EP3510089A1 - Multipurpose graphene-based composite - Google Patents
Multipurpose graphene-based compositeInfo
- Publication number
- EP3510089A1 EP3510089A1 EP17847829.3A EP17847829A EP3510089A1 EP 3510089 A1 EP3510089 A1 EP 3510089A1 EP 17847829 A EP17847829 A EP 17847829A EP 3510089 A1 EP3510089 A1 EP 3510089A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- graphene
- substrate
- based composite
- sodium metaborate
- hydrated sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 346
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 334
- 239000002131 composite material Substances 0.000 title claims abstract description 221
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims abstract description 160
- 239000000463 material Substances 0.000 claims abstract description 110
- 239000000758 substrate Substances 0.000 claims description 176
- 239000000203 mixture Substances 0.000 claims description 77
- 239000007788 liquid Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 49
- 238000000576 coating method Methods 0.000 claims description 40
- 239000003063 flame retardant Substances 0.000 claims description 36
- 238000005299 abrasion Methods 0.000 claims description 34
- 239000011521 glass Substances 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 229920000642 polymer Polymers 0.000 claims description 22
- 230000000845 anti-microbial effect Effects 0.000 claims description 17
- 239000012279 sodium borohydride Substances 0.000 claims description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
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- 238000009830 intercalation Methods 0.000 claims description 7
- 230000002687 intercalation Effects 0.000 claims description 7
- 229920001169 thermoplastic Polymers 0.000 claims description 7
- 229920001187 thermosetting polymer Polymers 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 238000010128 melt processing Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 description 36
- 230000000844 anti-bacterial effect Effects 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 16
- 239000010949 copper Substances 0.000 description 15
- 239000008188 pellet Substances 0.000 description 15
- 241000894006 Bacteria Species 0.000 description 13
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 239000003039 volatile agent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000428 dust Substances 0.000 description 8
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- 210000004027 cell Anatomy 0.000 description 7
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 230000000813 microbial effect Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000002411 thermogravimetry Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
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- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000004299 exfoliation Methods 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
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- 239000000779 smoke Substances 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
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- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
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- 230000008020 evaporation Effects 0.000 description 3
- 238000007706 flame test Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
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- RNLYVRKMBPOHNI-UNDPIUDWSA-N (2s)-5-(diaminomethylideneamino)-n-[11-[4-[4-[4-[11-[[2-[4-[(2r)-2-hydroxypropyl]triazol-1-yl]acetyl]amino]undecanoyl]piperazin-1-yl]-6-[2-[2-(2-prop-2-ynoxyethoxy)ethoxy]ethylamino]-1,3,5-triazin-2-yl]piperazin-1-yl]-11-oxoundecyl]-2-[4-[(2s)-2-methylbut Chemical compound N1=NC(C[C@@H](C)CC)=CN1[C@@H](CCCN=C(N)N)C(=O)NCCCCCCCCCCC(=O)N1CCN(C=2N=C(N=C(NCCOCCOCCOCC#C)N=2)N2CCN(CC2)C(=O)CCCCCCCCCCNC(=O)CN2N=NC(C[C@@H](C)O)=C2)CC1 RNLYVRKMBPOHNI-UNDPIUDWSA-N 0.000 description 2
- 241000203069 Archaea Species 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XOJVVFBFDXDTEG-UHFFFAOYSA-N Norphytane Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 2
- 238000001530 Raman microscopy Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000000843 anti-fungal effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000003873 derivative thermogravimetry Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- -1 ketone compounds Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002159 nanocrystal Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- MEUAVGJWGDPTLF-UHFFFAOYSA-N 4-(5-benzenesulfonylamino-1-methyl-1h-benzoimidazol-2-ylmethyl)-benzamidine Chemical compound N=1C2=CC(NS(=O)(=O)C=3C=CC=CC=3)=CC=C2N(C)C=1CC1=CC=C(C(N)=N)C=C1 MEUAVGJWGDPTLF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 230000005778 DNA damage Effects 0.000 description 1
- 231100000277 DNA damage Toxicity 0.000 description 1
- 241000206602 Eukaryota Species 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000006142 Luria-Bertani Agar Substances 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 125000004429 atom Chemical group 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 229940041514 candida albicans extract Drugs 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
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- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002118 epoxides Chemical group 0.000 description 1
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- 230000000855 fungicidal effect Effects 0.000 description 1
- 230000001408 fungistatic effect Effects 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
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- 150000002576 ketones Chemical class 0.000 description 1
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- 150000002632 lipids Chemical class 0.000 description 1
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- 239000002609 medium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 230000003641 microbiacidal effect Effects 0.000 description 1
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- 230000003647 oxidation Effects 0.000 description 1
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- 235000019319 peptone Nutrition 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000013207 serial dilution Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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Classifications
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
- C01B32/19—Preparation by exfoliation
- C01B32/192—Preparation by exfoliation starting from graphitic oxides
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
-
- 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
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
-
- 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
Definitions
- the present invention relates in general to graphene-based materials.
- the invention relates to a graphene-based composite, a substrate comprising the composite, a method of preparing the composite and applications of the composite.
- a common approach to providing such protection is to coat or treat the object with a protective material.
- objects are commonly coated with various paint products that can protect an object from corrosion, abrasive wear or bacteria fouling.
- Objects can also be treated with fire retardants to improve their fire resistance properties.
- Graphene is an allotrope of carbon having a one atom thick planar sheet structure of typically sp -bonded carbon atoms that are densely packed in a honeycomb to D crystal ladders.
- the covalently bonded carbon atoms typically form repeating units that comprise 6-membered rings, but can also form 5-membered rings and/or 7-membered rings.
- a layer of such covalently bonded carbon atoms is commonly referred to as a graphene "sheet”.
- Graphene may conveniently prepared synthetically or by exfoliation of graphite.
- the present invention therefore provides a graphene-based composite comprising graphene- based material intercalated with hydrated sodium metaborate.
- the present invention also provides a method of preparing a graphene-based composite, the method comprising (i) providing a liquid composition comprising graphene-based material and hydrated sodium metaborate, and (ii) removing liquid from the composition so as to retain the graphene-based material and hydrated sodium metaborate in the composition, wherein the process of removing liquid in step (ii) promotes intercalation of the hydrated sodium metaborate in the graphene-based material to afford the graphene-based composite.
- the present invention further provides a substrate comprising a graphene-based composite, the graphene -based composite comprising graphene-based material intercalated with hydrated sodium metaborate.
- the graphene-based composite in accordance with the invention has surprisingly been found to exhibit characteristics capable of imparting numerous improved properties to a substrate.
