those sheets are not produced by sonication, like in other works.
  • reaction factors affect it, control
  • isocyanate is one of the most promising ones.
  • the nature of hydroxide groups on fBNNS should allow fBNNS to react with isocyanate.
  • This reaction is proved by FTIR shown in FIG. 13.
  • FES EM shown in FIGS. 6A and 6B have peeled off and curved edges which are from decreased interactions between layers.
  • extended layer spacing is caused by inserting phenyl groups in between layers, which have a large volume than hydroxide groups.
  • XRD shows the increase of d spacing and change of peak shape (FIG. 7). Using pristine to perform this reaction produces no change on FTIR. This is also evidence of reaction of hydroxide group on fBNNS.
  • NMR can calculate average functionality of fBNNS. After optimizing the reaction condition, a scaled up reaction was performed.
  • BNNS can be a good nanofiller for a polymer matrix.
  • the nature of hydroxide groups on fBNNS allows it to react with isocyanate, an essential reaction to synthesize polyure thanes. So by initiating polymerization from BNO, a new method to fabricate BNNS filled polymeric materials is introduced by the present disclosure.
  • Thermoplastic polyurethanes have excellent mechanical and elastic properties, good hardness, high abrasion and chemical resistance. Then, fBNNS is added during the chain extension reaction and a composite will be obtained after the reaction is finished.
  • the present disclosure demonstrates for the first time the formation of large quantities of functionalized exfoliated boron nitride sheets.
  • hBN In addition to exfoliation, the functionalization of hBN has also drawn interest.
  • Some methods for functionalizing hBN include a method to form associations of hBN nanosheets with alkyl amines by first using a ball mill to cleave the sheets and produce defect sites and the use of hydrazine, hydrogen peroxide, nitric acid and sulfuric acid heated under pressure, followed by sonication, to produce 0.3 g L "1 suspensions of hBN.
  • hBN nanotubes Although not using hBN sheets, it was shown that at high temperatures hBN nanotubes slowly form defect sites that can be used to break the tubes into smaller segments to aid in solvent dispersion.
  • oxygen radicals in sonicated NMP solutions to attach hydroxyl groups to hBN.
  • FIG. 15A Shown in FIG. 15A is a vial containing pristine hBN in deionized water after bath sonication.
  • FIG. 15B shows BNO suspended in water with no sonication. There is no apparent water solubility with pristine hBN, while the hydroxylated material results in a cloudy suspension containing a small amount of precipitate on the bottom of the vial.
  • FIG. 15C shows an AFM image of these suspended sheets drop cast on an HOPG surface. The sheets are single layers, with lateral dimensions on the hundreds of nanometers length scale. A height histogram (FIG. 19) gives the sheet thickness to be about 0.69 nm. No
  • centrifugation is employed to fractionate the sheets for AFM imaging, and thus the image represents the entire population of the suspended material. This is in stark contrast to other methods that rely on centrifugation to separate the samples into fractions with different numbers of hBN layers.
  • the BNO is also investigated by transmission electron microscopy (TEM), Raman spectroscopy, and dynamic light scattering (DLS).
  • TEM images (FIGS. 20A-D) are in good agreement with the AFM analysis, and show single sheets with lateral dimensions of about 100-200 nm.
  • Raman analysis (FIG. 21) indicates a blue shift of 2 cm “1 in the E 2g phonon mode at 1369 cm "1 for the BNO
  • DLS (FIG. 22) analysis shows a mean diameter of about 360 nm.
  • FIG. 16A shows the FTIR spectra obtained at different stages of material synthesis.
  • the spectrum of pristine hBN Prior to heating, the spectrum of pristine hBN exhibits only the characteristic peaks of B-N in-plane stretching at 1370 cm “1 and B-N-B out of plane bending observed at 810 cm “1 , as shown Figure FIG. 16A(a).
