TW202340387A - Composite material including three-dimensional (3d) graphene - Google Patents
Composite material including three-dimensional (3d) graphene Download PDFInfo
- Publication number
- TW202340387A TW202340387A TW112111813A TW112111813A TW202340387A TW 202340387 A TW202340387 A TW 202340387A TW 112111813 A TW112111813 A TW 112111813A TW 112111813 A TW112111813 A TW 112111813A TW 202340387 A TW202340387 A TW 202340387A
- Authority
- TW
- Taiwan
- Prior art keywords
- composite material
- ppgma
- carbon particles
- carbon
- composite
- Prior art date
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 349
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 339
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 259
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 257
- 239000011148 porous material Substances 0.000 claims abstract description 125
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 67
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000012798 spherical particle Substances 0.000 claims abstract description 6
- 239000004743 Polypropylene Substances 0.000 claims description 49
- 229920001155 polypropylene Polymers 0.000 claims description 49
- -1 polypropylene Polymers 0.000 claims description 41
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 33
- 238000011068 loading method Methods 0.000 claims description 31
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 238000012805 post-processing Methods 0.000 claims description 13
- 238000005516 engineering process Methods 0.000 claims description 12
- 230000003993 interaction Effects 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 10
- 238000000748 compression moulding Methods 0.000 claims description 10
- 238000005452 bending Methods 0.000 claims description 8
- 238000001746 injection moulding Methods 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 7
- 239000011152 fibreglass Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000001175 rotational moulding Methods 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 238000001721 transfer moulding Methods 0.000 claims description 5
- 239000004711 α-olefin Substances 0.000 claims description 5
- 238000000071 blow moulding Methods 0.000 claims description 4
- 230000007423 decrease Effects 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 230000001965 increasing effect Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000002787 reinforcement Effects 0.000 claims description 4
- 238000007906 compression Methods 0.000 claims description 3
- 230000006835 compression Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000012778 molding material Substances 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 238000009787 hand lay-up Methods 0.000 claims 1
- 238000010107 reaction injection moulding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 30
- 239000003575 carbonaceous material Substances 0.000 description 24
- 238000001000 micrograph Methods 0.000 description 21
- 238000010586 diagram Methods 0.000 description 16
- 239000000945 filler Substances 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 11
- 230000006870 function Effects 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 230000002776 aggregation Effects 0.000 description 8
- 239000011162 core material Substances 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 7
- 229920000602 Poly[(isobutylene-alt-maleic acid, ammonium salt)-co-(isobutylene-alt-maleic anhydride)] Polymers 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229920000092 linear low density polyethylene Polymers 0.000 description 6
- 239000004707 linear low-density polyethylene Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920001169 thermoplastic Polymers 0.000 description 6
- 239000004416 thermosoftening plastic Substances 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- 229920001021 polysulfide Polymers 0.000 description 4
- 239000005077 polysulfide Substances 0.000 description 4
- 150000008117 polysulfides Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000004696 Poly ether ether ketone Substances 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229920002530 polyetherether ketone Polymers 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000012815 thermoplastic material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 2
- 229920003189 Nylon 4,6 Polymers 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229920006258 high performance thermoplastic Polymers 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000011156 metal matrix composite Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- UKQJDWBNQNAJHB-UHFFFAOYSA-N 2-hydroxyethyl formate Chemical compound OCCOC=O UKQJDWBNQNAJHB-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002928 artificial marble Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011153 ceramic matrix composite Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 229920000431 shape-memory polymer Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011145 styrene acrylonitrile resin Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 238000007666 vacuum forming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0013—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor using fillers dispersed in the moulding material, e.g. metal particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0011—Combinations of extrusion moulding with other shaping operations combined with compression moulding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Medicinal Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本揭示案通常係關於複合材料,並且更具體而言,係關於包括各種負載水準之樹脂、順丁烯二酸化共聚物、及3D石墨烯以便達成合意黏性機械性質的複合材料。 The present disclosure relates generally to composite materials, and more specifically to composite materials including various loading levels of resins, maleated copolymers, and 3D graphene to achieve desirable adhesive mechanical properties.
複合材料由兩種或兩種以上具有不同化學及/或物理性質之構成材料產生,該等材料可合併以使得複合材料具有不同於兩種或兩種以上構成材料之性質。在一些情況下,構成材料可保持分離及不同,從而可將複合材料與諸如混合物及固溶體之其他物質區分開來。在複合材料內,聚丙烯-有機黏土奈米複合物可使用諸如聚丙烯(PP)、順丁烯二酸酐修飾之聚丙烯寡聚物(PPgMA)、及由十八烷基銨修飾之黏土的三種構成材料之雙螺桿擠塑,經由熔體處理來製備。另外,可藉由改變奈米複合物上之PPgMA之百分比及/或PPgMA之功能化程度來使PP及奈米黏土相容。雖然已觀察到與習知材料有關的物理性能(例如,抗拉強度、韌性等)之一些增加,但是所評估複合物不包括三維(3D)石墨烯,其可賦予有益性質。複合材料中之改良為合乎需要的。 Composite materials are produced from two or more constituent materials with different chemical and/or physical properties that can be combined so that the composite material has properties different from those of the two or more constituent materials. In some cases, the constituent materials may remain separate and distinct, thereby distinguishing the composite from other substances such as mixtures and solid solutions. In composite materials, polypropylene-organoclay nanocomposites can use materials such as polypropylene (PP), maleic anhydride-modified polypropylene oligomer (PPgMA), and clay modified by stearyl ammonium. Twin-screw extrusion of three constituent materials is prepared by melt processing. In addition, PP and nanoclay can be made compatible by changing the percentage of PPgMA on the nanocomposite and/or the degree of functionalization of PPgMA. Although some increases in physical properties (eg, tensile strength, toughness, etc.) were observed with respect to conventional materials, the composites evaluated did not include three-dimensional (3D) graphene, which could impart beneficial properties. Improvements in composite materials are desirable.
提供此發明內容以便以簡化形式引入以下在實施方式中進一步描述的所選擇概念。此發明內容不意欲鑑別所主張標的物之關鍵特徵或必需特徵,亦不意欲限制所主張標的物之範圍。 This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to limit the scope of the claimed subject matter.
本揭示案所描述之標的物之一個創新態樣可實施為複合材料。例如, 在一些態樣中,複合材料可包括與聚丙烯接枝順丁烯二酸酐(PPgMA)混合之熱塑性樹脂的組合、在該組合中混合之複數個碳顆粒、及在複數個碳顆粒中形成之複數個孔隙。在一些情況下,複數個碳顆粒包括具有每單位體積相對較低濃度之碳顆粒的第一區域及具有每單位體積相對較高濃度之碳顆粒的第二區域。在一些態樣中,複數個碳顆粒中之至少一些具有暴露碳表面,該等表面具有經一或多種含氧基團來氧化並且鍵結至相鄰PPgMA分子上之分子位點的碳原子,其中複數個碳顆粒中之至少一些由複數個互連褶皺3D石墨烯片材或複數個非中空碳質球形顆粒(NHCS)中之一或多者形成,並且其中複合材料進一步包括80wt%與90wt%之間之熱塑性樹脂、0.5wt%與15wt%之間之PPgMA、及0.1wt%至7wt%之間之複數個碳顆粒。在一些情況下,複數個孔隙中之至少一些經組配成由PPgMA浸潤,碳原子之氧化與每單位體積與相鄰碳原子化學鍵結之至少一些PPgMA之增加相關。 One innovative aspect of the subject matter described in this disclosure may be implemented as a composite material. For example, In some aspects, the composite material may include a combination of a thermoplastic resin mixed with polypropylene grafted maleic anhydride (PPgMA), a plurality of carbon particles mixed in the combination, and a plurality of carbon particles formed in the Multiple pores. In some cases, the plurality of carbon particles includes a first region having a relatively low concentration of carbon particles per unit volume and a second region having a relatively high concentration of carbon particles per unit volume. In some aspects, at least some of the plurality of carbon particles have exposed carbon surfaces having carbon atoms oxidized through one or more oxygen-containing groups and bonded to molecular sites on adjacent PPgMA molecules, wherein at least some of the plurality of carbon particles are formed from one or more of a plurality of interconnected wrinkled 3D graphene sheets or a plurality of non-hollow carbonaceous spherical particles (NHCS), and wherein the composite material further includes 80wt% and 90wt Thermoplastic resin between 0.5wt% and 15wt%, PPgMA between 0.5wt% and 15wt%, and a plurality of carbon particles between 0.1wt% and 7wt%. In some cases, where at least some of the plurality of pores are configured to be wetted by PPgMA, oxidation of the carbon atoms is associated with an increase in at least some of the PPgMA chemically bonded to adjacent carbon atoms per unit volume.
在一些實行方案中,複合材料之密度在熱塑性樹脂之密度的+/-3%內。在一些態樣中,複合材料之密度至少部分地基於複數個孔隙之總孔隙體積。在一些其他情況下,複合材料具有500帕斯卡-秒(Pa-s)與2,100Pa-s之間之黏度。在一些態樣中,複合材料藉由注射模製來進行後處理。在一些情況下,按照ASTM D790,在23℃之溫度下,在1%割線模數值下,複合材料具有107,500磅/平方吋(PSI)與117,500PSI之間之抗彎模數。 In some implementations, the density of the composite material is within +/-3% of the density of the thermoplastic resin. In some aspects, the density of the composite material is based at least in part on the total pore volume of the plurality of pores. In some other cases, the composite material has a viscosity between 500 Pascal-seconds (Pa-s) and 2,100 Pa-s. In some aspects, the composite material is post-processed by injection molding. In some cases, according to ASTM D790, the composite material has a flexural modulus between 107,500 pounds per square inch (PSI) and 117,500 PSI at a 1% secant modulus value at a temperature of 23°C.
在一些其他實行方案中,在190℃之溫度下,複合材料具有4公克/min(g/min)至8g/min之間之可調熔體流動速率。在一些情況下,複合材料具有相對於原始大小的500%之最大拉伸伸長。在一些其他情況下,複數個碳顆粒中之至少一些與相鄰PPgMA分子相互作用增加複合材料之機械增強。在一些實行方案中,熱塑性樹脂包括線性低密度聚乙烯(LLDPE)樹脂、乙烯-丁烯共聚物、及α-烯烴。 In some other implementations, the composite material has an adjustable melt flow rate between 4 grams per minute (g/min) and 8 g/min at a temperature of 190°C. In some cases, the composite material has a maximum tensile elongation of 500% relative to the original size. In some other cases, at least some of the plurality of carbon particles interact with adjacent PPgMA molecules to increase the mechanical strengthening of the composite. In some implementations, thermoplastic resins include linear low density polyethylene (LLDPE) resins, ethylene-butylene copolymers, and alpha-olefins.
在一些實行方案中,複數個碳顆粒中之各者進一步包括複數個非三區段顆粒及複數個三區段顆粒,其中各三區段顆粒包括彼此纏結並且藉由中型孔隙來彼此分隔的複數個碳片段,及與一或多個相鄰非三區段顆粒或三區段顆粒聚結的可變形周界。在一些情況下,複數個碳顆粒中之各者進一步包括複數個聚集物,各聚集物包括接合在一起的多個三區段顆粒,各聚集物具有10奈米(nm)與10微米(μm)之間之範圍內的主要尺寸。在一些情況下,複數個碳顆粒中之各者進一步包括散佈在複數個聚集物中之複數個中型孔隙,各中型孔隙具有3.3奈米(nm)與19.3nm之間之主要尺寸。在一些情況下,複數個碳顆粒中之各者進一步包括複數個附聚物,各附聚物包括彼此接合之多個聚集物,並且各附聚物具有0.1μm與1,000μm之間之近似範圍內的主要尺寸。在一些情況下,複數個碳顆粒中之各者進一步包括散佈在複數個聚集物中之複數個大孔隙,各大孔隙具有0.1μm與1,000μm之間之主要尺寸。 In some implementations, each of the plurality of carbon particles further includes a plurality of non-three-segment particles and a plurality of three-segment particles, wherein each three-segment particle includes entangled with each other and separated from each other by mesopores. A plurality of carbon segments, and a deformable perimeter coalesced with one or more adjacent non-three-segment particles or three-segment particles. In some cases, each of the plurality of carbon particles further includes a plurality of aggregates, each aggregate including a plurality of three-segment particles joined together, each aggregate having a thickness of 10 nanometers (nm) and 10 micrometers (μm). ). In some cases, each of the plurality of carbon particles further includes a plurality of meso-sized pores dispersed within the plurality of aggregates, each meso-sized pore having a major dimension between 3.3 nanometers (nm) and 19.3 nm. In some cases, each of the plurality of carbon particles further includes a plurality of agglomerates, each agglomerate includes a plurality of aggregates joined to each other, and each agglomerate has an approximate range between 0.1 μm and 1,000 μm. Main dimensions within. In some cases, each of the plurality of carbon particles further includes a plurality of macropores dispersed within the plurality of aggregates, each macropore having a major dimension between 0.1 μm and 1,000 μm.
在其他實行方案中,三區段顆粒包括第一區段、第二區段、及第三區段,其中第一區段由第二區段囊封,並且第二區段由第三區段囊封。在一些情況下,第一區段具有近似1.5g/cc與5.0g/cc之間之密度,並且第二區段具有近似0.5g/cc與3.0g/cc之間之密度。在其他情況下,第一區段包括具有近似小於40nm之孔隙寬度的孔隙,第二區段包括具有近似小於35nm之孔隙寬度的孔隙,並且第三區段包括具有近似小於30nm之孔隙寬度的孔隙。在各種態樣中,複數個碳顆粒包括氮摻雜碳顆粒。 In other implementations, the three-segment particle includes a first segment, a second segment, and a third segment, wherein the first segment is encapsulated by the second segment, and the second segment is encapsulated by the third segment. Encapsulated. In some cases, the first section has a density between approximately 1.5 g/cc and 5.0 g/cc, and the second section has a density between approximately 0.5 g/cc and 3.0 g/cc. In other cases, the first segment includes pores with a pore width of approximately less than 40 nm, the second segment includes pores with a pore width of approximately less than 35 nm, and the third segment includes pores with a pore width of approximately less than 30 nm. . In various aspects, the plurality of carbon particles include nitrogen-doped carbon particles.
在一些其他實行方案中,PPgMA包括0.0wt%-1.3wt%之間之順丁烯二酸酐(MA),及98.7wt%-100wt%之間之聚丙烯(PP)。在一些情況下,在複合材料中包括碳顆粒增加複合材料之抗彎模數或抗拉強度。在一些態樣中,各孔隙具有0.05立方公分/公克(cm3/g)與1.5cm3/g之間之孔隙體積。 In some other implementations, PPgMA includes between 0.0wt% and 1.3wt% of maleic anhydride (MA), and between 98.7wt% and 100wt% of polypropylene (PP). In some cases, including carbon particles in the composite increases the flexural modulus or tensile strength of the composite. In some aspects, each pore has a pore volume between 0.05 cubic centimeters per gram (cm 3 /g) and 1.5 cm 3 /g.