- the composite demonstrates a unique ability to protect a variety of substrates from a range of different environmental/use conditions. Such improved properties imparted to the substrate are surprisingly superior to properties imparted to the substrate by each of the constituent components of the composite when used alone.
- substrates comprising the graphene-based composite can advantageously exhibit improved fire retardant properties, improved abrasion resistance and/or improved antimicrobial properties.
- the present invention therefore further provides a substrate with improved fire retardant properties, the substrate comprising a graphene-based composite, wherein the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the present invention also provides a substrate with improved abrasion resistance, the substrate comprising a graphene-based composite, wherein the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the present invention further provides a substrate with improved antimicrobial properties, the substrate comprising a graphene-based composite, wherein the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the present invention further provides a substrate with one or more improved properties, the substrate comprising a graphene-based composite, wherein the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the present invention also provides a method of improving one or more properties of a substrate, the method comprising providing the substrate with a graphene-based composite, wherein the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the substrate may comprise or be provided with the graphene-based composite by any suitable means.
- the substrate may be coated, impregnated, blended and/or compounded with the graphene-based composite.
- the graphene-based composite may comprise graphene-based material selected from graphene, graphene oxide, reduced graphene oxide, partially reduced graphene oxide and combinations thereof.
- Substrates suitable for use in accordance with the invention include those comprising cellulosic material, polymer, metal, ceramic, glass and combinations thereof.
- Figure 1 shows a schematic illustration of the graphene-based composite used in accordance with the invention
- Figure 2 shows a schematic illustration of (a) substrate provided with the graphene-based composite in accordance with the invention, and (b) fire retardant features afforded by the graphene-based composite used in accordance with the invention
- Figure 3 shows flammability testing of (a) paper, (b) paper treated with reduced graphene oxide, and (c) paper treated with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention
- Figure 4 shows a pine wood slat being subjected to a burn test (exposed to a butane flame for 12 seconds at a distance of 20mm), where (a) employs a pine wood slat and (b) employs a pine wood slat coated with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention; and
- Figure 5 shows a pellet formed from saw dust being subjected to a vertical burn test (UL-94), where (a) employs a pellet formed from saw dust and (b) employs a pellet formed from saw dust provided with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention;
- Figure 6 shows bacteria colonies at time zero and 24 hours presented on petri-dished coated with nothing (glass control), graphene oxide (GO control), reduced graphene oxide (rGO by ⁇ 2 ⁇ 2 ) (also a control), and the graphene-based composite according to the invention (rGO/SMB); and
- Figure 7 shows comparative characterization of adhesion and abrasion characteristics of the graphene-based composite according to the invention (rGO/SMB) relative to graphene oxide (GO-control) and reduced graphene oxide (rGO-control) on Cu and glass substrates.
- Figure 8 shows polymer (water soluble - PVA) sample being subjected to a burning test (UL- 94), where (top) employs a non-treated sample, and (bottom) employs a polymer sample impregnated with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention.
- Figure 9 shows polymer (oil soluble - polystyrene) sample being subjected to a burning test (UL-94), where (top) employs a non-treated sample, and (bottom) employs a polymer sample impregnated with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention.
- the present invention provides a unique graphene-based composite.
- the graphene -based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- graphene-based composite is intended to mean the composite has a composition comprising graphene, graphene oxide, partially reduced graphene oxide, reduced graphene oxide or a combination of two or more thereof.
- graphene-based material may therefore be used herein as a convenient reference to graphene (material or sheets), graphene oxide (material or sheets), partially reduced graphene oxide (material or sheets), reduced graphene oxide (material or sheets) or a combination of two or more thereof.
- Graphene oxide is an oxygenated form of graphene that is typically prepared by exfoliation of graphite oxide. Graphene oxide is considered to have a graphene-based structure that is substituted with oxygenated groups such as hydroxyl and epoxide. Graphene oxide may be prepared using a number of techniques such as the so called Brodie, Staudenmaier or Hummers methods. Graphene oxide may be reduced so as to form a reduced form of graphene oxide. Reduced graphene oxide is both chemically and physically different to graphene oxide due to the loss of its oxygenated groups. The degree to which graphene oxide is reduced can be varied, with that variation being reflected in the amount of oxygenated groups remaining.
- graphene oxide is not fully reduced it is often referred to in the art as partially reduced graphene oxide.
- Reduced and partially reduced graphene oxide are less hydrophilic than graphene oxide.
- Reduced graphene oxide is sometimes referred to in the art simply as graphene as an indication that substantially all oxygenated groups have been removed.
- Techniques for reducing or partially reducing graphene oxide are well known in the art. For example, graphene oxide can be reduced or partially reduced by chemical or thermal reduction.
- Graphene oxide, partially reduced graphene oxide and reduced graphene oxide have a covalently bonded carbon atom sheet structure similar to graphene.
- the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the composite per se will therefore comprise a plurality of graphene- based material sheets having intercalated there between hydrated sodium metaborate.
- a schematic illustration of the graphene-based composite is presented in Figure 1 which highlights the layered sheet structure of the graphene-based material and the hydrated sodium metaborate (NaB0 2 .xH 2 0) intercalated within the layered sheet structure.
- the graphene-based material being "intercalated" with hydrated sodium metaborate is meant the hydrated sodium metaborate resides as a solid in between and on layers of the graphene-based material sheet structure. In other words, the graphene-based material is intercalated with solid hydrated sodium metaborate.
- the graphene-based composite per se also presents as a solid.
- the layered sheet structure of the graphene-based material may comprise graphene, graphene oxide, partially reduced graphene oxide, reduced graphene oxide or a combination of two or more thereof.
- the graphene -based composite comprises one or both of graphene and reduced graphene oxide intercalated with hydrated sodium metaborate.
- Sodium metaborate used in accordance with the invention is "hydrated". By the sodium metaborate being hydrated is meant the sodium metaborate contains physically and/or chemically absorbed and/or bonded water such as water of crystallisation. Hydrated compounds are typically identified with the indicator .xH 2 0. Provided the hydrated sodium metaborate can be intercalated within the graphene-based material, there is no particular limitation on the physical form which the hydrated sodium metaborate may take.
- the graphene-based material is intercalated with hydrated sodium metaborate in the form of microparticles, nanoparticles, a film, a sheet or combinations thereof.
- nanoparticles are particles having a largest dimension of no more than lOOnm.
- microparticles are particles having a largest dimension of no more than lOOOnm.
- the largest dimension of the hydrated sodium metaborate will generally range from about 50-500nm.