  • the formation of boron-oxygen bonds in the heated material (before adding to water) is indicated in the FTIR spectrum FIG. 16A(b) by the B-O- H peak at -3200 cm "1 and the small in-plane peak near 1200 cm “1 .
  • the peak at 1200 cm “1 has been assigned previously to boron coordinated with three oxygen in an extended lattice. After washing with water (FIG. 16A(c)), the peak near 1200 cm “1 disappears while B-O-H peak remains, with a shoulder at about 3400 cm “1 indicating loss of the in-plane B-0 bonds.
  • the reason for the decreased B-O-H peak intensity seen near 3200 cm “1 before washing (FIG. 16A(b)), and after washing (FIG. 16A(c)), is not completely clear. It may be as simple as dryness of the samples, but storing in a vacuum oven prior to analysis did not appear to have an effect.
  • the loss of peak area may be attributed to the loss of small, highly functionalized sheets during the washing process.
  • a further explanation may be the presence of both N 2 BOH and NB(OH) 2 groups in the initial sample, with the washing step leading to the decomposition of NB(OH) 2 to boric acid. That the peaks correspond to hydroxyl groups is supported by FIG. 16A(d) however, as they completely disappear upon treatment with phenylisocyanate. The isocyanate is very reactive towards hydroxyl groups and results in the disappearance of the O-H stretch.
  • boric acid melts at 171°C and boils at 300°C. As the oxidation is run open to the air at 1000°C, the retention of formed boric acid is unlikely and would be observed as a loss of mass in the TGA.
  • FTIR spectra comparing boric acid with hydroxylated hBN indicates no significant formation of boric acid.
  • B2O 3 boron trioxide
  • hBN is thermally stable, and we find that at 800°C, no significant oxidation is observed. As the temperature is raised, there is an increase of mass with time, and the rate of oxidation increases with increasing temperature (FIG. 24). TGA studies indicate that when heated in air at temperatures at 1000°C, hBN gains mass for a period of time, followed by a leveling off (FIG. 16B, top). In contrast, when heated in an argon atmosphere at the same temperature, no mass change is observed (FIG. 16B, middle). Interestingly, when heated in a nitrogen atmosphere at 1000°C, the hBN losses mass (FIG. 16B, bottom). While no reaction is seen in an argon atmosphere, a stable oxidation product is formed in air.
  • Evidence for the formation of B-0 rather than N-0 bonds comes from X-ray photoelectron spectroscopy (XPS) shown in FIG. 16D.
  • XPS X-ray photoelectron spectroscopy
  • FIG. 17A shows pristine hBN with dimensions of microns and smooth surfaces and edges
  • FIG. 17B clearly shows the rough edges and "divots" on the surface corresponding to the size of the single sheets imaged by AFM in FIG. 15C.
  • FIG. 20C Similar results are also obtained by TEM (FIG. 20C), where roughly circular thin spots are seen decorating the previous (prior to heating) surface.
  • Electron-diffraction patterns of BNO reveal the typical six-fold symmetry structure of hBN.
  • FIG. 17C shows BNO sheets obtained by drop casting an aqueous suspension on a SEM stub. The images of the sheets are consistent with those obtained by AFM, but with the high concentration of sheets leading to sheet overlap.
  • Experimental - Samples were prepared by the thermal treatment of hexagonal boron nitride in air.
  • BN powder about 10 g, 99.5%, Alfa Aesar, used as received
  • the furnace was heated to about 1000°C and held at that temperature for about one hour in air. After cooling, the material was washed with hot water and dried.
  • Approximately 700 mg of BNO could be collected from 1 g washed hydroxylated BN powder after sonication and centrifugation.
  • FESEM measurements were performed using a JEOL JSM-6335F cold cathode field emission (12 kV) scanning electron microscope. TGA was carried out on a TA Instruments Q 500 Thermogravimetric Analyzer at a heating rate of about 10°C min "1 in a platinum pan. IR transmission measurements were conducted on a Nicolet 560 instrument coupled with SpectraTech IR Plan 0044-003 microscope. For X-ray diffraction (XRD) measurements, a Bruker AXS D2 Phaser was utilized. XPS measurements were performed using a 595 Scanning Auger Electron Spectrometer.