本揭示案描述之標的物之一或多個實行方案之細節在附圖及以下說明書中闡明。其他特徵、態樣、及優勢自說明書、附圖、及請求項變得顯而易知。注意以下圖式之相對尺寸可不按比例繪製。 Details of one or more implementations of the subject matter described in this disclosure are set forth in the accompanying drawings and the description below. Other features, aspects, and advantages will become apparent from the description, drawings, and claims. Note that the relative dimensions of the following figures are not drawn to scale.
100:顯微照片 100:Micrograph
110:顯微照片 110:Micrograph
115:碳顆粒 115: Carbon particles
116:碳附聚區域 116: Carbon agglomeration area
117:第一區域 117:First area
118:第二區域 118:Second area
119:額外區域 119:Extra area
120:顯微照片 120:Micrograph
126:均勻分散區域 126: Uniformly dispersed area
200:顯微照片 200:Micrograph
205:石墨烯材料 205:Graphene material
210:波浪狀或褶皺形態石墨烯材料 210: Wavy or wrinkled graphene material
300:顯微照片 300:Micrograph
305:基於微波能量之波浪狀及/或起皺石墨烯 305: Wave-shaped and/or wrinkled graphene based on microwave energy
310:sp3-雜交聚合物鏈 310:sp3-hybrid polymer chain
315:脊及谷 315: Ridges and valleys
400:顯微照片 400:Micrograph
405:碳顆粒 405: Carbon particles
410:第一多個孔隙 410:First multiple pores
415:二級碳顆粒 415: Secondary carbon particles
420:第二多個孔隙 420: The second plurality of pores
500A:三區段顆粒 500A: three-section particles
500B:三區段顆粒 500B: three-section particles
501:第一區段 501: First section
502:第二區段 502:Second section
503:第三區段 503: The third section
505:外部殼 505:External shell
511:孔隙 511:pore
512:孔隙 512:pore
513:孔隙 513:pore
600:圖表 600: Chart
700:顯微照片 700:Micrograph
702:碳結構 702:Carbon structure
704:聚集物 704: Aggregation
706:附聚物 706:Agglomerates
750:顯微照片 750:Micrograph
752:外部碳殼型結構 752:External carbon shell structure
754:其他碳殼型結構 754: Other carbon shell structures
756:碳結構 756:Carbon structure
758:核心區域 758:Core area
760:顯微照片 760:Micrograph
800:圖表 800: Chart
900:組態 900:Configuration
905:寬度 905:Width
910:第一多孔碳區域 910: First porous carbon region
911:第一非三區段顆粒 911: The first non-three-section particle
912:第一三區段顆粒 912: The first and third section particles
913:第一碳片段 913: First carbon fragment
914:中型孔隙 914:Medium pores
915:第一可變形周界 915: The first deformable perimeter
916:第一聚集物 916:First aggregate
917:第一附聚物 917: First agglomerate
918:大孔隙 918: Large pores
920:第二多孔碳區域 920: Second porous carbon region
921:第二非三區段顆粒 921: The second non-three-section particle
922:第二三區段顆粒 922: Second and third section particles
923:第二碳片段 923:Second carbon fragment
925:第二可變形周界 925: The second deformable perimeter
926:第二聚集物 926:Second aggregate
927:第二附聚物 927: Second agglomerate
1000:略圖 1000: Sketch
1005:化學結構組分 1005: Chemical structural components
1100:化學結構 1100:Chemical structure
1105:反應機制 1105:Reaction mechanism
1110:完成分子 1110:Complete numerator
1115:臭氧處理(氧化)石墨烯表面 1115: Ozone treatment (oxidation) of graphene surface
1200:圖表 1200: Chart
1300:圖表 1300: Chart
1400:圖表 1400: Chart
1500:條形圖 1500:Bar chart
1600:條形圖 1600:Bar chart
1700:圖表 1700: Chart
1800:圖表 1800: Chart
1900:圖表 1900: Chart
2000:圖表 2000: Charts
2100:圖表 2100: Chart
2200:圖表 2200: Chart
2300:操作 2300: Operation
2302:供應具有初始密度之熱塑性樹脂 2302: Supply of thermoplastic resin with initial density
2304:將聚丙烯接枝順丁烯二酸酐(PPgMA)之分散液在整個熱塑性樹脂中混合,該PPgMA由複數個互連PPgMA分子形成 2304: A dispersion of polypropylene grafted maleic anhydride (PPgMA), formed from a plurality of interconnected PPgMA molecules, is mixed throughout the thermoplastic resin.
2306:將複數個碳顆粒分佈在整個熱塑性樹脂及複數個互連PPgMA分子中,該複數個碳顆粒具有均勻分散在熱塑性樹脂與PPgMA之組合內的0.05立方公分/公克(cm3/g)與1.5cm3/g之間之孔隙體積 2306: Distribute a plurality of carbon particles throughout the thermoplastic resin and a plurality of interconnected PPgMA molecules, the plurality of carbon particles having a uniform distribution within the combination of the thermoplastic resin and PPgMA of 0.05 cubic centimeters per gram (cm3/g) and 1.5 Pore volume between cm3/g
2308:藉由旋轉模製來形成基於熱塑性樹脂、PPgMA、及複數個碳顆粒中之至少一些之組合的複合材料,其中藉由複數個碳顆粒中之至少一些來提供之碳原子與其相應相鄰互連PPgMA分子之間的化學鍵結經組配來增加複合材料之抗彎模數,同時將複合材料之最終密度保持在+/- 3%偏離熱塑性樹脂之初始密度的容許限度內,該容許限度基於孔隙體積 2308: Formation of a composite material based on a combination of a thermoplastic resin, PPgMA, and at least some of a plurality of carbon particles by rotational molding, wherein carbon atoms provided by at least some of the plurality of carbon particles are adjacent to their respective The chemical bonds between interconnected PPgMA molecules are configured to increase the flexural modulus of the composite while maintaining the final density of the composite within a tolerance of +/- 3% deviation from the initial density of the thermoplastic resin. Based on pore volume
2400:操作 2400: Operation
2402:在一或多個方向上壓縮該複合材料 2402: Compress the composite material in one or more directions
2404:基於複合材料之壓縮來形成片材或板材中之一或多者 2404: Compression of composite materials to form one or more sheets or plates
2500:操作 2500: Operation
2502:經由模頭來擠塑複合材料 2502: Extrusion of composite materials through the die
2504:基於複合材料之擠塑來形成物品 2504: Forming objects based on extrusion of composite materials
2600:操作 2600: Operation
2602:使用手工敷層過程或噴霧過程中之一或多者來製備模具 2602: Preparation of molds using one or more of a manual coating process or a spray process
2604:使用手壓輥來壓塑複合材料 2604: Compression molding of composite materials using hand rollers
2700:操作 2700:Operation
2702:乾燥複合材料來產生經乾燥之複合材料 2702: Drying composite materials to produce dried composite materials
2704:將經乾燥之複合材料***模具中 2704: Insert the dried composite material into the mold
2706:將額外樹脂及催化劑之混合物泵送至模具中 2706: Pump the additional resin and catalyst mixture into the mold
2800:操作 2800: Operation
2802:將複合材料之流***模具中 2802: Insert composite flow into mold
2804:將線性低密度聚乙烯(LLDPE)之流***模具中 2804: Insert linear low density polyethylene (LLDPE) stream into the mold
2806:將催化劑***模具中 2806: Insert the catalyst into the mold
2808:將複合材料、熱塑性樹脂、及催化劑在模具內混合 2808: Mix composite materials, thermoplastic resin, and catalyst in the mold
2900:操作 2900: Operation
2902:使用真空輔助樹脂傳遞模製(VARTM)技術對複合材料進行後處理,該技術包括使用真空,將複合材料抽吸至模具中 2902: Post-processing of composite materials using vacuum-assisted resin transfer molding (VARTM) technology, which involves using a vacuum to draw the composite material into the mold
3000:操作 3000: Operation
3002:經由圓筒形模具來擠塑複合材料以便產生複合線材 3002: Extrusion of composite materials through cylindrical molds to produce composite wires
3004:將複合線材沿著軸捲繞以便產生長纖維纏繞之複合物 3004: Winding composite wire along a shaft to produce long fiber wound composites
3100:操作 3100: Operation
3102:藉由傳送複合材料之線材穿過保持在22℃以上之浴,產生半熔融複合線材 3102: Semi-molten composite wire is produced by passing the wire of composite material through a bath maintained above 22°C.
3104:藉由經由一或多個導向器來傳送半熔融複合線材,形成物品 3104: Forming articles by conveying semi-molten composite wire through one or more guides
3200:操作 3200: Operation
3202:將複合材料切割成一或多個預定義圖案 3202: Cut composite material into one or more predefined patterns
3204:將一或多個預定義圖案鋪設在表面上 3204: Lay one or more predefined patterns on a surface
3206:使用心軸,在表面上之一或多個預定義圖案上軋製 3206: Using a mandrel, roll on one or more predefined patterns on the surface
3300:操作 3300: Operation
3302:形成複合材料之片材 3302: Sheets forming composite materials
3304:將切片玻璃纖維傾倒在複合材料片材頂部 3304: Pour sliced fiberglass on top of composite sheet
3306:用複合材料之額外層來覆蓋複合材料片材及切片玻璃纖維 3306: Covering composite sheets and sliced fiberglass with additional layers of composite material
3400:操作 3400: Operation
3402:將熔融狀態中之複合材料注射至模具中 3402: Inject the composite material in the molten state into the mold
3404:藉由將複合材料在模具內冷卻,自模具提取所形成產品 3404: Extracting the product from the mold by cooling the composite material in the mold
3500:操作 3500: Operation
3502:使用真空壓縮模製、旋轉模製、吹氣模製、或注射包覆模製中之一者,將複合材料模製成一或多個形狀 3502: Molding composite materials into one or more shapes using one of vacuum compression molding, rotational molding, blow molding, or injection overmolding
圖1示出根據一些實行方案,示範性複合材料之顯微照片。 Figure 1 shows a photomicrograph of an exemplary composite material, according to some implementations.
圖2示出根據一些實行方案,自石墨進行硫酸(H2SO4)剝離所產生之石墨烯材料之顯微照片。 Figure 2 shows a photomicrograph of graphene material resulting from sulfuric acid ( H2SO4 ) exfoliation from graphite, according to some implementations.
圖3示出根據一些實行方案,基於微波能量之波浪狀及/或起皺石墨烯之顯微照片。 Figure 3 shows a micrograph of wavy and/or wrinkled graphene based on microwave energy, according to some implementations.
圖4示出根據一些實行方案,示範性碳顆粒之顯微照片。 Figure 4 shows a photomicrograph of exemplary carbon particles, according to some implementations.
圖5A示出根據一些實行方案,示範性碳顆粒之略圖。 Figure 5A shows a schematic diagram of exemplary carbon particles, according to some implementations.
圖5B示出根據一些實行方案,代表圖5A之示範性碳顆粒之示範性階梯函數。 Figure 5B illustrates an exemplary step function representative of the exemplary carbon particles of Figure 5A, according to some implementations.
圖6示出根據一些實行方案,描繪示範性碳顆粒之孔隙體積相比於孔隙寬度之示範性分佈的圖表。 Figure 6 shows a graph depicting an exemplary distribution of pore volume versus pore width for exemplary carbon particles, according to some implementations.
圖7A示出根據一些實行方案,示範性碳顆粒、聚集物,及/或附聚物之顯微照片。 Figure 7A shows a photomicrograph of exemplary carbon particles, aggregates, and/or agglomerates, according to some implementations.
圖7B示出根據一些實行方案,示範性碳顆粒、聚集物,及/或附聚物之顯微照片。 Figure 7B shows a photomicrograph of exemplary carbon particles, aggregates, and/or agglomerates, according to some implementations.
圖8示出根據一些實行方案,描繪分散在示範性碳顆粒中之微孔隙及中型孔隙之累積孔隙體積相比於孔隙寬度的圖表。 Figure 8 shows a graph depicting cumulative pore volume versus pore width for micropores and mesopores dispersed in exemplary carbon particles, according to some implementations.
圖9示出根據一些實行方案,示範性碳顆粒之示範性組態。 Figure 9 illustrates an exemplary configuration of exemplary carbon particles, according to some implementations.
圖10示出根據一些實行方案,聚丙烯接枝順丁烯二酸酐(PPgMA)之化學結構之略圖。 Figure 10 shows a schematic diagram of the chemical structure of polypropylene grafted maleic anhydride (PPgMA), according to some implementations.
圖11示出根據一些實行方案,產生PPgMA及臭氧處理石墨烯表面之示範性化學反應機制。 Figure 11 illustrates an exemplary chemical reaction mechanism to produce PPgMA and ozone-treated graphene surfaces, according to some implementations.
圖12示出根據一些實行方案,描繪按照波數(cm-1)之強度(相對吸收率)之圖表。 Figure 12 shows a graph depicting intensity (relative absorbance) as a function of wave number (cm -1 ), according to some implementations.
圖13示出根據一些實行方案,描繪示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之抗彎模數(磅/平方吋,PSI)的圖表。 13 shows a graph depicting bending modulus (pounds per square inch, PSI) according to PPgMA loading level (ppH) relative to combined resin and filler weight for an exemplary composite, according to some implementations.
圖14示出根據一些實行方案,描繪示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(百分份數,ppH)之黏度(Pa˙s)的圖表。 Figure 14 shows a graph depicting viscosity (Pa˙s) of an exemplary composite as a function of PPgMA loading level (percent, ppH) relative to combined resin and filler weight, according to some implementations.
圖15示出根據一些實行方案,描繪示範性複合材料之未氧化碳材料(DX C/F)及臭氧(O3)處理碳顆粒之抗彎模數(PSI)的條形圖。 Figure 15 shows a bar graph depicting the bending modulus (PSI) of unoxidized carbon material (DX C/F) and ozone ( O3 ) treated carbon particles of an exemplary composite, according to some implementations.
圖16示出根據一些實行方案,描繪示範性複合材料之線性低密度聚乙烯(LLDPE)及聚丙烯(PP)之抗彎模數(PSI)的條形圖。 Figure 16 shows a bar graph depicting the flexural modulus (PSI) of linear low density polyethylene (LLDPE) and polypropylene (PP) of exemplary composites, according to some implementations.
圖17示出根據一些實行方案,描繪示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之抗彎模數(PSI)及斷裂伸長率(%)的圖表。 Figure 17 shows a graph depicting bending modulus (PSI) and elongation at break (%) as a function of PPgMA loading level (ppH) relative to combined resin and filler weight for an exemplary composite, according to some implementations.
圖18示出根據一些實行方案,示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH),所量測的超過純淨樹脂之抗彎模數增加百分比(%)的圖表。 Figure 18 shows a graph of measured percent increase (%) in flexural modulus over neat resin at PPgMA loading levels (ppH) relative to combined resin and filler weight for exemplary composites, according to some implementations. .
圖19示出根據一些實行方案,示範性複合材料之按照臭氧處理時間,臭氧(O3)處理過程中之氧含量(原子(at.)%)之圖表。 Figure 19 shows a graph of oxygen content (at.) % during ozone ( O3 ) treatment as a function of ozone treatment time for an exemplary composite material, according to some implementations.