- the graphene-based composite will comprise about 20 wt% to about 80 wt% graphene-based material and about 20 wt% to about 80 wt% intercalated hydrated sodium metaborate.
- the graphene-based composite may comprise one or more other components. In that case, the wt. % of the graphene-based material and/or the intercalated inorganic metal hydrate will be adjusted accordingly.
- the graphene-based material and hydrated sodium metaborate used in accordance with the invention can be sourced commercially or made by techniques known in the art.
- the graphene-based composite can conveniently be prepared by a method comprising (i) providing a liquid composition comprising graphene-based material and hydrated sodium metaborate, and (ii) removing liquid from the composition so as to retain the graphene-based material and hydrated sodium metaborate in the composition, wherein the process of removing liquid in step (ii) promotes intercalation of the hydrated sodium metaborate in the graphene- based material to afford the graphene-based composite.
- the composition will of course also comprise a liquid.
- the liquid may be organic (solvent), aqueous or a combination thereof.
- graphene-based material is substantially insoluble in most liquids, but can be readily dispersed within a liquid.
- the hydrated sodium metaborate may be soluble or insoluble in the liquid composition.
- the method of preparing the composite comprises (i) providing an aqueous liquid composition comprising graphene-based material and hydrated sodium metaborate, and (ii) removing water from the composition.
- Including hydrated sodium metaborate within a liquid dispersion of graphene-based material and removing liquid from the resulting composition allows for the hydrated sodium metaborate to become intercalated within the layered structure of the graphene-based material.
- liquid may be removed from the composition by any suitable means.
- liquid is removed from the composition by evaporation. If required, heat may be applied to the composition to promote such evaporation.
- the hydrated sodium metaborate is soluble in the liquid used for the composition
- removing the liquid from the composition will promote formation of hydrated sodium metaborate particles or crystals that intercalate within the layered structure of the graphene- based material.
- the hydrated sodium metaborate is insoluble in the liquid used for the composition
- removing the liquid from the composition will simply promote intercalation of the pre-existing hydrated sodium metaborate particles within the layered structure of the graphene-based material. In that case, the sodium metaborate particles used will of course be of a suitable size for such intercalation to occur.
- the hydrated sodium metaborate used to form the graphene-based composite may itself be pre-formed and introduced to the liquid composition provided for preparing the graphene- based composite.
- the hydrated sodium metaborate may be prepared in situ as part of the method of preparing the graphene-based composite.
- the liquid composition comprising graphene-based material and hydrated sodium metaborate may be provided by an aqueous liquid composition comprising graphene oxide and sodium borohydride, wherein the graphene oxide is reduced by the sodium borohydride to afford reduced graphene oxide and the hydrated sodium metaborate.
- the graphene-based composite is produced by (i) providing an aqueous liquid composition comprising graphene oxide and sodium borohydride, wherein the sodium borohydride reduces the graphene oxide to afford reduced graphene oxide and hydrated sodium metaborate, and (ii) removing water from the so formed composition so as to retain the graphene-based material and hydrated sodium metaborate in the composition, wherein the process of removing water in step (ii) promotes intercalation of the hydrated sodium metaborate in the graphene-based material to afford the graphene-based composite.
- the present invention provides a substrate with one or more improved properties, the substrate comprising a graphene-based composite, wherein the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the present invention also provides a method of improving one or more properties of a substrate, the method comprising providing the substrate with a graphene-based composite, wherein the graphene-based composite comprises graphene-based material intercalated with hydrated sodium metaborate.
- the one or more improved properties include, but are not limited to, improved fire retardant properties, improved abrasion resistance, improved antimicrobial properties.
- the graphene-based composite can advantageously provide improved properties to a variety of substrates.
- Substrates suitable for use in accordance with the invention include those comprising cellulosic material, polymer, metal, ceramic, glass and combinations thereof.
- cellulosic material examples include, but are not limited to, wood, paper, saw dust, and natural fibres.
- polymer examples include, but are not limited to, thermoset and thermoplastic polymers.
- polymer examples include, but are not limited to, polyolefins, polyamides, polyesters, polyvinyl alcohols, polystyrenes, polyacrylates, polyurethanes, polycarbonates, epoxy resins.
- metal examples include, but are not limited to, steel, copper, and aluminium.
- the substrate can take.
- the substrate can be in the shape of a sheet, film, plate, beam, particles, powder, plank or any formed product.
- the substrate comprising the graphene-based composite, or “providing” the substrate with the composite
- the composite is suitably physically associated with the substrate so as to impart an improved property.
- the substrate comprises or is provided with a graphene-based composite such that the composite is physically associated with the substrate.
- the graphene-based composite may be located on a surface of the substrate and/or within the substrate matrix.
- the substrate may comprise or be provided with the composite by the composite being coated on, absorbed or impregnated in and/or compounded with the substrate material.
- the composite may present as a coating on a surface of a substrate and/or the composite may be distributed throughout the substrate matrix material.
- the substrate may be provided with the graphene-based composite by any suitable means.
- the graphene-based composite may be used in a pre-formed state (i.e. in the form of the composite per se).
- the graphene-based composite may form part of a liquid composition that is coated on or impregnated in the substrate using application techniques well known to those skilled in the art.
- the liquid composition may comprise the graphene-based composite in the form of a dispersion within a liquid (organic (solvent), aqueous or a combination thereof).
- the graphene-based composite may also be used in the form of a solid (e.g.
- the substrate may be in the form of a thermoplastic polymer whereby the thermoplastic polymer is melt processed with the graphene-based material so as to provide for a thermoplastic polymer product comprising the graphene-based composite distributed throughout the thermoplastic polymer matrix.
- the graphene-based composite may also be blended with cellulosic material such as saw dust and the resulting blend compressed so as to form a so called reconstituted wood product comprising the graphene-based composite distributed throughout the product.
- cellulosic material such as saw dust
- the graphene-based composite can be prepared in situ using precursor components as part of the process of providing it to the substrate.
- graphene-based material may be dispersed in a liquid which also comprises the hydrated sodium metaborate.
- the resulting liquid composition can then be used to coat or impregnate the substrate. Removing liquid from the coated or impregnated liquid composition, while retaining the graphene-based material and hydrated sodium metaborate in the composition, can promote formation of the composite in situ.
- the substrate is provided with the graphene-based composite using precursor components of the graphene-based composite.
- precursor components of the graphene-based composite include graphene-based material and hydrated sodium metaborate.
- the hydrated sodium metaborate may not be intercalated with the graphene-based material but rather that intercalation occurs as part of the process of providing the substrate with the graphene-based composite.