  • XRD X-ray diffraction
  • the yield of the process was taken to be the amount of material suspended in water divided by the amount of precipitate. While the precipitate was hydroxylated as well, it was not exfoliated and thus did not suspend.
  • a typical determination of yield 15.2 mg of thermally treated material was placed in water and briefly bath sonicated. The suspension was then filtered, and about 5.0 mg of material was recovered from the filter, giving a yield of about 67%. The mass of the precipitate was utilized rather than the exfoliated material as sheets were retained in the filter material.
  • the biggest peak is the height at which most pixels of the image are the substrate. Therefore, the center of this peak is assigned height 0.
  • the second highest height in the image represents the height of the sheets, about 0.7nm.
  • the ratio of the areas under the peaks gives the ratio of substrate area vs. sheet area, about 15% of the substrate is covered with sheets. In this technique all sheets in the image are averaged, giving higher precision and being more representative than a single height profile.
  • TEM samples were prepared by drop casting the suspension with a low concentration, generally at about 0.1 mg/mL, onto a carbon grid and viewed in both transmission and diffraction mode on a FEI Tecnai T12 STEM.
  • DLS dynamic light scattering (DLS) using a NICOMP 300 Submicron Particle Sizer - Dynamic light scattering (DLS) was utilized to determine the particle size in the cloudy suspensions obtained by using a NICOMP 300 Submicron Particle Sizer.
  • the results shown below are in general agreement with the results obtained by AFM, with DLS indicating a somewhat larger size than the 100 nm length scale obtained by AFM.
  • the parameters used for the calculation of size by DLS are only estimates, and thus the AFM data is expected to be more reliable.
  • FIG. 23 gives a clear indication that boric acid is not the product we obtain when heating in air.
  • Study of hBN oxidation at different temperatures by TGA - Thermal gravimetric analysis was done at different temperatures to determine the optimal conditions for oxidation. Shown in FIG. 24 are three TGA traces run at constant temperature in air. Based on these results, our standard oxidations were performed at about 1000°C.
  • Another goal of this disclosure is to utilize the presently developed method for the functionalization and exfoliation of boron nitride to fabricate and/or commercialize a new class of flame retardant (e.g., for use in the plastics industry), boron nitride oxide (BNO).
  • flame retardants e.g., for use in the plastics industry
  • BNO boron nitride oxide
  • Current flame retardants either require very high loadings, compromising the properties of the product, or are banned or about to banned in the US and Europe due to environmental and health concerns (they can be utilized only at factories grandfathered in that continue to use them).
  • Boron nitride a synthetic material used in cosmetics and as a high temperature lubricant, after conversion to BNO, has the potential to replace many of the current flame retardants in this big market.
  • Boron nitride is a layered material, much like graphite, that is thermally conductive, but electrically insulating. It is also very chemically inert and does not burn in air until approximately 900°C (1652°F). It is believed that, in order to utilize successfully, it should be exfoliated to increase its surface area, and functionalized in order to be well dispersed in the composite. The present disclosure provides some routes to make and fabricate functionalized exfoliated sheets in a commercially viable way.
  • this project/disclosure has been approached by two simultaneous directions: (i) making composite materials using material produced in the laboratory and (ii) using larger-scale manufacturing to produce pilot plant scale BNO material.
  • PC polycarbonate
  • PMMA poly(methyl methacrylate)
  • PU polyurethane
  • nylon polycarbonate
  • Another approach to making the composites has been to graft polymers from the hydroxyl groups formed at the edges of the BNO sheets. This is expected to provide a filler material that will be well dispersed in the polymer, resulting in a more effective flame retardant at a much lower loading. Both PMMA and PU have been successfully attached to the edges of BN sheets.