圖20示出根據一些實行方案,示範性複合材料之量測密度(g/cm3)相比於理論密度(g/cm3)之圖表。 Figure 20 shows a graph of measured density (g/cm 3 ) versus theoretical density (g/cm 3 ) for an exemplary composite material, according to some implementations.
圖21示出根據一些實行方案,示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之抗彎模數(PSI)及黏度(Pa˙s)的圖表。 Figure 21 shows a graph of flexural modulus (PSI) and viscosity (Pa˙s) according to PPgMA loading level (ppH) relative to combined resin and filler weight for an exemplary composite, according to some implementations.
圖22示出根據一些實行方案,示範性複合材料之抗彎模數(PSI)及黏度(Pa˙s)碳負載(體積(vol.)%)之圖表。 Figure 22 shows a graph of flexural modulus (PSI) and viscosity (Pa˙s) carbon loading (vol. %) for an exemplary composite, according to some implementations.
圖23示出根據一些實行方案,描繪產生複合材料之示範性操作之流程圖。 Figure 23 shows a flowchart depicting exemplary operations for producing composite materials, according to some implementations.
圖24示出根據一些實行方案,描繪形成複合材料之示範性操作之流程圖。 Figure 24 shows a flowchart depicting exemplary operations for forming a composite material, according to some implementations.
圖25示出根據一些實行方案,描繪擠塑複合材料之示範性操作之流程圖。 Figure 25 shows a flowchart depicting exemplary operations for extruding composite materials, according to some implementations.
圖26示出根據一些實行方案,描繪壓塑複合材料之示範性操作之流程圖。 Figure 26 shows a flow diagram depicting exemplary operations for compression molding composite materials, according to some implementations.
圖27示出根據一些實行方案,描繪將額外樹脂及催化劑之混合物泵送至模具中之示範性操作之流程圖。 Figure 27 shows a flow diagram depicting exemplary operations for pumping a mixture of additional resin and catalyst into a mold, according to some implementations.
圖28示出根據一些實行方案,描繪將複合材料流***模具中之示範性操作的流程圖。 28 shows a flow diagram depicting exemplary operations for inserting a composite material stream into a mold, according to some implementations.
圖29示出根據一些實行方案,描繪對複合材料進行後處理之示範性操作之流程圖。 Figure 29 shows a flowchart depicting exemplary operations for post-processing composite materials, according to some implementations.
圖30示出根據一些實行方案,描繪經由圓筒形模具來擠塑複合材料之示範性操作之流程圖。 Figure 30 shows a flow diagram depicting exemplary operations for extruding a composite material through a cylindrical die, according to some implementations.
圖31示出根據一些實行方案,描繪用複合材料來形成物品之示範性操作之流程圖。 31 illustrates a flowchart depicting exemplary operations for forming an article from a composite material, according to some implementations.
圖32示出根據一些實行方案,描繪圖案化複合材料之示範性操作之流程圖。 Figure 32 shows a flowchart depicting exemplary operations for patterning composite materials, according to some implementations.
圖33示出根據一些實行方案,描繪對複合材料進行後處理之示範性操作之流程圖。 Figure 33 shows a flowchart depicting exemplary operations for post-processing composite materials, according to some implementations.
圖34示出根據一些實行方案,描繪自含有複合材料之模具提取所形成產品之示範性操作的流程圖。 34 shows a flowchart depicting exemplary operations for extracting a formed product from a mold containing a composite material, according to some implementations.
圖35示出根據一些實行方案,描繪將複合材料模製成一或多種形狀之示範性操作的流程圖。 35 shows a flowchart depicting exemplary operations for molding composite materials into one or more shapes, according to some implementations.
各個附圖中之相同參考編號及名稱指示相同元件。 The same reference numbers and names in the various drawings identify the same elements.
本專利申請案主張題為「COMPOSITE MATERIAL INCLUDING THREE-DIMENSIONAL(3D)GRAPHENE」並且2022年3月30日提交之美國專利申請案第17/708,574號、題為「A CONTAINER FORMED OF A COMPOSITE MATERIAL INCLUDING THREE-DIMENSIONAL(3D)GRAPHENE」並且2022年3月30日提交之美國專利申請案第17/708,599號、題為「METHOD OF PRODUCING A COMPOSITE MATERIAL INCLUDING THREE-DIMENSIONAL(3D)GRAPHENE」並且2022年3月30日提交之美國專利申請案第17/708,621號、及題為「COMPOSITE MATERIAL INCLUDING THREE-DIMENSIONAL(3D)GRAPHENE AND MALEATED COPOLYMERS」並且2022年3月30日提交之美國專利申請案第17/708,645號的優先權,該等申請案全部被指派給其受讓人。所有先前申請案之揭示內容被視為本專利申請案之一部分並且以引用方式併入本專利申請案。 This patent application is entitled "COMPOSITE MATERIAL INCLUDING THREE-DIMENSIONAL (3D) GRAPHENE" and U.S. Patent Application No. 17/708,574, filed on March 30, 2022, entitled "A CONTAINER FORMED OF A COMPOSITE MATERIAL INCLUDING THREE" -DIMENSIONAL(3D)GRAPHENE" and U.S. Patent Application No. 17/708,599, entitled "METHOD OF PRODUCING A COMPOSITE MATERIAL INCLUDING THREE-DIMENSIONAL(3D)GRAPHENE" filed on March 30, 2022 and filed on March 30, 2022 U.S. Patent Application No. 17/708,621 filed on March 30, 2022, and U.S. Patent Application No. 17/708,645 entitled "COMPOSITE MATERIAL INCLUDING THREE-DIMENSIONAL (3D) GRAPHENE AND MALEATED COPOLYMERS" filed on March 30, 2022 priority, all such applications are assigned to its assignee. The disclosures of all prior applications are considered a part of this patent application and are incorporated by reference into this patent application.
出於描述本揭示案之創新態樣之目的,以下描述針對一些示範性實行方案。然而,普通熟習此項技術者容易認識到本文中之教示可以許多不同方式來應用。所描述實行方案可以任何類型之材料來實施並且可用於提供用於保護箱子、冷卻器、手機、手電筒、旅行裝備、行李箱、酒具、背包、或類似物的成型材料。因此,所揭示實行方案不被本文提供之實例限制,而是實情為涵蓋所附申請專利範圍預期的所有實行方案。另外,將不詳細描述或將省略本揭示案之熟知要素以免混淆本揭示案之相關細節。 For the purpose of describing innovative aspects of the present disclosure, the following description is directed to some exemplary implementations. However, those of ordinary skill in the art will readily recognize that the teachings herein may be applied in many different ways. The described embodiments can be implemented in any type of material and can be used to provide molded materials for protecting cases, coolers, cell phones, flashlights, travel gear, luggage, wine bottles, backpacks, or the like. Accordingly, the disclosed implementations are not limited to the examples provided herein, but are intended to cover all implementations contemplated by the scope of the appended claims. Additionally, well-known elements of the disclosure will not be described in detail or will be omitted so as not to obscure the relevant details of the disclosure.
如上所述,複合材料由兩種或兩種以上具有不同化學及/或物理性質之構成材料產生。典型工程複合材料包括鋼筋混凝土及磚石複合木材諸如膠合板,增強塑膠諸如纖維增強聚合物或玻璃纖維陶瓷基質複合物(例如,複合陶瓷及金屬基質)、金屬基質複合物(MMC)及/或其他先進複合材料。複合材料往往比普通材料或它們的構成(例如,成型)材料更便宜、更輕、更堅固及/或更耐用。 As mentioned above, composite materials are produced from two or more constituent materials with different chemical and/or physical properties. Typical engineering composites include reinforced concrete and masonry, composite wood such as plywood, reinforced plastics such as fiber-reinforced polymer or fiberglass ceramic matrix composites (e.g., composite ceramic and metal matrix), metal matrix composites (MMC), and/or others Advanced composite materials. Composite materials tend to be cheaper, lighter, stronger and/or more durable than conventional materials or the materials of which they are composed (eg, molded).
複合材料可在諸如感測、驅動、計算、及通訊之廣泛多種最終使用應用領域中應用於複合物(「機器人材料」)中。複合材料亦可用於建造及/或形成建築物、橋樑、結構(例如,船體及游泳池面板)、賽車車身、淋浴間、浴缸、儲水箱、仿花崗岩、人造大理石水槽及工作台面、或類似物。複合材料可用於一般汽車應用,例如外露鑲板及衝擊吸收(例如,用於保險槓)。對於可在苛刻環境(例如外層空間)中以每小時1,000多哩之速度行駛的航天器及/或飛機而言,可產生一些複合材料。 Composite materials can be used in composites ("robotic materials") in a wide variety of end-use applications such as sensing, actuation, computing, and communications. Composites may also be used to construct and/or form buildings, bridges, structures (e.g., boat hulls and swimming pool panels), race car bodies, shower stalls, bathtubs, water storage tanks, imitation granite, cultured marble sinks and countertops, or the like . Composite materials can be used in general automotive applications such as exposed paneling and impact absorption (e.g., for bumpers). For spacecraft and/or aircraft that can travel at speeds of over 1,000 miles per hour in harsh environments such as outer space, some composite materials can be produced.
將剛性及脆性的基於環氧之碳纖維增強聚合物層壓物與可撓性熱塑性層壓物交織在一起可增加複合材料之韌性,並且由此增加抗衝擊性。此等交織複合物表現出形狀記憶行為而不需要額外形狀記憶聚合物及/或形狀記憶合金,諸如PVC及與聚苯乙烯交織之碳纖維增強聚合物層壓物。複合材料可包括各種類型或類別,諸如夾層結構複合材料,其可藉由將兩個相對較薄及剛性表層連接至輕質及較厚核心來形成。雖然複合材料之核心材料可為相對較弱的,但是在保持相對較低密度的同時,其較高厚度可為夾層複合物提供相對較高抗彎剛度。 Interweaving rigid and brittle epoxy-based carbon fiber reinforced polymer laminates with flexible thermoplastic laminates increases the composite's toughness and, thus, impact resistance. These interwoven composites exhibit shape memory behavior without the need for additional shape memory polymers and/or shape memory alloys, such as PVC and carbon fiber reinforced polymer laminates interwoven with polystyrene. Composite materials may include various types or categories, such as sandwich structural composites, which may be formed by joining two relatively thin and rigid skin layers to a lightweight and thicker core. Although the core material of the composite may be relatively weak, its relatively high thickness may provide the sandwich composite with relatively high bending stiffness while maintaining a relatively low density.
另外,聚乙烯(PE)及聚丙烯(PP)摻合物似乎增加聚合物廢物回收效率,同時保持總體生產量可持續性。然而,因為聚烯烴為熱力學不可混合的,所以與各種均聚物之特性相比,其可形成性能降低(例如,韌性較小等)的二元系統。PE/PP摻合物相容化可用於開發高效能及具有成本效益之產品,諸如藉由使用反應性及/或非反應性相容化技術來增加PE/PP摻合物之脆性至延性轉變。然而,採用此等技術得到之產品往往不能滿足具有相對較高需求的商業應用之要求。為瞭解決此問題,一些PE/PP摻合物修飾可包括增強合成或天然填充劑以便具有定製性質。 Additionally, polyethylene (PE) and polypropylene (PP) blends appear to increase polymer waste recycling efficiency while maintaining overall throughput sustainability. However, because polyolefins are thermodynamically immiscible, they can form binary systems with reduced properties (eg, less toughness, etc.) compared to the properties of various homopolymers. PE/PP blend compatibilization can be used to develop high-performance and cost-effective products, such as by increasing the brittle to ductile transition of PE/PP blends using reactive and/or non-reactive compatibilization techniques . However, products obtained using such technologies often fail to meet the requirements of commercial applications with relatively high demands. To address this issue, some PE/PP blend modifications may include enhancing synthetic or natural fillers to have customized properties.
本揭示案之態樣認識到某些複合材料可受益於在各種摻合物中均勻地併入碳顆粒。遺憾地,相對較高碳負載水準(例如,>10重量百分數(wt%))可導 致碳材料之不當聚集(例如,結塊),從而可導致黏度不受控制地增加並且超過客戶提供之流變規範。雖然碳顆粒之相對不可預測及不可控制之聚集可不合意地改變複合材料之物理性質(例如,韌性),但是不含碳之複合材料可能不具有碳可提供的某些物理性質(諸如受控脆性)。 Aspects of the present disclosure recognize that certain composite materials may benefit from the uniform incorporation of carbon particles in various blends. Unfortunately, relatively high carbon loading levels (e.g., >10 weight percent (wt%)) can lead to Causes improper aggregation (e.g., agglomeration) of carbon materials, which can cause uncontrolled increases in viscosity and exceed customer-supplied rheology specifications. Although the relatively unpredictable and uncontrollable aggregation of carbon particles can undesirably alter the physical properties of the composite (e.g., toughness), composites that do not contain carbon may not possess some of the physical properties that carbon can provide (such as controlled brittleness). ).
本文揭示之標的物之各種態樣涉及複合材料,其可由與聚丙烯接枝順丁烯二酸酐(PPgMA)混合之熱塑性樹脂之組合來形成。碳顆粒可在該組合中混合。以此方式,複合材料可包括80wt%與90wt%之間之熱塑性樹脂、0.5wt%與15wt%之間之PPgMA、及0.1wt%至7wt%之間之碳顆粒。各碳顆粒可由互連三維(3D)石墨化材料(例如,被稱為「3D石墨烯」)形成,該等材料在沒有種子顆粒的情況下自成核。另外,各碳顆粒可具有暴露碳表面,該表面具有鍵結至相鄰PPgMA分子上之分子位點的碳原子。至少一些碳原子可經一或多種含氧基團來氧化。在一些情況下,氧化碳原子可增加每單位體積與相鄰碳原子化學鍵結之PPgMA分子,並且因此碳原子與PPgMA分子之間之相互作用可將複合材料密度保持在熱塑性樹脂密度之+/- 3%內且/或產生可預測流變概況,諸如具有2,100帕斯卡-秒(Pa˙S)與近似700Pa˙S之間之黏度水準。 Various aspects of the subject matter disclosed herein relate to composite materials that may be formed from a combination of thermoplastic resins mixed with polypropylene grafted maleic anhydride (PPgMA). Carbon particles can be mixed in the combination. In this manner, the composite material may include between 80 and 90 wt% thermoplastic resin, between 0.5 and 15 wt% PPgMA, and between 0.1 and 7 wt% carbon particles. Each carbon particle can be formed from interconnected three-dimensional (3D) graphitized materials (eg, known as "3D graphene") that self-nucleate without seed particles. Additionally, each carbon particle may have an exposed carbon surface with carbon atoms bonded to molecular sites on adjacent PPgMA molecules. At least some of the carbon atoms can be oxidized via one or more oxygen-containing groups. In some cases, oxidized carbon atoms can increase the number of PPgMA molecules chemically bonded to adjacent carbon atoms per unit volume, and thus the interaction between carbon atoms and PPgMA molecules can maintain the composite density at +/- the density of the thermoplastic resin. Within 3% and/or produces predictable rheological profiles, such as having viscosity levels between 2,100 Pascal-seconds (Pa˙S) and approximately 700 Pa˙S.