- the graphene-based composite or precursor components thereof may be provided in the form of a coating composition which is applied to the substrate using conventional techniques such as spraying, dip coating, doctor blade and/or brushing.
- the coating composition may be in the form of a paint composition.
- a liquid composition comprising the graphene-based composite or precursor components thereof may be used to impregnate the substrate.
- the graphene-based composite per se may be blended with the substrate material, with that resulting blend optionally being further processed such as being compressed or extruded.
- the substrate is provided with the graphene-based composite by coating the substrate with a composition comprising the graphene-based composite or precursor components thereof. Coating the substrate with the composition may be performed by techniques such as spraying, dip coating, doctor blade and/or brushing.
- the substrate is provided with the graphene-based composite by impregnating the substrate with a composition comprising the graphene-based composite or precursor components thereof. Impregnation of the substrate with the composition may be performed by soaking the substrate in the composition.
- the composition comprising the graphene-based composite for coating or impregnating the substrate may be a liquid composition.
- the liquid component of the composition may be organic (solvent), aqueous or a combination thereof. That composition may comprise other components such as polymer.
- the substrate is a thermoplastic polymer and it is provided with the graphene-based composite by melt processing the polymer with the graphene-based composite.
- the substrate is a thermoset polymer and it is provided with the graphene-based composite by blending the graphene-based composite with precursor materials used to make the thermoset polymer.
- Precursor materials used to make thermoset polymer include monomer and pre -polymer that is polymerised and crosslinked to form the thermoset polymer matrix.
- the substrate is provided with the graphene-based composite by coating or impregnating the substrate with a liquid composition comprising the graphene-based composite.
- the substrate is provided with the graphene-based composite by (i) coating or impregnating the substrate with a liquid composition comprising the graphene- based material and the hydrated sodium metaborate, and (ii) removing liquid from the coated or impregnated liquid composition while retaining the graphene-based material and hydrated sodium metaborate in the composition so as to form and provide the graphene-based composite.
- the substrate is provided with the graphene-based composite by (i) coating or impregnating the substrate with an aqueous composition comprising the graphene- based material and hydrated sodium metaborate, and (ii) removing water from the coated or impregnated liquid composition so as to form and provide the graphene-based composite.
- the hydrated sodium metaborate used to form the graphene-based composite may be pre-formed and introduced to the liquid composition provided for preparing the graphene-based composite.
- the hydrated sodium metaborate may be prepared in situ as part of the process of preparing or forming the graphene-based composite.
- precursor components of the graphene-based composite can also include a precursor compound(s) for preparing the hydrated sodium metaborate.
- Precursor compounds to hydrated sodium metaborate can include sodium borohydride which is oxidised, sodium carbonate in combination with borax, and sodium tetraborate in combination with sodium hydroxide.
- the substrate is provided with the graphene-based composite by (i) providing an aqueous liquid composition comprising graphene oxide and sodium borohydride, wherein the graphene oxide is reduced by the sodium borohydride to afford reduced graphene oxide and hydrated sodium metaborate, (ii) coating or impregnating the substrate with the aqueous liquid composition provided for in step (i), and (iii) removing water from the coated or impregnated aqueous liquid composition so as to form and provide the graphene-based composite.
- the invention may further comprise providing the substrate with hydrated sodium metaborate that does not form part of the graphene-based composite per se.
- the substrate will comprise the graphene-based composite and also hydrated sodium metaborate that does not form part of the graphene-based composite.
- the substrate used is impregnated with hydrated sodium metaborate.
- the substrate is impregnated with hydrated sodium metaborate and can then also be impregnated and/or coated with the graphene-based composite.
- Providing the substrate with hydrated sodium metaborate that does not form part of the graphene-based composite per se can further enhance fire retardant properties of the substrate.
- the graphene composite may be provided in the form of film of average thickness depending on the desired application.
- the graphene composite film may have a thickness of up to 500 microns.
- the graphene-based composite according to the present invention can impart improved fire retardant properties to a substrate.
- the substrate can comprise or be provided with the graphene-based composite as herein described.
- Relevant fire retardant properties are those well known in the art and include ignitability and burn rate of a substrate, release of toxic/flammable volatiles from a substrate upon the substrate being exposed to an ignition source such as fire or extreme heat, self-extinguishing and intumescent properties, char formation/yield and oxygen barrier properties.
- a substrate provided with the graphene -based composite in accordance with the invention has been found to exhibit one or more of reduced ignitability, a lower burn rate, a pronounced intumescent effect, and reduced release of toxic/flammable volatiles upon being exposed to an ignition source, relative to the same substrate that has not been provided with the graphene-based composite according to the invention.
- Fire retardant properties of a substrate can be determined using techniques know in the art. Such techniques include TGA, STA, UL-94, calorimeter, limiting oxygen index (LOI) measurements.
- TGA TGA
- STA STA
- UL-94 calorimeter
- LOI limiting oxygen index
- a substrate that exhibits the improved fire retardant properties according to the present invention will of course be a substrate that in its own right is flammable.
- the present invention can provide a flammable substrate with improved fire retardant properties.
- flammable substrates include those comprising cellulosic material, polymer and combinations thereof.
- cellulosic material examples include those herein described.
- Examples of polymer include those herein described.
- the flammable substrate comprises cellulosic material, polymeric material or a combination thereof.
- the excellent fire retardant properties imparted to the substrate by the graphene-based composite are believed to operate through a number of mechanisms. Without wishing to be limited by theory, it is believed the hydrated sodium metaborate functions as a heat sink as it undergoes endothermic dehydration releasing water into the surrounding environment. That in turn is believed to promote a unique intumescent effect.
- the graphene-based material is believed to function synergistically to promote fire resistance by providing at least four combined functions, including (i) preventing access of oxygen to the flammable substrate, (ii) providing self-extinguishing properties, (iii) preventing escape of toxic and flammable volatiles from the substrate, and (iv) exhibiting char formation and an intumescent effect.
- the graphene-based material is believed to also act as a carbon donor to create a physical barrier between the unburnt substrate and a flame to thereby protect the substrate.
- the hydrated sodium metaborate is believed to promote a high degree of binding between layers of the graphene-based material and also between the substrate and the composite graphene-based composite, thereby providing for a robust fire retardant system. This is particularly useful where the composite is provided in the form of a coating on a substrate.
- Figure 2 (a) represents a substrate coated with a graphene-based composite in accordance with the invention.
- the graphene-based composite coating can be seen as comprising the graphene-based material intercalated with hydrated sodium metaborate.