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Abstract

L'invention concerne l'élaboration et l'utilisation de matériaux à base de nitrure de bore. L'invention propose ainsi, d'une part des systèmes ou procédés intéressants permettant de modifier le nitrure de bore, c'est-à-dire de le fonctionnaliser et de l'exfolier, et d'autre part des systèmes ou procédés d'utilisation de celui-ci. L'invention concerne plus particulièrement des systèmes ou procédés permettant de modifier le nitrure de bore hexagonal et de l'utiliser dans des matériaux de charge. D'une façon générale, l'invention porte sur l'élaboration ou l'utilisation de matières de charge polymères à base de nitrure de bore. Par certains de ses modes de réalisation, l'invention propose des systèmes ou procédés permettant l'exfoliation du nitrure de bore hexagonal destiné à l'emploi comme matière de charge dans des composites polymères, notamment comme nanomatériau de charge. Ce matériau ininflammable, transparent, et à grande aire de surface, convient comme produit ignifugeant. En outre, les matériaux à base de nitrure de bore selon la présente invention, notamment les composites polymères comprenant du nitrure de bore hexagonal, conviendront à une large gamme d'applications. L'invention concerne enfin la fonctionnalisation du nitrure de bore pour l'utiliser comme composant de composite.
PCT/US2014/017420 2013-02-20 2014-02-20 Procédé de modification du nitrure de bore, et utilisation du nitrure de bore modifié WO2014130687A1 (fr)

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WO2017044354A1 (fr) * 2015-09-09 2017-03-16 Pepsico, Inc. Procédé de production de polymères comprenant du nitrure de bore hexagonal
RU2614012C1 (ru) * 2016-03-03 2017-03-22 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Способ получения нанотрубок нитрида бора
WO2017093731A1 (fr) * 2015-12-02 2017-06-08 The University Of Manchester Matériaux bidimensionnels oxygénés
WO2018030124A1 (fr) * 2016-08-09 2018-02-15 三菱瓦斯化学株式会社 Particules de nitrure de bore hexagonal à surface rugueuse, procédé de production de celles-ci, composition, feuille de résine, préimprégné, stratifié plaqué de feuille métallique, et carte de circuit imprimé
WO2017117238A3 (fr) * 2015-12-30 2018-02-15 Saint-Gobain Ceramics & Plastics, Inc. Particules de nitrure modifiées, particules de nitrure à fonctionnalité oligomère, composites à base de polymère et leurs procédés de formation
JP2019137581A (ja) * 2018-02-09 2019-08-22 三菱瓦斯化学株式会社 表面粗化六方晶窒化ホウ素粒子、組成物、硬化物、単層樹脂シート、積層樹脂シート、プリプレグ、金属箔張積層板、プリント配線板、封止用材料、繊維強化複合材料及び接着剤
US10501322B2 (en) * 2016-12-19 2019-12-10 Wisconsin Alumni Research Foundation Mixed oxygen and organic compound treatment for functionalizing oxygen onto the surface of boron nitride
CN112029262A (zh) * 2020-04-15 2020-12-04 重庆门朵新材料科技有限公司 一种氮化硼增强水性聚氨酯高导热高阻隔材料及安全套