圖1示出根據一些實行方案,示範性複合材料之顯微照片100。顯微照片100包括第一顯微照片110,其描繪不含聚丙烯接枝順丁烯二酸酐(PPgMA)之複合材料;及第二顯微照片120,其描繪包括氮摻雜(n-摻雜)碳顆粒及5.0百分份數(ppH)之負載水準之聚丙烯接枝順丁烯二酸酐(PPgMA)的複合材料。第一顯微照片110描繪可叢集在一起以便形成碳附聚區域116之一或多個實例的碳顆粒115。複合材料中之碳附聚可導致黏度不受控制地增加,通常超過所需流變規範並且因此對於許多最終使用應用領域而言,為不合需要的。或者,顯微照片120描繪在均勻分散區域126之一或多個實例中的碳顆粒115。碳顆粒115在整個均勻分散區域126中之相對均勻分佈可歸因於包括PPgMA,其可浸潤碳顆粒115
中之孔隙區域(為簡單起見未展示)。因此,碳顆粒115可至少部分地藉由例如互連PPgMA分子單元來分離以便形成均勻分散區域126,從而可導致複合材料具有可預測流變概況,諸如可預測密度及/或黏度值。
Figure 1 shows a
在一些態樣中,複合材料可藉由注射模製來進行後處理並且作為用於箱子、冷卻器、手機外殼、手電筒、旅行裝備、行李箱、酒具、背包、或類似物的成型材料來使用。另外,顯微照片120描述之複合材料可在多個行業中之各種最終使用應用領域中用作成型材料,該等應用領域包括(但是不限於)農業、建築、地板清潔機械、水處理、戶外(例如草坪及園藝)、環境產品、船舶、航空航天、娛樂設備、體育設備、玩具、家具、醫療、消費品、大型容器、水箱、箱子或類似物。在一些情況下,用於產生複合材料之製造方法包括旋轉模製、注射模製、吹氣模製、真空成形、熱成形、擠塑、增材製造(例如3D打印)、聚合物鑄造、或另一種合適製造方法。 In some aspects, the composite material can be post-processed by injection molding and used as a molding material for cases, coolers, cell phone cases, flashlights, travel gear, luggage, barware, backpacks, or the like. use. Additionally, the composite material depicted in photomicrograph 120 may be used as a molding material in a variety of end-use applications in a variety of industries, including, but not limited to, agriculture, construction, floor cleaning machinery, water treatment, outdoor (such as lawn and garden), environmental products, marine, aerospace, entertainment equipment, sports equipment, toys, furniture, medical, consumer products, large containers, tanks, boxes or similar. In some cases, manufacturing methods used to create composite materials include rotational molding, injection molding, blow molding, vacuum forming, thermoforming, extrusion, additive manufacturing (e.g., 3D printing), polymer casting, or Another suitable manufacturing method.
在一些情況下,複合材料藉由熱塑性樹脂及順丁烯二酸化共聚物、順丁烯二酸共聚物,及/或順丁烯二酸化聚合物之組合來形成。在一些態樣中,熱塑性樹脂可為或包括線性低密度聚乙烯(LLDPE)樹脂,包括乙烯-丁烯共聚物及/或α-烯烴。在一些其他態樣中,熱塑性樹脂可為或包括任何類型之聚乙烯系統,包括LLDPE、線性聚乙烯(LPE)、茂金屬聚乙烯(mPE)、高密度聚乙烯(HDPE)、超高分子量(UHMW)聚乙烯(PE)(UHMWPE)、耐綸、聚丙烯、聚醚醚酮(PEEK)、或類似物。熱塑性樹脂亦可為或包括任何類型之半晶質及非晶質熱塑性材料。 In some cases, composite materials are formed from a combination of a thermoplastic resin and a maleated copolymer, a maleic acid copolymer, and/or a maleated polymer. In some aspects, the thermoplastic resin may be or include linear low density polyethylene (LLDPE) resin, including ethylene-butylene copolymers and/or alpha-olefins. In some other aspects, the thermoplastic resin can be or include any type of polyethylene system, including LLDPE, linear polyethylene (LPE), metallocene polyethylene (mPE), high density polyethylene (HDPE), ultra-high molecular weight ( UHMW) polyethylene (PE) (UHMWPE), nylon, polypropylene, polyetheretherketone (PEEK), or the like. Thermoplastic resins may also be or include any type of semi-crystalline and amorphous thermoplastic materials.
示範性半晶質熱塑性材料可為不透明的、可撓的、及耐化學的並且包括標準熱塑性塑膠(例如,聚丙烯(PP)、高密度聚乙烯(PE-HD或HDPE)、低密度聚乙烯(PE-LD或LDPE),及/或線性低密度聚乙烯(PE-LLD或LLDPE))、工程化熱塑性塑膠(例如,耐綸46或聚醯胺46(PA46)、聚鄰苯二甲醯胺(PPA)、間規聚苯乙烯(SPS)、熱塑性彈性體(TPE)、聚對苯二甲酸丁二醇酯(PBT)、聚對苯二
甲酸乙二醇酯(PET)、聚甲醛(POM)、耐綸6,6或聚醯胺6,6及耐綸6或聚醯胺6(分別為PA66及PA6),及/或高效能熱塑性塑膠(例如,聚醚酮(PEK)、PEEK、聚苯硫醚(PPS),及/或聚丙烯11/12(PP 11/12))。
Exemplary semi-crystalline thermoplastic materials can be opaque, flexible, and chemically resistant and include standard thermoplastics (e.g., polypropylene (PP), high-density polyethylene (PE-HD or HDPE), low-density polyethylene (PE-LD or LDPE), and/or linear low-density polyethylene (PE-LLD or LLDPE)), engineered thermoplastics (e.g., nylon 46 or polyamide 46 (PA46), polyphthalate Amine (PPA), syndiotactic polystyrene (SPS), thermoplastic elastomer (TPE), polybutylene terephthalate (PBT), polyterephthalate
Ethylene glycol formate (PET), polyoxymethylene (POM),
示範性非晶質熱塑性材料可為透明、脆性、及不耐化學的並且包括標準熱塑性塑膠(例如,丙烯腈丁二烯苯乙烯(ABS)、聚苯乙烯高抗沖(PS-HI)、聚苯乙烯(PS),及/或聚氯乙烯(PVC))、工程化熱塑性塑膠(例如,聚碳酸酯(PC)、聚碳酸酯聚對苯二甲酸乙二醇酯(PC/PET)、(PC)聚碳酸酯及(ABS)丙烯腈-丁二烯-苯乙烯之熱塑性合金(PC/ABS)、經修飾之聚苯醚(m-PPE)、聚(甲基丙烯酸甲酯)(PMMA),及/或苯乙烯丙烯晴(SAN)),及/或高效能熱塑性塑膠(例如,聚醯胺-醯亞胺(PAI)、聚苯碸(PPSU)、聚碸(PSU),及/或聚醚碸(PES))。 Exemplary amorphous thermoplastic materials may be clear, brittle, and chemically resistant and include standard thermoplastics (e.g., acrylonitrile butadiene styrene (ABS), polystyrene high impact (PS-HI), poly Styrene (PS), and/or polyvinyl chloride (PVC)), engineered thermoplastics (e.g., polycarbonate (PC), polycarbonate polyethylene terephthalate (PC/PET), ( PC) polycarbonate and (ABS) thermoplastic alloy of acrylonitrile-butadiene-styrene (PC/ABS), modified polyphenylene ether (m-PPE), poly(methyl methacrylate) (PMMA) , and/or styrene acrylonitrile (SAN)), and/or high-performance thermoplastics (e.g., polyamide-imide (PAI), polyphenylene glycol (PPSU), polystyrene (PSU), and/or Polyether styrene (PES)).
在一些實行方案中,熱塑性樹脂可與聚丙烯接枝順丁烯二酸酐(PPgMA)(或「順丁烯二酸化聚丙烯」)混合。在一些情況下,PPgMA可具有80重量百分數(wt%)與99.9wt%之間之PP含量,並且順丁烯二酸酐(MA)含量之對應餘量在20wt%與0.01wt%之間。在一些其他實行方案中,熱塑性樹脂可與聚丙烯-共-丙烯酸(PP-共-AA)、聚乙烯-共-丙烯酸(PE-共-AA)或與順丁烯二酸化共聚物混合,該等順丁烯二酸化共聚物包括例如聚乙烯接枝順丁烯二酸酐(PE-g-MA)、聚乙烯-alt-順丁烯二酸酐(PE-alt-MA)、聚異戊二烯接枝順丁烯二酸酐(PI-g-MA)、聚苯乙烯接枝順丁烯二酸酐(PS-g-MA)、或聚苯乙烯-嵌段-聚(乙烯-ran-丁烯)-嵌段-聚苯乙烯接枝順丁烯二酸酐。在此等實行方案中,順丁烯二酸化共聚物可具有80重量百分數(wt%)與99.9wt%之間之聚合物(例如,PP、PE、聚異戊二烯(PI)、或PS含量及20wt%與0.01wt%之間之順丁烯二酸酐(MA)含量,並且因此複合材料可包括98.7wt%-100wt%之間之聚丙烯(PP)及0.0wt%-1.3wt%之間之順丁烯二酸酐(MA)。 In some implementations, the thermoplastic resin may be blended with polypropylene grafted maleic anhydride (PPgMA) (or "maleated polypropylene"). In some cases, PPgMA may have a PP content between 80 weight percent (wt%) and 99.9 wt%, with a corresponding balance of maleic anhydride (MA) content between 20 wt% and 0.01 wt%. In some other implementations, the thermoplastic resin can be blended with polypropylene-co-acrylic acid (PP-co-AA), polyethylene-co-acrylic acid (PE-co-AA), or with maleated copolymers, such as Maleated copolymers include, for example, polyethylene-grafted maleic anhydride (PE-g-MA), polyethylene-alt-maleic anhydride (PE-alt-MA), polyisoprene-grafted Maleic anhydride (PI-g-MA), polystyrene-grafted maleic anhydride (PS-g-MA), or polystyrene-block-poly(ethylene-ran-butene)-blocked Segment-polystyrene grafted with maleic anhydride. In such implementations, the maleated copolymer may have a polymer (e.g., PP, PE, polyisoprene (PI), or PS content between 80 weight percent (wt%) and 99.9 wt% and a maleic anhydride (MA) content between 20wt% and 0.01wt%, and therefore the composite material may include between 98.7wt%-100wt% polypropylene (PP) and between 0.0wt%-1.3wt% Maleic anhydride (MA).
在一些實行方案中,可將碳顆粒115混合以使得複合材料包括80wt%與90wt%之間之熱塑性樹脂、0.5wt%與15wt%之間之PPgMA、及0.1wt%至7wt%之間之碳顆粒。碳顆粒中之各者可包括化學鍵結至熱塑性樹脂及/或PPgMA之相鄰原子的碳原子,並且因此,PPgMA可為碳顆粒與熱塑性樹脂之間之相容劑。在一些態樣中,碳顆粒包括具有每單位體積相對較低濃度之碳顆粒的第一區域117及具有每單位體積相對較高濃度之碳顆粒的第二區域118。第一區域117可與第二區域118相鄰定位。在一些情況下,碳顆粒具有一或多個額外區域119,其各自具有與緊鄰前一個區域不同(例如,更高或更低)的濃度水準。第一區域117、第二區域118、及一或多個額外區域119中之任何一者或多者可被設定成與任何其他區域相同或不同的大小。以此方式,可對碳顆粒115進行組織以便在整個複合材料中獲得每單位體積之預定義濃度水準。 In some implementations, the carbon particles 115 may be mixed such that the composite material includes between 80 wt% and 90 wt% thermoplastic resin, between 0.5 wt% and 15 wt% PPgMA, and between 0.1 wt% and 7 wt% carbon. Particles. Each of the carbon particles may include carbon atoms chemically bonded to adjacent atoms of the thermoplastic resin and/or PPgMA, and thus, PPgMA may be a compatibilizer between the carbon particles and the thermoplastic resin. In some aspects, the carbon particles include a first region 117 having a relatively low concentration of carbon particles per unit volume and a second region 118 having a relatively high concentration of carbon particles per unit volume. The first region 117 may be positioned adjacent the second region 118 . In some cases, the carbon particles have one or more additional regions 119, each of which has a different (eg, higher or lower) concentration level than the immediately preceding region. Any one or more of the first area 117, the second area 118, and the one or more additional areas 119 may be set to the same or a different size than any other area. In this manner, the carbon particles 115 can be organized to achieve predefined concentration levels per unit volume throughout the composite material.
在一些實行方案中,碳顆粒115具有暴露碳表面,該等表面具有鍵結至相鄰PPgMA分子上之分子位點的碳原子(為簡單起見未展示)。碳原子可經一或多種含氧基團來氧化。碳原子與其相鄰PPgMA分子之間之相互作用可將複合材料之密度保持在熱塑性樹脂之密度之+/-3%內。孔隙可在至少一些碳顆粒115內及/或在該等碳顆粒、熱塑性樹脂、及PPgMA之間形成,以使得至少一些孔隙可由PPgMA浸潤。在一些態樣中,各孔隙可具有0.05立方公分/公克(cm3/g)與1.5cm3/g之間之孔隙體積。另外,碳原子之氧化可增加每單位體積的PPgMA與相鄰碳原子之化學鍵結。在一些情況下,碳顆粒可由一或多種互連褶皺3D石墨烯片材或非中空碳球形顆粒(NHCS)形成。 In some implementations, carbon particles 115 have exposed carbon surfaces with carbon atoms bonded to molecular sites on adjacent PPgMA molecules (not shown for simplicity). Carbon atoms can be oxidized via one or more oxygen-containing groups. The interaction between the carbon atoms and their neighboring PPgMA molecules keeps the density of the composite material within +/- 3% of the density of the thermoplastic resin. Pores may be formed within at least some of the carbon particles 115 and/or between the carbon particles, the thermoplastic resin, and PPgMA such that at least some of the pores may be wetted by the PPgMA. In some aspects, each pore can have a pore volume between 0.05 cubic centimeters per gram (cm 3 /g) and 1.5 cm 3 /g. In addition, the oxidation of carbon atoms can increase the chemical bonding between PPgMA and adjacent carbon atoms per unit volume. In some cases, the carbon particles may be formed from one or more interconnected wrinkled 3D graphene sheets or non-hollow carbon spherical particles (NHCS).
複合材料可藉由一或多種物理、化學、機械,及/或其他性質來表徵。例如,複合材料之密度可至少部分地基於孔隙之總孔隙體積。在一些情況下,至少一些碳原子可與相鄰PPgMA分子化學反應,從而改變複合材料之流變性質。以此方式,複合材料可具有基於熱塑性樹脂、PPgMA、及至少一些碳顆粒之黏 度。在一些態樣中,複合材料之黏度可基於複合材料內之碳顆粒之負載水準。在一些其他態樣中,複合材料之黏度可與複合材料內之PPgMA之負載水準之增加成比例地減少。 Composite materials can be characterized by one or more physical, chemical, mechanical, and/or other properties. For example, the density of the composite material may be based at least in part on the total pore volume of the pores. In some cases, at least some of the carbon atoms can react chemically with adjacent PPgMA molecules, thereby changing the rheological properties of the composite. In this way, composite materials can have adhesives based on thermoplastic resin, PPgMA, and at least some carbon particles. Spend. In some aspects, the viscosity of the composite material may be based on the loading level of carbon particles within the composite material. In some other aspects, the viscosity of the composite may decrease proportionally with increasing loading levels of PPgMA within the composite.