- Figure 2 (b) illustrates the graphene-based composite coated substrate of Figure 2 (a) being exposed to fire.
- the graphene-based composite used in accordance with the invention is believed to provide numerous mechanisms by which improved fire retardant properties are imparted to the substrate.
- the intercalated hydrated sodium metaborate is believed to not only facilitate good adhesion between the layers of the graphene-based material structure, but also facilitate adhesion of the graphene-based composite to the substrate.
- Such adhesive properties provide for a robust fire retardant system.
- the strongly adhered layered structure of the graphene-based composite is believed to impede the transmission of oxygen to the substrate thereby reducing the potential for the substrate to catch fire.
- the strongly adhered layered structure of the graphene -based composite is believed to impede the release of volatile components from the substrate (e.g. CH 4 ) that can be toxic and also fuel the fire.
- the hydrated sodium metaborate can undergo endothermic dehydration thereby functioning as a heat sink and also releasing water into the surrounding environment. This in turn is believed to promote a unique intumescent effect.
- Such collective features of the graphene -based composite have been found to function as a highly effective, efficient and robust fire retardant system.
- the excellent fire retardant properties imparted by the graphene -based composite are clearly illustrated in Figure 3 which presents results of a series of flame tests.
- Figure 3(a) tests the base paper sample
- Figure 3(b) tests the base paper sample coated with only reduced graphene oxide
- Figure 3(c) tests the base paper sample coated with a graphene -based composite in accordance with the invention, the composite comprising reduced graphene oxide intercalated with hydrated sodium metaborate.
- the base paper sample and the paper coated with reduced graphene oxide readily ignite and are fully combusted after about 10 seconds.
- the paper sample coated with graphene-based composite in accordance with the invention fails to ignite upon being exposed to a naked flame for at least 120 seconds.
- Figure 4 shows a pine wood slat being subjected to a burn test (exposed to a butane flame for 12 seconds at a distance of 20mm), where (a) employs a pine wood slat and (b) employs a pine wood slat coated with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention.
- the untreated pine wood slat can be seen to be almost completely combusted after 30 seconds, while the pine wood slat coated with the composite in accordance with the invention can be seen to only be effected by the flame at its point of contact, with the fire not propagating and the remainder of the slat being largely undamaged.
- Figure 5 shows a pellet formed from saw dust being subjected to a vertical burn test (UL-94), where (a) employs a pellet formed from saw dust and (b) employs a pellet formed from saw dust provided with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention.
- the coated pellet (b) displayed excellent fire-retardancy with no flame propagation behaviour. No flaming or glowing combustion was observed for the composite treated sample, hence those samples were graded as V-0. The burning of the composite treated sample ceased instantly with no vertical lift of the flame, whereas the untreated sawdust pellet showed higher degree of flammable properties that continued till the end (up to the holding clamp) with an approximate linear burning rate of 0.5 mm/s.
- Figures 8 and 9 show how flammable polymer (PVA and polystyrene - top) can be provided with fire retardant properties (bottom) by being compounded with a reduced graphene oxide/hydrated sodium metaborate composite in accordance with the invention.
- the graphene-based composite according to the present invention can impart improved antimicrobial properties, such as antibacterial and/or antifungal properties, to a substrate.
- the substrate can be provided with the graphene-based composite as herein described.
- Relevant antimicrobial characteristics are those well known in the art and include the prevention or reduction in the colonisation of microbes such as bacteria or fungi on the substrate.
- a substrate comprising the graphene-based composite in accordance with the invention has been found to prevent or reduce colonisation of microbes such as bacteria and fungi, relative to the same substrate that does not comprise the graphene-based composite according to the invention.
- a substrate comprising the graphene-based composite in accordance with the invention has been found to exhibit microbicidal or microbiostatic properties, for example bacteriostatic, bactericidal, fungistatic and/or fungicidal properties.
- Antimicrobial properties of a substrate can be determined by techniques know in the art.
- a substrate that exhibits the improved antimicrobial properties according to the present invention will of course be a substrate that in its own right is susceptible to microbial colonisation.
- the present invention can provide a substrate that is susceptible to microbial colonisation with improved antibacterial properties.
- substrates that are susceptible to microbial colonisation include those comprising cellulosic material, polymer, glass, metal, ceramic and combinations thereof.
- substrates that are susceptible to microbial colonisation include those comprising cellulosic material, polymer, glass, metal, ceramic and combinations thereof.
- cellulosic material include those herein described.
- Examples of polymer include those herein described.
- Examples of glass include those herein described.
- Examples of metal include those herein described.
- the antimicrobial properties of a substrate comprising the graphene-based composite in accordance with the invention are antibacterial and/or antifungal properties.
- microbe or associated terms such as "microbial” and “microbial organism” is intended to mean any organism that exists as a microscopic cell that is included within the domains of archaea bacteria or eukarya. Accordingly, the term is intended to encompass prokaryotic or eukaryotic cells or organisms having a microscopic size and includes bacteria, archaea and eubacteria of all species as well as eukaryotic microorganisms such as yeast and fungi. Relevant microbes also include Gram-positive bacteria and Gram-negative bacteria.
- the excellent antimicrobial properties imparted to the substrate by the graphene-based composite are believed to operate through a number of mechanisms. Without wishing to be limited by theory, it is believed the antimicrobial properties relate to the destructive lipid extraction by the sharp edged graphene-based material which destroys the microbe membrane integrity and intertwining microbe pores that creates perturbation of the cell membrane, and charge transfer between the graphene-based material sheet and microbial cells causing DNA damage. Furthermore, the presence of the hydrated sodium metaborate in the composite is also believed to impart an antimicrobial effect in itself. Where the substrate is comes into contact with an aqueous environment, hydrated sodium metaborate can advantageously be slowly leached form the composite to impart such an antimicrobial effect. Accordingly, the composite as a whole is believed to impart effective antimicrobial character to the substrate.
- Figure 6 shows bacteria colonies at time zero and 24 hours presented on petri-dished coated with nothing (glass control), graphene oxide (GO control), reduced graphene oxide (rGO by ⁇ 2 ⁇ 2 ), and the graphene-based composite according to the invention (rGO/SMB). Only the rGO/SMB sample showed a significant reduction in bacteria colonisation after 24 hours. Improved abrasion resistance properties of a substrate
- the graphene-based composite according to the present invention can impart improved abrasion resistance properties to a substrate.
- the substrate can be provided with the graphene-based composite as herein described.
- abrasion resistance characteristics are those well known in the art and include measuring the amount of wear upon being subjected to an abrasive force.