KR20210048640A (ko) 2019-10-23 2021-05-04 한국과학기술연구원 질화붕소나노물질을 포함하는 다공성 복합체 및 이의 제조방법
CN112919431A (zh) * 2021-02-07 2021-06-08 辽东学院 一种高产率、高结晶度的六方氮化硼纳米片及其制备方法
CN112955403A (zh) * 2018-08-16 2021-06-11 Cpi创新服务有限公司 生产含氮化硼的流体的方法

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US10189940B2 (en) 2015-09-09 2019-01-29 Pepsico, Inc. Process for providing polymers comprising hexagonal boron nitride
WO2017044354A1 (fr) * 2015-09-09 2017-03-16 Pepsico, Inc. Procédé de production de polymères comprenant du nitrure de bore hexagonal
WO2017093731A1 (fr) * 2015-12-02 2017-06-08 The University Of Manchester Matériaux bidimensionnels oxygénés
TWI671364B (zh) * 2015-12-30 2019-09-11 美商聖高拜陶器塑膠公司 改質氮化物顆粒、寡聚物官能化氮化物顆粒及基於聚合物之複合材料
CN108602985A (zh) * 2015-12-30 2018-09-28 圣戈本陶瓷及塑料股份有限公司 改性的氮化物颗粒、寡聚物官能化的氮化物颗粒、聚合物类复合物以及其形成方法
US10584231B2 (en) 2015-12-30 2020-03-10 Saint-Gobain Ceramics & Plastics, Inc. Modified nitride particles, oligomer functionalized nitride particles, polymer based composites and methods of forming thereof
JP2019506480A (ja) * 2015-12-30 2019-03-07 サン−ゴバン セラミックス アンド プラスティクス，インコーポレイティド 修飾窒化物粒子、オリゴマー機能化窒化物粒子、ポリマー系複合材、及びこれらの形成方法
WO2017117238A3 (fr) * 2015-12-30 2018-02-15 Saint-Gobain Ceramics & Plastics, Inc. Particules de nitrure modifiées, particules de nitrure à fonctionnalité oligomère, composites à base de polymère et leurs procédés de formation
TWI681004B (zh) * 2015-12-30 2020-01-01 美商聖高拜陶器塑膠公司 改質氮化物顆粒、寡聚物官能化氮化物顆粒、基於聚合物之複合材料及其形成方法
RU2614012C1 (ru) * 2016-03-03 2017-03-22 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Способ получения нанотрубок нитрида бора
JPWO2018030124A1 (ja) * 2016-08-09 2019-06-06 三菱瓦斯化学株式会社 表面粗化六方晶窒化ホウ素粒子及びその製造方法、並びに、組成物、樹脂シート、プリプレグ、金属箔張積層板、プリント配線板
WO2018030124A1 (fr) * 2016-08-09 2018-02-15 三菱瓦斯化学株式会社 Particules de nitrure de bore hexagonal à surface rugueuse, procédé de production de celles-ci, composition, feuille de résine, préimprégné, stratifié plaqué de feuille métallique, et carte de circuit imprimé
JP7055279B2 (ja) 2016-08-09 2022-04-18 三菱瓦斯化学株式会社 表面粗化六方晶窒化ホウ素粒子及びその製造方法、並びに、組成物、樹脂シート、プリプレグ、金属箔張積層板、プリント配線板
US10501322B2 (en) * 2016-12-19 2019-12-10 Wisconsin Alumni Research Foundation Mixed oxygen and organic compound treatment for functionalizing oxygen onto the surface of boron nitride
JP2019137581A (ja) * 2018-02-09 2019-08-22 三菱瓦斯化学株式会社 表面粗化六方晶窒化ホウ素粒子、組成物、硬化物、単層樹脂シート、積層樹脂シート、プリプレグ、金属箔張積層板、プリント配線板、封止用材料、繊維強化複合材料及び接着剤
CN112955403A (zh) * 2018-08-16 2021-06-11 Cpi创新服务有限公司 生产含氮化硼的流体的方法
KR20210048640A (ko) 2019-10-23 2021-05-04 한국과학기술연구원 질화붕소나노물질을 포함하는 다공성 복합체 및 이의 제조방법
CN112029262A (zh) * 2020-04-15 2020-12-04 重庆门朵新材料科技有限公司 一种氮化硼增强水性聚氨酯高导热高阻隔材料及安全套
CN112919431A (zh) * 2021-02-07 2021-06-08 辽东学院 一种高产率、高结晶度的六方氮化硼纳米片及其制备方法
CN112919431B (zh) * 2021-02-07 2023-07-18 辽东学院 一种高产率、高结晶度的六方氮化硼纳米片及其制备方法

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