在一些態樣中,複合材料可具有2,100帕斯卡-秒(Pa-s)與500Pa-s之間之黏度。在一些情況下,在複合材料中包括碳顆粒可增加複合材料之抗彎模數及/或抗拉強度。例如,按照ASTM D.790,在23℃之溫度下,在1%割線模數值下,複合材料可具有107,500磅/平方吋(PSI)與117,500PSI之間之抗彎模數。在一些情況下,複合材料可具有500%之最大拉伸伸長。在190℃之溫度下,複合材料可具有4公克/min(g/min)至8g/min之間之可調熔體流動速率。另外,複合材料之抗拉強度可比不包括碳顆粒之複合材料高30%至100%。至少一些碳原子可藉由與PPgMA分子化學反應來改變與熱塑性樹脂及PPgMA分子之周圍原子相關的化學鍵結行為。例如,每百分之一份(1ppH)PPgMA,至少一些碳顆粒與其相應相鄰PPgMA分子之間之相互作用可增加複合材料之機械增強達1,000PSI至1,100PSI。 In some aspects, the composite material can have a viscosity between 2,100 Pascal-seconds (Pa-s) and 500 Pa-s. In some cases, including carbon particles in the composite can increase the flexural modulus and/or tensile strength of the composite. For example, according to ASTM D.790, at a temperature of 23°C and a 1% secant modulus value, a composite material can have a flexural modulus between 107,500 pounds per square inch (PSI) and 117,500 PSI. In some cases, the composite material may have a maximum tensile elongation of 500%. At a temperature of 190°C, the composite material can have an adjustable melt flow rate between 4 grams/min (g/min) and 8g/min. In addition, the tensile strength of composite materials can be 30% to 100% higher than composite materials that do not include carbon particles. At least some of the carbon atoms can change the chemical bonding behavior associated with the thermoplastic resin and surrounding atoms of the PPgMA molecules by chemically reacting with the PPgMA molecules. For example, interactions between at least some carbon particles and their corresponding adjacent PPgMA molecules can increase the mechanical strengthening of the composite by as much as 1,000 PSI to 1,100 PSI per one percent (1 ppH) PPgMA.
在至少一個實行方案中,碳顆粒可由為簡單起見未展示的一或多個非三區段顆粒及/或三區段顆粒形成。在一些情況下,三區段顆粒中之各者可由為簡單起見未展示的藉由中型孔隙來分隔之纏結碳片段形成。在與一或多個非三區段顆粒及/或三區段顆粒聚結後,可形成可變形周界。另外,碳顆粒可由聚集物及附聚物形成及/或包括聚集物及附聚物。在一些情況下,各聚集物包括經接合之三區段顆粒及10奈米(nm)與10微米(μm)之間之主要尺寸。在一些情況下,中型孔隙散佈在整個聚集物中,並且各中型孔隙可具有3.3奈米(nm)與19.3nm之間之主要尺寸。各附聚物可包括經接合之聚集物,其各自具有近似0.1μm與1,000μm之間之主要尺寸。在一些情況下,大孔隙散佈在整個聚集物中,並且各大孔隙可具有0.1μm與1,000μm之間之主要尺寸。在一些態樣中,至少一 些碳顆粒充當複合材料之奈米增強構件。以此方式,MA可與至少一些奈米增強構件反應。另外,PP可增加至少一些奈米增強構件與熱塑性樹脂之間之界面相互作用。 In at least one implementation, the carbon particles may be formed from one or more non-three-segment particles and/or three-segment particles not shown for simplicity. In some cases, each of the three-segment particles may be formed from entangled carbon segments separated by mesopores, not shown for simplicity. A deformable perimeter may be formed upon coalescence with one or more non-three-segment particles and/or three-segment particles. Additionally, the carbon particles may be formed from and/or include aggregates and agglomerates. In some cases, each aggregate includes joined three-segment particles with major dimensions between 10 nanometers (nm) and 10 micrometers (μm). In some cases, mesopores are dispersed throughout the aggregate, and each mesopore can have a major dimension between 3.3 nanometers (nm) and 19.3 nm. Each agglomerate may comprise joined aggregates, each having a major dimension between approximately 0.1 μm and 1,000 μm. In some cases, macropores are dispersed throughout the aggregate, and each macropore can have a major size between 0.1 μm and 1,000 μm. In some forms, at least one These carbon particles act as nano-reinforcement building blocks for composite materials. In this way, MA can react with at least some nanoreinforcement building blocks. In addition, PP can increase the interfacial interaction between at least some nanoreinforcement components and the thermoplastic resin.
圖2示出根據一些實行方案,自石墨進行硫酸(H2SO4)剝離所產生之石墨烯材料205之顯微照片200。在一些態樣中,至少一些石墨烯材料205與石墨烯材料205之一或多個額外實例聚結並且產生圖1描述之至少一些碳顆粒115。在一些其他態樣中,至少一些石墨烯材料205之形狀及/或形態為及/或類似於平坦奈米片。另外,至少一些石墨烯材料205可具有「波浪狀」或「褶皺」形態210,其可指示至少一些平坦奈米片藉由一或多個規定角度(而不是筆直、平坦、或180°角度)來鄰接,從而可導致每單位體積之表面積與體積比相對高於非波浪狀或非褶皺石墨烯材料。
Figure 2 shows a
圖3示出根據一些實行方案,基於微波能量之波浪狀及/或起皺石墨烯305之顯微照片300。在一些情況下,至少一些基於微波能量之波浪狀及/或起皺石墨烯305可與本身之一或多個額外實例聚結以便產生圖1之顯微照片120描述之至少一些碳顆粒115。另外,至少一些基於微波能量之波浪狀及/或起皺石墨烯305可為圖2之石墨烯材料205之一個實例。在一些態樣中,基於微波能量之波浪狀及/或起皺石墨烯305之至少一些石墨烯奈米片可鄰接在一起以便界定各種脊及谷315。以此方式,至少一些脊及谷315可在基於微波能量之波浪狀及/或起皺石墨烯305內產生可撓性得以增加之區域,其可適合於由例如聚合物(例如,PPgMA及/或類似物)浸潤。在一些態樣中,sp3-雜交聚合物鏈310(例如,聚乙烯,PE),可表現出相對於sp2-C鏈共軛聚合物(例如,聚(對伸苯基)的增加之可撓性。
Figure 3 shows a
圖4示出根據一些實行方案,示範性碳顆粒之顯微照片400。在一些態樣中,至少一些碳顆粒405可各自為藉由圖1之顯微照片120來描述之碳顆
粒115中之一或多者之一個實例。另外,至少一些碳顆粒405可在石墨烯材料205及/或基於微波能量之波浪狀及/或起皺石墨烯305之多個實例聚結後形成。在一些情況下,碳顆粒405可藉由在碳顆粒405之相鄰實例之間形成之第一多個孔隙410來彼此分隔。如圖4展示,碳顆粒405中之各者可為多孔結構,其含有藉由重疊二級碳顆粒415來產生的額外多個孔隙(例如,包括第二多個孔隙420)。在各種實行方案中,第一多個孔隙410之平均大小可大於第二多個孔隙420之平均大小。在各種實行方案中,第二多個孔隙可足夠大以便使得PPgMA分子及/或其他物質能夠浸潤至少一些碳顆粒405,由此產生例如圖1之顯微照片120描述之複合材料。
Figure 4 shows a
圖5A示出根據一些實行方案,圖4展示之碳顆粒(例如,三區段顆粒)之實例之略圖。在各種實行方案中,三區段顆粒500A可為藉由圖1之顯微照片120來描述之碳顆粒115中之任何一者或多者之一個實例。三區段顆粒500A可包括三個離散區段諸如(但是不限於)第一區段501、第二區段502、及第三區段503。在一些態樣中,區段501-503中之各者包圍及/或囊封前一個區段。例如,第一區段501可由第二區段502包圍或囊封,並且第二區段502可由第三區段503包圍或囊封。第一區段501可對應於三區段顆粒500A之內部區域,第二區段502可對應於三區段顆粒500A之中間過渡區域,並且第三區段503可對應於三區段顆粒500A之外部區域。在一些態樣中,三區段顆粒500A可包括響應於與一或多個相鄰非三區段顆粒及/或三區段顆粒500A之接觸而變形的可滲透殼505。
Figure 5A shows a schematic diagram of an example of the carbon particles (eg, three-segment particles) shown in Figure 4, according to some implementations. In various implementations,
在一些實行方案中,第一區段501可具有相對較低密度、相對較低電導性、及相對較高孔隙率,第二區段502可具有中等密度、中等電導性、及中等孔隙率,並且第三區段503可具有相對較高密度、相對較高電導性、及相對較低孔隙率。在一些態樣中,第一區段501可具有近似1.5g/cc與5.0g/cc之間之
碳材料密度,第二區段502可具有近似0.5g/cc與3.0g/cc之間之碳材料密度,並且第三區段503可具有近似0.0與1.5g/cc之間之碳材料密度。在其他態樣中,第一區段501可包括具有近似0與40nm之間之寬度的孔隙,第二區段502可包括具有近似0與35nm之間之寬度的孔隙,並且第三區段503可包括具有近似0與30nm之間之寬度的孔隙。在一些其他實行方案中,第二區段502可不針對三區段顆粒500A來加以界定。在一個實行方案中,第一區段501可具有近似0nm與100nm之間之主要尺寸D1,第二區段502可具有近似20nm與150nm之間之主要尺寸D2,並且第三區段503可具有近似200nm之主要尺寸D3。
In some implementations, the
本揭示案之態樣認識到三區段顆粒500A之獨特佈局及第一區段501、第二區段502、及第三區段503之相對尺寸、孔隙率、及電導性可加以選擇及/或修改在最大限度地減少多硫化合物穿梭效應與最大化主機電池之比容量之間達成所需平衡。具體而言,在一些態樣中,在一個區段與另一個區段之間,孔隙可在大小及體積方面得以減少。在一些實行方案中,三區段顆粒可完全由具有一系列孔徑及孔隙分佈(例如,孔隙密度)的一個區段來組成。對於圖5A之實例,與第一區段501或第一孔隙率區域相關之孔隙511具有相對較大寬度並且可定義為大孔隙,與第二區段502或第二孔隙率區域相關之孔隙512具有中等大小寬度並且可定義為中型孔隙,並且與第三區段503或第三孔隙率區域相關之孔隙513具有相對較小寬度並且可定義為微孔隙。
Aspects of the present disclosure recognize that the unique layout of the three-
可將成組的三區段顆粒500A接合在一起以便形成聚集物(為簡單起見未展示),並且聚集物之群組可接合在一起以便形成附聚物(為簡單起見未展示)。在一些實行方案中,複數個中型孔隙可散佈在藉由碳顆粒500A之相應群組來形成的整個聚集物中。在一些態樣中,第一孔隙率區域可至少部分地由第二孔隙率區域囊封以使得相應聚集物可包括一或多個中型孔隙及一或多個大孔隙。在一個實行方案中,各中型孔隙可具有3.3奈米(nm)與19.3nm之間之主要
尺寸,並且各大孔隙可具有0.1μm與1,000μm之間之主要尺寸。在一些情況下,三區段顆粒500A可包括彼此纏結並且藉由至少一些中型孔隙來彼此分隔的碳片段。
Groups of three-
在一些實行方案中,三區段顆粒500A可包括界面活性劑或聚合物,包括苯乙烯丁二烯橡膠、聚偏二氟乙烯、聚丙烯酸、羧基甲基纖維素、聚乙烯吡咯啶酮,及/或聚乙酸乙烯酯中之一或多者,該聚合物可充當將成組的碳材料接合在一起的黏合劑。在其他實行方案中,三區段顆粒500A可包括安置在至少一些孔隙內之凝膠相電解質或固相電解質。
In some implementations,
在一些實行方案中,三區段顆粒500A可具有10m2/g至3,000m2/g之間之近似範圍中之暴露碳表面之表面積及/或10m2/g至3,000m2/g之間之近似範圍中之複合表面積(包括微觀局限於孔隙內之其他物質諸如PPgMA)。在一個實行方案中,在12,000鎊/平方吋(psi)之壓力下,包括多個三區段顆粒500A之物質組成物可具有100S/m至20,000S/m之間之近似範圍中之電導性及近似1:5至10:1之間之硫碳重量比。
In some implementations, the three-
圖5B示出根據一些實行方案,代表圖5A之三區段顆粒之示範性階梯函數。如論述,分佈在整個三區段顆粒500A中之孔隙可具有不同大小、體積、或分佈。在一些實行方案中,平均孔隙體積可基於三區段顆粒500A之中心與相鄰區段之間之距離而減少,例如,以使得與第一區段501或第一孔隙率區域相關之孔隙具有相對較大體積或孔徑,與第二區段502或第二孔隙率區域相關之孔隙具有中等體積,並且與第三區段503或第三孔隙率區域相關之孔隙具有相對較小體積。與接近於周邊之區域相比,內部區域具有較高孔隙體積。具有較高孔隙體積之區域提供較高硫負載,而較低孔隙體積外部區域減輕在電池循環期間的多硫化物之遷移。在圖5B之實例中,內部區域中之平均孔隙體積為近似3cc/g,
最外層區域中之平均孔隙體積為近似0.5cc/g並且中間區域中之平均孔隙體積在0.5cc/g與3cc/g之間。
Figure 5B illustrates an exemplary step function representing the three-segment particles of Figure 5A, according to some implementations. As discussed, the pores distributed throughout the three-
圖6示出根據一些實行方案,描繪示範性碳顆粒之孔隙體積相比於孔隙寬度之示範性分佈的圖表。如圖表600描述,與相對較高孔隙體積相關之孔隙可具有相對較低孔隙寬度,例如,以使得孔隙寬度通常隨著孔隙體積減少而增加。在一些態樣中,具有小於近似1.0nm之孔隙寬度之孔隙可被稱為微孔隙,具有近似3與11nm之間之孔隙寬度的孔隙可被稱為中型孔隙,並且具有大於近似24nm之孔隙寬度之孔隙可被稱為大孔隙。
Figure 6 shows a graph depicting an exemplary distribution of pore volume versus pore width for exemplary carbon particles, according to some implementations. As depicted in
圖7A示出根據一些實行方案,圖4及/或圖5A描述之示範性碳顆粒、聚集物,及/或附聚物之顯微照片700。在一些態樣中,圖7A描述之碳顆粒可為圖1之顯微照片120描述之碳顆粒115及/或本揭示案描述之其他碳顆粒的一個實例。在一些實行方案中,碳結構702中之各者可具有藉由各種整體式碳生長及/或分層來包圍的基本上中空核心區域。在一些態樣中,整體式碳生長及/或分層可為參考圖2至4來描述之各種碳結構、生長及/或分層之實例。在一些情況下,碳結構702可包括以不同密度及/或濃度水準來組織的多個同心多層富勒烯及/或類似形狀碳結構。例如,碳結構702中之各者之實際最終形狀、大小、及石墨烯組態可視各種製造過程而定。在一些態樣中,碳結構702可表現出不良水溶性。因此,在一些實行方案中,非共價功能化可用於改變碳結構702之一或多種可分散性性質而不影響潛在碳奈米材料之固有性質。在一些態樣中,潛在碳奈米材料可為成型sp2碳奈米材料。在一些實行方案中,碳結構702中之各者可具有近似20與500nm之間之直徑。在各種實行方案中,碳結構702之群組可聚結及/或接合在一起以便形成聚集物704。另外,聚集物704之群組可聚結及/或接合在一起以便形成附聚物706。在一些態樣中,碳結構702、聚集物704,及/
或附聚物706中之一或多者可用於形成圖1之顯微照片120描述之碳顆粒115中之一或多者。
Figure 7A shows a
圖7B示出根據一些實行方案,由碳材料形成之聚集物之顯微照片750。在一些實行方案中,聚集物760可為圖7A之聚集物704中之一者之實例。在一個實行方案中,外部碳殼型結構752可與藉由其他碳殼型結構754來提供之碳融合在一起以便形成碳結構756。成組的碳結構756可彼此聚結及/或接合以便形成聚集物760。在一些態樣中,碳結構756中之各者之核心區域758可為可調的,例如,因為核心區域758可包括不同規定濃度水準之互連石墨烯結構及/或碳顆粒,如參考圖5A及/或圖5B所描述。在一些實行方案中,一些碳結構756可在外部碳殼型結構752處或附近具有近似0.1g/cc與2.3g/cc之間的第一濃度之互連碳。碳結構756中之各者可具有孔隙以便傳送向內朝向核心區域758延伸之鋰陽離子(Li+)。 Figure 7B shows a photomicrograph 750 of aggregates formed from carbon material, according to some implementations. In some implementations, aggregate 760 may be an example of one of aggregates 704 of Figure 7A. In one implementation, outer carbon shell 752 may be fused with carbon provided by other carbon shells 754 to form carbon structure 756 . Groups of carbon structures 756 may coalesce and/or join to each other to form aggregates 760 . In some aspects, the core region 758 of each of the carbon structures 756 may be tunable, for example, because the core region 758 may include different prescribed concentration levels of interconnected graphene structures and/or carbon particles, as shown in FIG. 5A and/or as described in Figure 5B. In some implementations, some of the carbon structures 756 may have a first concentration of interconnected carbon between approximately 0.1 g/cc and 2.3 g/cc at or near the outer carbon shell structure 752 . Each of the carbon structures 756 may have pores to transport lithium cations (Li + ) extending inward toward the core region 758 .