- a substrate comprising the graphene-based composite in accordance with the invention has been found to exhibit improved abrasive wear, relative to the same substrate that does not comprise the graphene-based composite according to the invention.
- Abrasion resistance of a substrate can be determined by techniques know in the art. Such techniques include ASTM D4060.
- a substrate that exhibits the improved abrasion resistance according to the present invention will of course be a substrate that in its own right is susceptible to abrasion.
- the present invention can provide a substrate that is susceptible to abrasion with improved abrasion resistance.
- substrates that are susceptible to abrasion resistance include those comprising cellulosic material, polymer, glass, metal, ceramic and combinations thereof.
- cellulosic material examples include those herein described.
- polymer examples include those herein described.
- Examples of glass include those herein described.
- Examples of metal include those herein described.
- Ceramic examples include those herein described.
- the excellent abrasion resistance imparted to the substrate by the graphene-based composite are believed to operate through a number of mechanisms. Without wishing to be limited by theory, it is believed the abrasion resistance operates through a combination of lubricity afforded by the graphene based material, the strong internal binding of the composite structure afforded by the hydrated sodium metaborate, and the strong binding of the graphene-based composite to the substrate also afforded by the hydrated sodium metaborate. Accordingly, the composite as a whole is believed to impart a robust abrasion resistant system to the substrate.
- FIG. 7 shows comparative characterization of adhesion and abrasion characteristics of the graphene-based composite according to the invention (rGO/SMB) relative to graphene oxide (GO-control) and reduced graphene oxide (rGO-control) on Cu and glass substrates.
- Parts (a- d) show cross-cut scratch tape adhesion test (ASTM D3359-09e2) of coating deposited on the Cu and glass substrate, with (a & d) being GO (control), (b & e) being rGO (control), and (c & f) being rGO/SMB.
- Parts (a-d) illustrate the varied adhesion between graphene-based composite and the substrate, with parts (c & f) showing the best results with little if no damage to the graphene-based composite after the adhesion test.
- Part (g) shows abrasion type after abrasion test that combines micro dents and parallel groves identified on the coated surface
- part (h) shows the weight loss behaviour with different abrasion length of the coated surface.
- Graphite flakes ( ⁇ 45 ⁇ ) were chemically exfoliated following the improved Hummers method.
- the complete reaction was performed using a 9: 1 ratio of H 2 S0 4 /H 3 P0 4 (360:40 ml) with 18 g of KMn0 4 for the oxidation of 3 g of graphite flakes.
- Exfoliation proceeded at 50 °C while stirring for 12 h. The solution was then cooled to room temperature and poured onto ice cubes (300 ml) with 3 ml of 30% H 2 O 2 .
- Reduced-GO was prepared by reducing 50 ml of aqueous dispersion of GO (3.5 mg/ml) with a certain amount of NaBH 4 as reducing agent to form a mixer of O. l mol L "1 NaBH 4 and then refluxed and stirred at 60 °C for 8 hr. The reaction simultaneously produced hydrated sodium metaborate resulted from the hydrolysis of NaBH 4 in the solution (shown in Equation 1).
- the final solution contains rGO and hydrated-SMB that form the graphene based composite upon removing water by curing with heat.
- Graphene Oxide was chemically reduced following the methods provided in the literature using Hydrazine (N2H4) in aqueous solution of GO (1 ⁇ for 3 mg of GO). Subsequently, hydrated- sodium metaborate was mixed from external sources to prepare aqueous solution of reduced-GO and dissolved hydrated-SMB varying the composition percentage between 40 to 80 wt%.
- the prepared rGO/SMB solution was deposited on the substrate by drop casting or spraying method on copper flat plates (3 cm x 3 cm x 0.2 cm) and glass slides (2.5 cm X 3.5 cm) covering the entire area (from edge to edge) and then dried in the oven at 60 °C for 3 h. Comparative coatings with control solutions of GO, rGO and were prepared using the same conditions. For abrasion testing, the coated graphene-based surfaces were placed under Taber abrasion test (ASTM D4060).
- Scanning electron microscope (SEM-FEI QUANTA 450, Japan) was used to analyze the GO and rGO surface morphology, as well as to measure the coating thickness of the vertically aligned sample at an accelerating voltage of 5 KV.
- the energy dispersive X-ray (EDX) unit was used to capture the elemental peaks of rGO coatings containing sodium metaborate crystals at 5.0 KV.
- a high resolution Philips CM200, Transmission Electron Microscope (TEM), Japan was used for imaging the exfoliated GO flakes at 200 KV.
- TEM sample was prepared by dispersing the synthesized GO in ethanol to form a homogeneous dispersion.
- a Nikon Optical Petrographic Microscope (LV100 POL, USA) was used to analyze the cross-cut surfaces in order to mark the adhesion grade. Vibrational stretching mode of different oxygen functional groups in GO and rGO were studied by Fourier transform infrared spectroscopy (FTIR) (Nicolet 6700 Thermo Fisher, USA). TGA (Thermogravimetric analysis) and DTG (Derivative Thermogravimetry) of treated and untreated sawdust were analysed by a TA instruments (Q-500, Tokyo, Japan) in air atmosphere. The temperature was raised from ambient temperature to 600 °C at a rate of 5 °C/min for the combustion in air environment.
- FTIR Fourier transform infrared spectroscopy
- TGA Thermogravimetric analysis
- DTG Derivative Thermogravimetry
- Thermogravimetric analysis coupled with Fourier transform infrared (TGA-FTIR) for the real time analysis of multiple gas phase compounds released from the combustion samples were done by a PerkinElmer TG-IR EGA System connected to TL 8000 (TG-IR EGA, PerkinElmer Ltd, UK). The operation is accomplished in air atmosphere for an approximately sample mass of 16 mg at a rate of 6 °C/min.
- the adhesion of rGO/SMB coatings to the metal (Cu) and glass (microscope slide) substrates were measured according to the standard tape test ASTM D3359-09e2.
- the cross-cut adhesion test kit (QFH-HG600) was purchased from Biuged Laboratory Instruments (Guangzhou, China) .
- the cutting tool blade comprised eleven teeth spaced 1.0 mm apart.
- Coated substrates were placed on the lab bench supported by the guide rail before using the cutting tool. After the cross-cut pattern was applied (at approximately 90°) any detached flakes of the coating were removed with the kit's brush and scotch tape was placed over the cross-cut with gentle pressure.
- the cut samples were examined with a high magnification microscope (Nikon- Petrographic Microscope) and rated according to the ASTM rating scheme.