在一些實行方案中,碳結構756中之各者之孔隙可具有近似0.0nm與0.5nm之間、近似0.0與0.1nm之間、近似0.0與6.0nm之間、或近似0.0與35nm之間的寬度或尺寸。各碳結構756亦可在核心區域758處或附近具有不同於第一濃度的第二濃度。例如,第二濃度可包括同心配置的多個相對較低密度碳區域。在一個實行方案中,第二濃度可在近似0.0g/cc與1.0g/cc之間或近似1.0g/cc與1.5g/cc之間,低於第一濃度。在一些態樣中,第一濃度與第二濃度之間之關係可用於在將硫或多硫化物限制在相應電極內與最大化鋰陽離子(Li+)之傳送之間達成平衡。例如,在鋰-硫電池之操作循環期間,硫及/或多硫化物可行進穿過第一濃度並且至少暫時地被限制及/或散佈在整個第二濃度中。 In some implementations, the pores of each of the carbon structures 756 may have a diameter between approximately 0.0 nm and 0.5 nm, between approximately 0.0 and 0.1 nm, between approximately 0.0 and 6.0 nm, or between approximately 0.0 and 35 nm. Width or size. Each carbon structure 756 may also have a second concentration at or near core region 758 that is different from the first concentration. For example, the second concentration may include a plurality of concentrically arranged regions of relatively lower density carbon. In one implementation, the second concentration may be between approximately 0.0 g/cc and 1.0 g/cc or between approximately 1.0 g/cc and 1.5 g/cc, lower than the first concentration. In some aspects, the relationship between the first concentration and the second concentration can be used to strike a balance between confining sulfur or polysulfides within the respective electrode while maximizing the transport of lithium cations (Li + ). For example, during an operating cycle of a lithium-sulfur battery, sulfur and/or polysulfides may travel through the first concentration and be at least temporarily confined and/or dispersed throughout the second concentration.
在一些實行方案中,至少一些碳結構756可包括CNO氧化物,該等氧化物經組織成整體式及/或互連生長並且在熱反應器中產生。例如,碳結構756可根據以下示範性配方用鈷奈米顆粒裝飾:可將乙酸鈷(II)(C4H6CoO4),乙酸之 鈷鹽(經常發現如四水合物Co(CH3CO2)2.4H2O,可縮寫為Co(Oac)2.4H2O,以對應於40.40wt%碳(涉及CNO形式中之碳)之近似59.60wt%之比率流至熱反應器中,導致CNO氧化物上之活性位點用鈷來功能化,相應地展示15,000x水準之鈷裝飾CNO。在一些實行方案中,用於產生碳#29及/或鈷裝飾CNO之合適氣體混合物可包括以下步驟: In some implementations, at least some carbon structures 756 may include CNO oxides that are organized into monolithic and/or interconnected growth and produced in a thermal reactor. For example, carbon structure 756 may be decorated with cobalt nanoparticles according to the following exemplary formulation: Cobalt(II) acetate (C 4 H 6 CoO 4 ), a cobalt salt of acetate (often found as the tetrahydrate Co(CH 3 CO 2 ) 2.4H 2 O, which may be abbreviated as Co(Oac) 2.4H 2 O, flows into the thermal reactor at a rate of approximately 59.60 wt% corresponding to 40.40 wt% carbon (relating to carbon in the form of CNO), Resulting in active sites on the CNO oxide being functionalized with cobalt, correspondingly exhibiting 15,000x levels of cobalt-decorated CNO. In some implementations, suitable gas mixtures for producing carbon #29 and/or cobalt-decorated CNO may include Following steps:
●氬吹掃0.75標準立方呎/分鐘(scfm)持續30min; ●Argon purge 0.75 standard cubic feet per minute (scfm) for 30 minutes;
●將氬吹掃改變為0.25scfm以便進行運作; ●Changed argon purge to 0.25scfm for operation;
●溫度增加:25℃至300℃ 20分鐘;及 ●Temperature increase: 25℃ to 300℃ for 20 minutes; and
●溫度增加:300℃-500℃ 15分鐘。 ●Temperature increase: 300℃-500℃ for 15 minutes.
參考圖7A及7B描述之碳材料可包括或另外由石墨烯之一或多個實例來形成,其可包括單層碳原子,其中各原子結合至蜂窩結構中之三個鄰居。單層可為受限在一個維度中,諸如在凝聚相之表面內或處的不連續材料。例如,石墨烯可僅在x及y平面(並且不在z平面中)向外生長。以此方式,石墨烯可為二維(2D)材料,其包括一個或多個層,其中各層中之原子強烈鍵結(諸如藉由複數個碳-碳鍵)至同一層中之相鄰原子。 The carbon materials described with reference to Figures 7A and 7B may include or otherwise be formed from one or more instances of graphene, which may include a single layer of carbon atoms where each atom is bonded to three neighbors in a honeycomb structure. A single layer may be a discontinuous material that is confined in one dimension, such as within or at the surface of the condensed phase. For example, graphene can grow outward only in the x and y planes (and not in the z plane). In this manner, graphene can be a two-dimensional (2D) material that includes one or more layers in which atoms in each layer are strongly bonded (such as by a plurality of carbon-carbon bonds) to adjacent atoms in the same layer. .
在一些實行方案中,石墨烯奈米片(例如,在碳結構756中之各者中所包括的成型結構)可包括石墨烯之多個實例,諸如第一石墨烯層、第二石墨烯層、及第三石墨烯層,全部在垂直方向上在彼此的頂部疊加。可被稱為GNP之石墨烯奈米片中之各者可具有1nm與3nm之間之厚度,並且可具有近似100nm至100μm範圍內之橫向尺寸。在一些實行方案中,石墨烯奈米片可藉由輥對輥(「R2R」)生產,藉由依序配置的多個電漿噴霧炬來產生。在一些態樣中,R2R生產可包括在作為軋製片材來處理之連續基材上沉積,包括將2D材料傳遞至單獨基材。在一些情況下,用於所描述R2R過程中之電漿噴霧炬可噴灑不同濃度水準之碳材料以便產生特定濃度水準之石墨烯奈米片。因此,R2R過程可提
供精細水準之可調性,以便產生圖1之顯微照片120描述之碳顆粒115、圖4之顯微照片400描述之碳顆粒405,及/或如在本揭示案中別處描述之其他碳顆粒。
In some implementations, graphene nanosheets (eg, shaped structures included in each of carbon structures 756) may include multiple instances of graphene, such as a first graphene layer, a second graphene layer , and a third graphene layer, all vertically stacked on top of each other. Each of the graphene nanosheets, which may be referred to as GNPs, may have a thickness between 1 nm and 3 nm, and may have lateral dimensions in the range of approximately 100 nm to 100 μm. In some implementations, graphene nanosheets can be produced by roll-to-roll ("R2R") production by multiple plasma spray torches arranged in sequence. In some aspects, R2R production may include deposition on a continuous substrate processed as a rolled sheet, including transferring 2D materials to individual substrates. In some cases, the plasma spray torch used in the described R2R process can spray different concentration levels of carbon material to produce specific concentration levels of graphene nanosheets. Therefore, the R2R process can provide
Provides a fine level of adjustability to produce carbon particles 115 depicted in micrograph 120 of Figure 1, carbon particles 405 depicted in
圖8示出根據一些實行方案,描繪分散在圖4之顯微照片400描述之碳顆粒405中之微孔隙及中型孔隙之累積孔隙體積相比於孔隙寬度的圖表800。如本文使用,「碳1」係指主要包括微孔隙(諸如在主要尺寸方面小於5nm)的結構化碳材料,並且「碳2」係指主要包括中型孔隙(諸如在主要尺寸方面在近似20nm至50nm之間)的結構化碳材料。在一些實行方案中,適合用於本文揭示電池中之一者中之電極可被製備成具有圖表800描述之孔徑相比於孔隙分佈。
Figure 8 shows a
圖9示出根據一些實行方案,圖4描述之示範性碳顆粒之示範性組態900。在一些實行方案中,組態900可為圖1之顯微照片120、第一區域117、第二區域118、一或多個額外區域119描述之碳顆粒115,或在本揭示案中別處描述之其他碳顆粒之一或多個附聚物的一個實例。在一個實行方案中,組態900包括第一多孔碳區域910及與第一多孔碳區域910相鄰定位的第二多孔碳區域920。第一多孔碳區域910可由第一濃度水準之碳材料形成,並且第二多孔碳區域920由與第一濃度水準之碳材料不同的第二濃度水準之碳材料形成。例如,第二多孔碳區域920可具有比第一多孔碳區域910更低濃度水準之碳材料,如圖9展示。在一些態樣中,額外多孔碳區域(為簡單起見,未在圖9中展示)可與至少第二多孔碳區域920耦合。
Figure 9 illustrates an
具體而言,此等額外多孔碳區域可在遠離第一多孔碳區域910之方向上,以碳材料之濃度水準逐步降低之順序來配置,以便提供完全可調性。亦即,在一個實行方案中,第二多孔碳區域920可朝向所需區域(例如,圖1之顯微照片120描述之第一區域117)並且組態900之第一多孔碳區域910可按照客戶規範來定位。以此方式,更緻密碳區域,諸如第一多孔碳區域910,可有助於碳材料之相鄰接觸點之間的相對較低水準之物質(例如,PPgMA及/或類似者),同時
更稀疏碳區域,諸如第二多孔碳區域920,可有助於相對較高水準之物質浸潤。在一些實行方案中,與第二多孔碳區域920耦合並且與其相鄰定位的額外碳區域可具有比第二多孔碳區域920更低的碳材料密度。以此方式,更低密度之額外碳區域可適應更高水準之鋰離子傳送,以便例如允許調節包括組態900之複合材料之各種性能特性。
Specifically, these additional porous carbon regions may be configured in order of decreasing concentration levels of carbon material away from the first porous carbon region 910 to provide full tunability. That is, in one implementation, the second porous carbon region 920 can be oriented toward a desired region (eg, the first region 117 depicted in the photomicrograph 120 of FIG. 1 ) and the first porous carbon region 910 of the
在一個實行方案中,第一多孔碳區域910可包括第一非三區段顆粒911。第一多孔碳區域內之第一非三區段顆粒911之組態為一個示範性組態。對於非三區段顆粒而言,其他佈局、取向、對準及/或類似者為可能的。在一些態樣中,各非三區段顆粒可為在本揭示案中別處揭示之一或多種碳材料的實例。第一多孔碳區域910亦可包括第一三區段顆粒912,如圖9展示,其散佈在整個第一非三區段顆粒911中或以任何其他佈局、取向、或組態來定位。各第一三區段顆粒912可為圖5A之三區段顆粒500A之一個實例。另外或替代,各第一三區段顆粒912可包括彼此纏結並且藉由中型孔隙914來彼此分隔的第一碳片段913。各三區段顆粒可具有經組配來與相鄰第一非三區段顆粒911及/或第一三區段顆粒912聚結的第一可變形周界915。
In one implementation, first porous carbon region 910 may include first non-tri-section particles 911 . The configuration of the first non-three-segment particles 911 within the first porous carbon region is an exemplary configuration. For non-three-segment particles, other layouts, orientations, alignments, and/or the like are possible. In some aspects, each non-three-segment particle may be an example of one or more carbon materials disclosed elsewhere in this disclosure. The first porous carbon region 910 may also include first three-segment particles 912, as shown in Figure 9, dispersed throughout the first non-three-segment particles 911 or positioned in any other layout, orientation, or configuration. Each first three-segment particle 912 may be an example of the three-
第一多孔碳區域910亦可包括第一聚集物916,其中各聚集物包括接合在一起的多個第一三區段顆粒912。在一或多個特定實例中,各第一聚集物可具有10奈米(nm)與10微米(μm)之間之範圍內的主要尺寸。中型孔隙914可散佈在整個第一複數個聚集物中,其中各中型孔隙具有3.3奈米(nm)與19.3nm之間之主要尺寸。另外,第一多孔碳區域910可包括第一附聚物917,其中各附聚物包括彼此接合的多個第一聚集物916。在一些態樣中,各第一附聚物917可具有0.1μm與1,000μm之間之近似範圍內的主要尺寸。大孔隙918可散佈在整個第一聚集物916中,其中各大孔隙可具有0.1μm與1,000μm之間之主要尺寸。在
一些實行方案中,以上論述碳材料、同素異形體及/或結構中之一或多者可為圖7A及7B展示之一或多個實例。
The first porous carbon region 910 may also include first aggregates 916, where each aggregate includes a plurality of first three-segment particles 912 joined together. In one or more specific examples, each first aggregate can have a major dimension ranging between 10 nanometers (nm) and 10 micrometers (μm).
第二多孔碳可包括第二非三區段顆粒921,其可為第一非三區段顆粒911之一個實例。第二多孔碳區域920可包括第二三區段顆粒922,其各自可為第一三區段顆粒912中之各者的一個實例且/或可為圖5A之三區段顆粒500A的一個實例。另外或替代,各第二三區段顆粒922可包括彼此纏結並且藉由中型孔隙914來彼此分隔之第二碳片段923。各第二三區段顆粒922可具有經組配來與一或多個相鄰第二非三區段顆粒921或第二三區段顆粒922聚結的第二可變形周界925。
The second porous carbon may include second non-tri-segment particles 921 , which may be an example of the first non-tri-segment particles 911 . The second porous carbon region 920 may include second three-segment particles 922 , each of which may be an instance of each of the first three-segment particles 912 and/or may be one of the three-
另外,第二多孔碳區域920可包括第二聚集物926,其中各第二聚集物926可包括接合在一起的多個第二三區段顆粒922。在一或多個特定實例中,各第二聚集物926可具有10奈米(nm)與10微米(μm)之間之範圍內的主要尺寸。中型孔隙914可散佈在整個第二聚集物926中,各中型孔隙可具有3.3奈米(nm)與19.3nm之間之主要尺寸。此外,第二多孔碳區域920可包括第二附聚物927,各第二附聚物927可包括彼此接合的多個第二聚集物926,其中各附聚物可具有0.1μm與1,000μm之間之近似範圍內的主要尺寸。大孔隙918可散佈在整個第二複數個聚集物中,其中各大孔隙具有0.1μm與1,000μm之間之主要尺寸。在一些實行方案中,以上論述碳材料、同素異形體及/或結構中之一或多者可為圖9A及9B展示之一或多個實例。
Additionally, the second porous carbon region 920 may include second aggregates 926, wherein each second aggregate 926 may include a second plurality of three-segment particles 922 joined together. In one or more specific examples, each second aggregate 926 may have a major dimension ranging between 10 nanometers (nm) and 10 micrometers (μm).
在一個實行方案中,第一多孔碳區域910及/或第二多孔碳區域920可包括選擇性可滲透殼(為簡單起見,未在圖9中展示),其可分別在第一多孔碳區域910或第二多孔碳區域920上形成分離液相。電解質,諸如本揭示案揭示之任何電解質,可分散在第一多孔碳區域及/或第二多孔碳區域內以便進行與鋰-硫電池放電-充電操作循環相關的鋰離子傳送。 In one implementation, the first porous carbon region 910 and/or the second porous carbon region 920 may include a selectively permeable shell (not shown in FIG. 9 for simplicity), which may be located in the first porous carbon region, respectively. A separated liquid phase is formed on the porous carbon region 910 or the second porous carbon region 920 . An electrolyte, such as any electrolyte disclosed herein, may be dispersed within the first porous carbon region and/or the second porous carbon region to facilitate lithium ion transport associated with the discharge-charge operating cycle of a lithium-sulfur battery.
在一或多個特定實例中,在12,000鎊/平方吋(psi)之壓力下,第一多孔碳區域910可具有500S/m至20,000S/m之間之近似範圍中之電導性。在12,000鎊/平方吋(psi)之壓力下,第二多孔碳區域920可具有0S/m至500S/m之間之近似範圍中之電導性。第一附聚物917及/或第二附聚物927可包括藉由一或多種基於聚合物之黏合劑來彼此連接的聚集物。
In one or more specific examples, the first porous carbon region 910 may have a conductivity in an approximate range of between 500 S/m and 20,000 S/m at a pressure of 12,000 pounds per square inch (psi). At a pressure of 12,000 pounds per square inch (psi), the second porous carbon region 920 may have an electrical conductivity in an approximate range of between 0 S/m and 500 S/m. The
在一些態樣中,各第一三區段顆粒912可具有圍繞第一三區段顆粒912之中心來定位的第一孔隙率區域(為簡單起見,未在圖9中展示)。類似地,各第二三區段顆粒922可具有圍繞第二三區段顆粒922之中心來定位的第一孔隙率區域(為簡單起見,未在圖9中展示)。第一孔隙率區域可包括第一孔隙。第二孔隙率區域(為簡單起見,未在圖9中展示)可包圍第一孔隙率區域。第二孔隙率區域可包括第二孔隙。在一個實行方案中,第一孔隙可定義第一孔隙密度,並且第二孔隙可定義不同於第一孔隙密度的第二孔隙密度。 In some aspects, each first three-segment particle 912 may have a first porosity region positioned about the center of the first three-segment particle 912 (not shown in Figure 9 for simplicity). Similarly, each second three-segment particle 922 may have a first porosity region positioned about the center of the second three-segment particle 922 (not shown in Figure 9 for simplicity). The first porosity region may include first pores. A second porosity region (not shown in Figure 9 for simplicity) may surround the first porosity region. The second porosity region may include second pores. In one implementation, the first pores may define a first pore density, and the second pores may define a second pore density that is different from the first pore density.
在一些態樣中,中型孔隙914可分組成第一中型孔隙及第二中型孔隙(為簡單起見,均未在圖9中展示)。在一或多個特定實例中,第一中型孔隙可具有第一中型孔隙密度,並且第二中型孔隙可具有不同於第一中型孔隙密度的第二中型孔隙密度。另外,大孔隙918可分組成可具有第一孔隙密度之第一大孔隙,及可具有不同於第一孔隙密度之第二孔隙密度的第二大孔隙(為簡單起見,均未在圖9中展示)。
In some aspects,
圖10示出根據一些實行方案,聚丙烯接枝順丁烯二酸酐(PPgMA)之化學結構組分1005之略圖1000。PPgMA為包括聚丙烯(PP)及順丁烯二酸酐(MA)的2組分分子。在一些態樣中,PPgMA可以珠粒形式提供並且具有近似3,900之數量平均分子量(Mn)及近似9,100之重量平均分子量(Mw),如藉由凝膠滲透層析法(GPC)來確定。典型複合材料組成物可包括近似8wt%-10wt% MW之負載水準,並且餘量為PP。在一些情況下,在近似190℃之溫度下,PPgMA之量測黏 度可為近似4.0泊。PPgMA可具有近似156℃之熔點(mp)及在25℃下0.934g/mL之近似密度。 Figure 10 shows a schematic diagram 1000 of the chemical structural components 1005 of polypropylene grafted maleic anhydride (PPgMA), according to some implementations. PPgMA is a 2-component molecule including polypropylene (PP) and maleic anhydride (MA). In some aspects, PPgMA may be provided in bead form and have a number average molecular weight ( Mn ) of approximately 3,900 and a weight average molecular weight ( Mw ) of approximately 9,100, as determined by gel permeation chromatography (GPC) . Typical composite compositions may include loading levels of approximately 8 wt%-10 wt% MW, with the balance being PP. In some cases, the measured viscosity of PPgMA can be approximately 4.0 poise at a temperature of approximately 190°C. PPgMA may have a melting point (mp) of approximately 156°C and an approximate density of 0.934 g / mL at 25°C.
圖11示出根據一些實行方案之示範性化學結構1100,包括產生圖10描述之PPgMA及臭氧處理石墨烯表面的化學反應機制1105。例如,如藉由化學反應機制1105來展示,MA可充當反應性基團並且經由開環反應,與一或多種其他化學物質(例如,己-1-醇)反應,從而可產生一或多種中間產物,其經歷一或多個額外化學反應以便產生完成分子1110。在一些態樣中,完成分子1110可與完成分子1110之其他實例化學反應以便產生併入圖1之複合材料中之PPgMA。
Figure 11 illustrates an
在一些實行方案中,圖1之複合材料可併入至少一些碳顆粒115。在一些態樣中,碳顆粒115具有暴露碳表面(例如,臭氧處理(氧化)石墨烯表面1115)及鍵結至相鄰PPgMA分子上之分子位點的碳原子。至少一些碳原子可經一或多種含氧基團來氧化。藉由氧化碳原子,每單位體積的更多PPgMA分子可與相鄰碳原子化學鍵結。以此方式,碳原子與PPgMA分子之間之相互作用可將複合材料密度保持在熱塑性樹脂密度之+/- 3%內且具有可預測流變概況(諸如具有2,100帕斯卡-秒(Pa˙S)與近似700Pa˙S)之間之黏度水準。 In some implementations, the composite material of Figure 1 may incorporate at least some carbon particles 115. In some aspects, carbon particles 115 have carbon atoms with exposed carbon surfaces (eg, ozone-treated (oxidized) graphene surfaces 1115) and bonded to molecular sites on adjacent PPgMA molecules. At least some of the carbon atoms can be oxidized via one or more oxygen-containing groups. By oxidizing carbon atoms, more PPgMA molecules per unit volume can chemically bond with adjacent carbon atoms. In this way, the interaction between carbon atoms and PPgMA molecules can maintain composite density within +/- 3% of the thermoplastic resin density with a predictable rheology profile (such as having a 2,100 Pascal-second (Pa˙S) and approximately 700Pa˙S).
圖12示出根據一些實行方案,描繪按照波數(cm-1)之強度(相對吸收率)之圖表1200。圖表1200指示圖1之複合材料之示範性所觀察性質。如圖表1200描述,氧化石墨烯、PPgMA枝接石墨烯、及純淨PPgMA中之各者具有不同強度。
Figure 12 shows a
圖13示出根據一些實行方案,描繪圖1之示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之抗彎模數(PSI)之圖表1300。圖表1300指示圖1之複合材料之示範性所觀察性質。如圖表1300描述,純淨樹脂(例如,不含任何碳負載水準之熱塑性樹脂)、1體積(vol.)%碳顆粒負載、
及3vol.%碳顆粒負載中之各者具有按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之不同抗彎模數(PSI)概況。
Figure 13 shows a
圖14示出根據一些實行方案,描繪圖1之示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(百分份數,ppH)之黏度(Pa˙s)的圖表1400。圖表1400指示圖1之複合材料之示範性所觀察性質。如圖表1400描述,1體積(vol.)%碳顆粒負載及3vol.%碳顆粒負載中之各者具有按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之不同黏度(Pa˙s)。
Figure 14 shows a
圖15示出根據一些實行方案,描繪圖1之示範性複合材料之未氧化碳材料(DX C/F)及臭氧(O3)處理碳顆粒之抗彎模數(PSI)之條形圖1500。條形圖1500指示圖1之複合材料之示範性所觀察性質。
Figure 15 shows a
圖16示出根據一些實行方案,描繪圖1之示範性複合材料之線性低密度聚乙烯(LLDPE)及聚丙烯(PP)之抗彎模數(PSI)之條形圖1600。條形圖1600指示圖1之複合材料之示範性所觀察性質。如條形圖1600描述,PP具有比LLDPE更高的PSI。將LLDPE與PP摻合可增加其對於例如圖1之碳顆粒115的增強。在一些情況下,LLDPE與PP之組合可浸潤至碳顆粒115之開放多孔區域中(及/或如相對於圖9之組態900來描述)以便增強複合材料之物理性質。
Figure 16 shows a
圖17示出根據一些實行方案,描繪圖1之示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之抗彎模數(PSI)及斷裂伸長率(%)的圖表1700。圖表1700指示圖1之複合材料之示範性所觀察性質。
Figure 17 illustrates flexural modulus (PSI) and elongation at break (%) of the exemplary composite of Figure 1 as a function of PPgMA loading level (ppH) relative to combined resin and filler weight, according to some implementations.
圖18示出根據一些實行方案,圖1之示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH),所量測的超過純淨樹脂之抗彎模數增加百分比(%)的圖表1800。圖表1800指示圖1之複合材料之示範性所觀察性質。
Figure 18 illustrates the measured percent increase in flexural modulus (%) over neat resin at PPgMA loading levels (ppH) relative to combined resin and filler weight for the exemplary composite of Figure 1, according to some implementations. )
圖19示出根據一些實行方案,圖1之示範性複合材料之按照臭氧處理時間(分鐘(min.)),臭氧(O3)處理過程中之氧含量(原子(at.)%)的圖表1900。圖表1900指示在臭氧處理(例如,氧化藉由暴露碳表面來提供之碳原子)期間觀察到的圖1之複合材料之示範性性質。
Figure 19 illustrates a graph of oxygen content (at. %) during ozone ( O3 ) treatment as a function of ozone treatment time (minutes (min.)) for the exemplary composite of Figure 1, according to some implementations. 1900.
圖20示出根據一些實行方案,圖1之示範性複合材料之量測密度(g/cm3)相比於理論密度(g/cm3)之圖表2000。圖表2000指示圖1之複合材料之示範性所觀察性質。
FIG. 20 shows a
圖21示出根據一些實行方案,圖1之示範性複合材料之按照相對於組合樹脂及填充劑重量之PPgMA負載水準(ppH)之抗彎模數(PSI)及黏度(Pa˙s)的圖表2100。圖表2100指示圖1之複合材料之示範性所觀察性質。
Figure 21 shows a graph of bending modulus (PSI) and viscosity (Pa˙s) as a function of PPgMA loading level (ppH) relative to combined resin and filler weight for the exemplary composite of Figure 1, according to some implementations. 2100.