- a quantitative assessment of the antibacterial efficiency of GO, rGO and rGO/SMB coated glass swatches was done against gram-negative bacteria E. coli (ATCC 25922) according to the AATCC test method 100-2004. Bare glass slide and GO coated slides were performed as primary and secondary controls. Regarding the coated samples, the glass slides (2.5 cm x 2.0 cm) were drop cast with 0.8 ml solution at an original concentration of 3 mg/ml of graphene derivatives. Coated and uncoated samples were separately placed in a sterile micro plate (6 wells) and inoculated with 0.35 mL of overnight incubated bacterial suspension (10 CFU/mL).
- each sample was placed in a 50 mL of saline solution (0.85% (w/v)) and was strongly shaken for 1 min. To measure the number of bacteria at zero time, the samples were placed in saline solution immediately after inoculation. The total bacterial count was determined by serial dilution and pour plate method using Luria-Bertani agar medium plates (10 g peptone, 5 g yeast extract, 10 g NaCl and distilled water up to 1 L; pH-7) incubated at 37 °C for 48 h. The antibacterial efficiency of all samples was calculated using Equation (2):
- R is the bacterial reduction percentage
- Co and C 24 are the bacterial count immediately after inoculation and after incubation for 24 h, respectively.
- the prepared aqueous solution of rGO/SMB makes a homogeneous mixture where SMB is dissolved state.
- 2.6 g of purified pine sawdust 500 ⁇ to 1 mm were treated with the 50 ml of rGO/SMB into a beaker and kept stirring for 5 hour at 70 °C.
- the dried sawdust sample was impregnated with SMB and found well coated with the rGO/SMB composite.
- the test for smoke and volatiles suppression was carried out inside a one end closed glass cylinder of 4 cm inner diameter so that the smoke and volatiles can be visually observed.
- Two small beakers (10 ml) containing 300 mg of preheated (at 80 °C) sawdust (treated and untreated) were placed on a hot surface (300 °C).
- the hot plate was allowed to be thermally stable at 300 °C for 10 min before placing the samples.
- the beakers with samples were covered by two similar glass cylinders for the observation.
- the instant reaction of samples placed on the hot plate was recorded for 30 min by a high definition video camera (Sony HDR-PJ260).
- both the untreated and treated sawdust 80 mg were placed on a screen mesh well-set above a Bunsen burner (3 cm apart from the tip of burner) to be in contact to the flame.
- the flame height and gas flow of Bunsen burner was set by keeping a half quarterly opened air hole that is constant for both type of the samples and placed in the middle of the flame.
- the combustion phenomena self-igniting, flame propagation were recorded for further analysis by a high definition video camera (Sony HDR- PJ260).
- pellets of a dimension of 120 mm x 13 mm x 3.5 mm were made out of untreated and treated sawdust under a hydraulic pressure of 5 ton.
- the fire retardant behaviour of these pellets were assessed by UL-94 standardized vertical burning tests. Five specimens of each type of samples were measured to ensure reproducibility of data and to grade their flammability. The time until the flame extinguished itself and the distance the burn propagated have been measured, then figured out the linear burning rate in mm per minute.
- the exfoliation of GO sheets from graphite was determined by transmission electron microscope (TEM).
- TEM transmission electron microscope
- the simultaneous reduction of GO and formation of SMB by hydrolysis of NaBH 4 forms an aqueous solution of rGO/SMB.
- the presence of hydrated-SMB between (intercalated) and on top of the rGO sheets was confirmed by TEM.
- EDX Electro-dispersive X-ray
- of the so formed graphene -based composite showed elemental peaks of boron (B), carbon (C), oxygen (O) and sodium (Na) at 0.185, 0.277, 0.523 and 1.040 KeV, respectively confirming the existence of SMB on the rGO surfaces.
- Thermogravimetric analysis of GO and rGO/SMB composite shows significant difference in the mass loss profiles.
- the GO sample shows a first stage mass loss (14.45 %) from ambient temperature to 100 °C due to the evaporation of water molecules in the GO structure, which is slightly greater than rGO/SMB at this stage.
- the GO sample In the second stage between 100 °C to 250 °C, the GO sample has a massive mass loss (54.68 %) principally attributed to the removal of oxygen functional groups, whereas the rGO/SMB shows 25.72 % loss caused by the release of additional water molecules from the hydrated- SMB.
- the anhydrous sodium metaborate and rGO exists when the temperature exceeds 350 °C.
- the modification and coating of pine-sawdust was achieved by a solution treatment of an aqueous-rGO that contains dissolved-SMB.
- the loading was performed by soaking sawdust into the rGO/SMB solution.
- the dried mass of the treated sample increased by -14.67 % which did not make a huge difference in the total heat released ( ⁇ 460 Cal/gram) between the samples which was determined by a high pressure (3000 KPa) oxygenated combustion of both the untreated and treated sawdust in a bomb calorimeter.
- the evolution of gaseous products and volatiles suppression was analysed by FTIR.
- the presence of water above 250 °C was caused by the cleavage of aliphatic hydroxyl groups confirmed by the appearance of bands at 4000 - 3500 cm " '.
- the characteristic peaks at 3000 - 2730 cm “1 indicated the existence of methane, which was evolved between 250 °C to 300 °C as a result of cracking methoxyl (OCH 3 -) and methyl (CH 3 -).
- the methylene group (- CH 2 -) at high temperature also generated methane (CH 4 ).
- the intensity peak of carbon dioxide (C0 2 ) enhances at 2400-2260 cm “1 .
- the large amount of C0 2 release is caused by the cracking of cellulose and lignin, and the carbonized char burning at this temperature.
- the incomplete combustion of the pine sawdust also generated carbon monoxide (CO) as identified at 2260 -1990 cm -1 between the temperatures from 300 °C to 350 °C.
- Absorptions at 900 and 650 cm -1 were assigned to C-H stretching for aromatic hydrocarbons.
- the organic volatile compounds aldehyde or ketone, phenols, alkanes, alkenes and aromatic hydrocarbon
- Water content was identified at 4000 - 500 cm "1 since the beginning of the heating process from 100 to 350 °C as the treated sawdust contained relatively more water molecules because of the presence of hydrated sodium metaborate.
- the bonded water molecules were released in two steps; once between 83 and 155 °C and second between 249 and 280 °C.
- the intensity of other gases (CH 4 , C0 2 , CO, organic compounds) released from the treated samples were significantly lower at the selected temperatures possibly attributed to the impermeable gaseous barrier effect from the graphene-base composite.
- the barrier effect of the graphene- base composite has also been realized by a visual inspection when the treated and untreated samples were placed on a hot plate set at 300 °C for 30 min after a preheating at 80 °C to ensure the loss of additional moisture.
- the untreated sawdust begun to release smoke (possibly C0 2 ) and moisture (from aliphatic hydroxyl groups) at 3 min and the release of other organic volatiles (yellow and brown) was also observed between 10 to 20 min, whereas, the treated sawdust showed no significant release of observable organic volatiles.
- the coated and modified loose sawdust also exhibits outstanding performance to resist flame propagation, when 80 mg of samples were placed on the screen mesh above a Bunsen burner at a distance of 3 cm from the tip of the burner.
- the untreated sawdust started to propagate a flame between 15 to 20 s that was reinforced at 25 s and finally burned out within 70 s.
- the treated sawdust samples showed no self-ignition behaviour during the burning for 100 s.
- the fire-retardant behaviour was further assessed by vertical burning tests (UL-94) using the samples (120 mm x 13 mm x 3.5 mm) made from uncoated and coated sawdust.
- the coated wooden pellet displayed excellent fire-retardancy with no flame propagation behaviour for the wooden pellet made from the treated sawdust. No flaming and glowing combustion was observed for each of the five treated specimens; hence the material is graded as V-0.
- Each burning for the treated specimen ceased instantly with no vertical lift of the flame, whereas the untreated sawdust pellet showed higher degree of flammable properties that continued till the end (up to the holding clamp) with an approximate linear burning rate of 0.5 mm/s.
- the rGO/SMB composite is demonstrated to exhibit a very high degree of fire retardant properties when applied on a flammable rag paper.
- the hydrated-SMB with graphene showed efficient intumescent effect and self-extinguishing properties to protect the underneath flammable material from fire for an extended period of time.
- Graphene material in two forms namely reduced Graphene Oxide (GO) prepared by chemical, thermal reduction or any other process, or graphene prepared synthetically or from graphite by electrochemical, thermal/mechanical or any other process, were used to make graphene fire- retardant composite solution.
- Graphene aqueous solution with a concentration of 2-10% was mixed with hydrated- sodium metaborate to make dissolved hydrated-SMB varying the composition percentage between 10 to 80 wt%.
- Composite formulation (powder based) were prepared using solution based formulation-A by drying followed by grinding the formed products by grinder or ball milling to form fine powder composed with graphene sheets decorated with inorganic metal hydrates such as SMB nanoparticles. Preparation of non flammable polymer materials (part A)
- Water soluble polymer materials e.g. polyvinyl alcohol (PVA)
- PVA polyvinyl alcohol
- Solvent soluble polymer materials e.g. polystyrene
- Solvent soluble polymer materials in the form of pellets, granules or powder was dissolved in DMF and mixed with formulation- A or powder based formulation-B, with concentration 20wt% to 50 wt% of the mixture. The mixture was stirred at 115 °C for 3 hours followed by casting or extrusion process to make non-flammable polymer (see Figure 9).
- the overall thickness of the rGO/SMB coatings fabricated for the cross-cut adhesion test was ⁇ 2 ⁇ as determined by optical profilometry and SEM.
- Table 1 shows the adhesion performance of the coated samples with different comparative coating formulations rated following the standard ASTM-class for both copper (Cu) and glass substrates. These results show that the rGO/SMB coating had the best adhesion to both the Cu and glass surfaces, also as shown in Figure 7 (b) and (e) as determined by the cross-cut adhesion test followed by the scotch tape procedure.
- Control (N 2 H 4 reduced) rGO coatings were prepared to compare with the rGO/SMB coating to examine the inherent adhesion of the material to the Cu and glass substrates.
- the coatings made from the sample (rGO-N 2 H 4 ) failed to show appreciable minimal adhesion (ASTM class 0B) to either of the Cu and glass substrates.
- the deposition of rGO with and without SMB revealed that the coating without SMB did not have any adhesion properties as determined by the cross-cut adhesion test.
- the ASTM adhesion of GO and rGO (reducing agent N 2 H 4 ) on both the Cu and glass substrates was found to be OB (considered as undefined or no adhesion), whereas the rGO/SMB sample showed an ASTM adhesion rating of 4B (less than 5 % cross cut area was demonstrated as affected) for both the Cu and glass substrate.
- the rGO/SMB coating was also applied to other metals (i.e. aluminium (Al), stainless steel) and results confirmed that the adhesion is independent to the metal substrate.
- the adhesion strength between the metal plate and coating is likely formed between the native metal oxide and borate interface.
- the abrasion test results a minimal weight loss (6.33 mg/cm 2 , max m ) after the completion of -3000 cycles under a load of 250 g of each wheel.
- the surface morphology of rGO/SMB sample before and after the abrasion test have been shown in Figure 7 (g and h) for the comparison where SMB-crystals were found to be homogeneously distributed on both the abrasive and non-abrasive surface. Patterns of the wear damage could be clearly classified as parallel grooves and multiple indentations as shown by the red arrows in Figure 7 (h).
- the micro indentation is created from the loss of SMB-crystal during the abrasion test.
- a Raman mapping of the abrasive surface was performed to analyse the area percentage of components occupied in the inner coating layers, which showed that about 71 % was occupied by rGO and 29 % for SMB-crystals.
- the antibacterial properties of the uncoated (glass slide) and coated (GO, rGO- N 2 H 4 and rGO/SMB) samples were evaluated by AATCC Test Method 100-2004.
- the bacterial strain similarly grew well on all tested samples at zero time, while the growth was further enhanced only on the uncoated (control) sample after 24 h.
- Other samples containing graphene derivatives showed strong antibacterial activity at a uniform concentration of GO as the starting material (3 mg/ml) after 24 h ( Figure 6).
- GO was found to reduce 85.34 % E. coli colonies, whereas rGO- N 2 H 4 was less effective (54.47 %) than GO.
- the antibacterial ability of rGO/SMB (99.9%) outperformed the GO and rGO-N 2 H 4 coatings.
- the presence of SMB on/in the rGO sheets increases the wettability (-32° WCA) of the rGO/SMB composite coating in comparison to the rGO-N 2 H 4 coating ((-84° WCA) that may reinforce the interaction between the graphene sheets and bacterium.
- a strong antibacterial effect of the graphene-based composite has been demonstrated showing almost 100 % resistance against the colonization of E.coli bacteria with significantly better performance compared with the GO and the rGO used as a control.
- the results suggest that surface wettability should be taken as an active parameter that may affect the antibacterial properties the graphene based composite.
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