圖22示出根據一些實行方案,圖1之示範性複合材料之抗彎模數(PSI)及黏度(Pa˙s)碳負載(體積(vol.)%)之圖表2200。圖表2200指示圖1之複合材料之示範性所觀察性質。
Figure 22 shows a
圖23示出根據一些實行方案,描繪產生圖1之顯微照片120描述之複合材料之示範性操作2300的流程圖。在各種實行方案中,操作2300可在一或多個反應器中執行,並且一或多個反應器可包括熱反應器腔室、電漿反應器、噴霧乾燥器、霧化器、或任何其他合適化學處理設備。在一些態樣中,藉由供應具有初始密度之熱塑性樹脂,操作2300開始於方塊2302處。藉由將聚丙烯接枝順丁烯二酸酐(PPgMA)之分散液在整個熱塑性樹脂中混合,操作在方塊2304處繼續,PPgMA由複數個互連PPgMA分子形成。藉由將複數個碳顆粒分佈在整個熱塑性樹脂及複數個互連PPgMA分子中,操作在方塊2306處繼續,複數個碳顆粒具有均勻分散在熱塑性樹脂與PPgMA之組合內的0.05立方公分/公克(cm3/g)與1.5cm3/g之間之孔隙體積。藉由旋轉模製來形成基於熱塑性樹脂、PPgMA、及複數個碳顆粒中之至少一些之組合的複合材料,操作在方塊2308處
繼續,其中藉由複數個碳顆粒中之至少一些來提供之碳原子與其相應相鄰互連PPgMA分子之間的化學鍵結經組配來增加複合材料之抗彎模數,同時將複合材料之最終密度保持在+/- 3%偏離熱塑性樹脂之初始密度的容許限度內,其中容許限度基於孔隙體積。
23 shows a flowchart depicting
圖24示出根據一些實行方案,描繪形成圖23產生之複合材料之示範性操作2400之流程圖。在各種實行方案中,操作2400可在模具及/或模製設備中執行。在一些態樣中,藉由在一或多個方向上壓縮複合材料,操作2400在方塊2402處開始。藉由基於複合材料之壓縮來形成片材或板材中之一或多者,操作在方塊2404處繼續。
Figure 24 shows a flowchart depicting
圖25示出根據一些實行方案,描繪擠塑圖23產生之複合材料之示範性操作2500之流程圖。在各種實行方案中,操作2500可在材料擠塑機中執行。在一些態樣中,藉由經由模頭來擠塑複合材料,操作2500在方塊2502處開始。藉由基於複合材料之擠塑來形成物品,操作在方塊2504處繼續。
25 illustrates a flow diagram depicting an
圖26示出根據一些實行方案,描繪壓塑圖23產生之複合材料之示範性操作2600之流程圖。在各種實行方案中,操作2600可在模具中執行。在一些態樣中,藉由使用手工敷層過程或噴霧過程中之一或多者來製備模具,操作2600在方塊2602處開始。藉由使用手壓輥來壓塑複合材料,操作在方塊2604處繼續。
26 illustrates a flow diagram depicting an
圖27示出根據一些實行方案,描繪將額外樹脂及催化劑之混合物泵送至用於形成圖23產生之複合材料之模具中之示範性操作2700的流程圖。在各種實行方案中,操作2700可在模具中執行。在一些態樣中,藉由乾燥複合材料來產生經乾燥之複合材料,操作2700在方塊2702處開始。藉由將乾燥複合材料***模具中,操作在方塊2704處繼續。藉由將額外樹脂及催化劑之混合物泵送至模具中,操作在方塊2706處繼續。
Figure 27 shows a flow diagram depicting an
圖28示出根據一些實行方案,描繪將圖23產生之複合材料流***模具中之示範性操作2800的流程圖。在各種實行方案中,操作2800可在模具中執行。在一些態樣中,藉由將複合材料流***模具中,操作2800在方塊2802處開始。藉由將線性低密度聚乙烯(LLDPE)流***模具中,操作在方塊2804處繼續。藉由將催化劑***模具中,操作在方塊2806處繼續。藉由將複合材料、熱塑性樹脂、及催化劑在模具內混合,操作在方塊2808處繼續。
Figure 28 shows a flowchart depicting
圖29示出根據一些實行方案,描繪對圖23產生之複合材料進行後處理之示範性操作2900之流程圖。在各種實行方案中,操作2800可在真空輔助樹脂傳遞模製(VARTM)設備中執行。在一些態樣中,藉由使用真空輔助樹脂傳遞模製(VARTM)技術對複合材料進行後處理,操作2900在方塊2902處開始,該技術包括使用真空,將複合材料抽吸至模具中。
Figure 29 shows a flowchart depicting
圖30示出根據一些實行方案,描繪經由圓筒形模具來擠塑複合材料之示範性操作3000之流程圖。在各種實行方案中,操作3000可在模具中執行。在一些態樣中,藉由經由圓筒形模具來擠塑複合材料以便產生複合線材,操作3000在方塊3002處開始。藉由將複合線材沿著軸捲繞以便產生長纖維纏繞之複合物,操作在方塊3004處繼續。
30 shows a flow diagram depicting an
圖31示出根據一些實行方案,描繪使用圖23產生之複合材料來形成物品之示範性操作3100之流程圖。在各種實行方案中,操作3100可在加熱浴中執行。在一些態樣中,藉由傳送複合材料之線材穿過保持在22℃以上之浴,從而產生半熔融複合線材,操作3100在方塊3102處開始。藉由經由一或多個導向器來傳送半熔融複合線材,從而形成物品,操作在方塊3104處繼續。
31 shows a flow diagram depicting
圖32示出根據一些實行方案,描繪圖案化圖23產生之複合材料之示範性操作3200之流程圖。在各種實行方案中,操作3200可在圖案化工具中或上執行。在一些態樣中,藉由將複合材料切割成一或多個預定義圖案,操作3200
在方塊3202處開始。藉由將一或多個預定義圖案鋪設在表面上,操作在方塊3204處繼續。藉由使用心軸,在表面上之一或多個預定義圖案上軋製,操作在方塊3206處繼續。
Figure 32 shows a flowchart depicting
圖33示出根據一些實行方案,描繪對圖23產生之複合材料進行後處理之示範性操作3300之流程圖。在各種實行方案中,操作3300可在圖案化工具中或上執行。在一些態樣中,藉由形成複合材料片材,操作3300在方塊3302處開始。藉由將切片玻璃纖維傾倒在複合材料片材頂部,操作在方塊3304處繼續。藉由用額外複合材料層來覆蓋複合材料片材及切片玻璃纖維,操作在方塊3306處繼續。
33 shows a flowchart depicting
圖34示出根據一些實行方案,描繪自含有圖23產生之複合材料之模具提取所形成產品之示範性操作3400的流程圖。在各種實行方案中,操作3400可在材料擠塑機中執行。在一些態樣中,藉由將熔融狀態中之複合材料注射至模具中,操作3400在方塊3402處開始。藉由將複合材料在模具內冷卻,自模具提取所形成產品,操作在方塊3404處繼續。
34 shows a flow diagram depicting
圖35示出根據一些實行方案,描繪將圖23產生之複合材料模製成一或多個形狀之示範性操作3500的流程圖。在各種實行方案中,操作3500可在模具中執行。在一些態樣中,藉由使用真空壓縮模製、旋轉模製、吹氣模製、或注射包覆模製中之一者,將複合材料模製成一或多個形狀,操作3500在方塊3502處開始。
35 shows a flowchart depicting
如本文所用,提及條目清單「中之至少一者」或「中之一或多者」之片語係指彼等條目之任一組合,包括單一成員。舉例而言,「a、b或c中之至少一者」意欲涵蓋以下可能性:僅a、僅b、僅c、a及b之組合、a及c之組合、b及c之組合以及a及b及c之組合。 As used herein, phrases referring to "at least one of" or "one or more of" a list of items refer to any combination of those items, including a single member. For example, "at least one of a, b or c" is intended to cover the following possibilities: only a, only b, only c, a combination of a and b, a combination of a and c, a combination of b and c, and a and the combination of b and c.
結合本文中揭示之實行方案描述之各種說明性組件、邏輯、邏輯區塊、模組、電路、操作及演算法程序可實施為電子硬體、韌體、軟體,或硬體、韌體或軟體之組合,包括本說明書中揭示之結構及其結構等效物。硬體、韌體及軟體之可互換性已就功能性大體描述,且在以上所述各種說明性組件、區塊、模組、電路及過程中示出。此功能性是否以硬體、韌體或軟體來實施視應用及強加於整個系統之設計約束而定。 The various illustrative components, logic, logic blocks, modules, circuits, operations, and algorithmic processes described in connection with the implementation disclosed herein may be implemented as electronic hardware, firmware, software, or as hardware, firmware, or software Combinations include the structures disclosed in this specification and their structural equivalents. The interchangeability of hardware, firmware, and software has been generally described in terms of functionality and illustrated in the various illustrative components, blocks, modules, circuits, and processes described above. Whether this functionality is implemented in hardware, firmware, or software depends on the application and the design constraints imposed on the overall system.
一般熟習此項技術者可容易明白對本揭示案所描述之實行方案的各種修改,且本文所定義之一般原則可適用於其他實行方案而不脫離本揭示案之精神或範疇。因此,申請專利範圍不欲限於本文所示實行方案,而應被賦予與本揭示內容、本文揭示之原則及新穎特徵一致的最寬範疇。 Various modifications to the implementations described in this disclosure will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other implementations without departing from the spirit or scope of this disclosure. Accordingly, the scope of patent claims is not intended to be limited to the implementations shown herein, but is to be accorded the broadest scope consistent with the disclosure, principles and novel features disclosed herein.
另外,本說明書中在單獨實行方案之情形中描述的各種特徵亦可在單一實行方案中組合地實施。相反,在單一實行方案之情形中描述的各種特徵亦可在多個實行方案中分開地實施或在任何合適子組合中實施。因此,儘管特徵可在上文彼此組合來加以描述,且甚至最初以此方式主張,但是來自所主張組合之一或多個特徵在一些情況下可自該組合去除,且所主張組合可涉及子組合或子組合之變型。 In addition, various features described in this specification in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Thus, although features may be described above in combination with each other, and even originally claimed in this manner, one or more features from the claimed combination may in some cases be removed from that combination, and the claimed combination may involve sub- Variations of combinations or subcombinations.
類似地,雖然操作在圖式中以特定次序描繪,但是此不應當理解為要求此等操作以所展示之特定次序或以順序次序來執行,或執行所有所示出之操作來達成合意結果。此外,附圖可以流程圖或程序框圖之形式示意性地描繪一或多個示範性過程。然而,未描繪之其他操作可併入示意性說明的示範性過程中。例如,可以在任何所示操作之前、之後、同時或之間執行一或多個附加操作。在一些情況下,多任務及平行處理可為有利的。此外,上述實行方案中之各種系統組件之分開不應理解為在所有實行方案中都要求此分開,且應瞭解,所描述之程式組件及系統通常可在單一產品中整合在一起或封裝至多個產品中。 Similarly, although operations are depicted in the drawings in a specific order, this should not be understood as requiring that such operations be performed in the specific order shown or in sequential order, or that all illustrated operations be performed to achieve satisfactory results. Additionally, the figures may schematically depict one or more exemplary processes in the form of flowcharts or block diagrams. However, other operations not depicted may be incorporated into the schematically illustrated exemplary processes. For example, one or more additional operations may be performed before, after, concurrently with, or between any illustrated operations. In some cases, multitasking and parallel processing can be advantageous. Furthermore, the separation of various system components in the above implementations should not be construed as requiring such separation in all implementations, and it is understood that the program components and systems described may often be integrated together in a single product or packaged into multiple in the product.
100:顯微照片 100:Micrograph
110:顯微照片 110:Micrograph
115:碳顆粒 115: Carbon particles
116:碳附聚區域 116: Carbon agglomeration area
117:第一區域 117:First area
118:第二區域 118:Second area
119:額外區域 119:Extra area
120:顯微照片 120:Micrograph
126:均勻分散區域 126: Uniformly dispersed area
Claims (90)
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/708,599 | 2022-03-30 | ||
US17/708,599 US11674031B1 (en) | 2022-03-30 | 2022-03-30 | Container formed of a composite material including three-dimensional (3D) graphene |
US17/708,645 | 2022-03-30 | ||
US17/708,574 | 2022-03-30 | ||
US17/708,645 US11591457B1 (en) | 2022-03-30 | 2022-03-30 | Composite material including three-dimensional (3D) graphene and maleated copolymers |
US17/708,621 | 2022-03-30 | ||
US17/708,574 US12006388B2 (en) | 2022-03-30 | 2022-03-30 | Composite material including three-dimensional (3D) graphene |
US17/708,621 US11813774B2 (en) | 2022-03-30 | 2022-03-30 | Method of producing a composite material including three-dimensional (3D) graphene |
Publications (1)
Publication Number | Publication Date |
---|---|
TW202340387A true TW202340387A (en) | 2023-10-16 |
Family
ID=86052386
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW112111813A TW202340387A (en) | 2022-03-30 | 2023-03-28 | Composite material including three-dimensional (3d) graphene |
Country Status (2)
Country | Link |
---|---|
TW (1) | TW202340387A (en) |
WO (1) | WO2023192794A1 (en) |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4225769B2 (en) * | 2002-11-19 | 2009-02-18 | 日本合成化学工業株式会社 | Resin composition |
JP7001472B2 (en) * | 2014-07-30 | 2022-01-19 | ラトガース,ザ ステート ユニバーシティ オブ ニュー ジャージー | Graphene reinforced polymer matrix complex |
CN106349658B (en) * | 2016-08-22 | 2018-04-06 | 广东纳路纳米科技有限公司 | The plastic composite being modified based on three-dimensional grapheme and its preparation |
US10472497B2 (en) * | 2018-02-28 | 2019-11-12 | Lyten, Inc. | Composite materials systems containing carbon and resin |
CN109280268A (en) * | 2018-09-10 | 2019-01-29 | 安徽嘉美包装有限公司 | A kind of polypropylene plastics of superior performance and preparation method thereof |
US11489161B2 (en) * | 2019-10-25 | 2022-11-01 | Lyten, Inc. | Powdered materials including carbonaceous structures for lithium-sulfur battery cathodes |
US11309545B2 (en) * | 2019-10-25 | 2022-04-19 | Lyten, Inc. | Carbonaceous materials for lithium-sulfur batteries |
JP2023512804A (en) * | 2020-02-06 | 2023-03-29 | ライテン・インコーポレイテッド | Composite material system |
-
2023
- 2023-03-22 WO PCT/US2023/064838 patent/WO2023192794A1/en unknown
- 2023-03-28 TW TW112111813A patent/TW202340387A/en unknown
Also Published As
Publication number | Publication date |
---|---|
WO2023192794A1 (en) | 2023-10-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11674031B1 (en) | Container formed of a composite material including three-dimensional (3D) graphene | |
US11591457B1 (en) | Composite material including three-dimensional (3D) graphene and maleated copolymers | |
Zhang et al. | The superior mechanical and physical properties of nanocarbon reinforced bulk composites achieved by architecture design–a review | |
KR101712506B1 (en) | Manufacturing Method of Filament for 3D Print and Filament | |
KR101090729B1 (en) | Highly conductive resin composition having carbon composite | |
TW200533706A (en) | Compositions comprising carbon nanotubes and articles formed therefrom | |
CN110612323A (en) | Multifunctional nanocomposites enhanced with impregnated honeycomb carbon nanostructures | |
CN1224505C (en) | Article and mfg. process for article having individual material properties | |
WO2003078528A1 (en) | Conductive resin molding | |
CN109563274B (en) | Method for preparing nano-silver particle-impregnated nano-silver organic-inorganic composite resin and antibacterial water pipe prepared by using same | |
TW202340387A (en) | Composite material including three-dimensional (3d) graphene | |
US11813774B2 (en) | Method of producing a composite material including three-dimensional (3D) graphene | |
US12006388B2 (en) | Composite material including three-dimensional (3D) graphene | |
JP2019155634A (en) | Method for producing composite intermediate material | |
CN103450532A (en) | Preparation method of polyethylene PE nanoscale reinforced and modified particles | |
CN106146910A (en) | A kind of modified composite material in 3 D-printing | |
CN103214730A (en) | Polymer-based carbon nanotube orientation enhanced functional material and its preparation method and device | |
KR101947867B1 (en) | Carbon composite material and method for manufacturing thereof | |
CN107082956A (en) | A kind of talcum powder master batch | |
KR102076232B1 (en) | Bio-synthetic Wood Made of Waste Plastics And a Method of Manufacturing the Same | |
JP2018070855A (en) | Method for producing injection foam molding of carbon fiber reinforced and modified polyester resin | |
Stoeffler et al. | The effect of clay dispersion on the properties of LLDPE/LLDPE‐g‐MAH/montmorillonite nanocomposites | |
CN108219349A (en) | A kind of 3D printing modified ABS resin and preparation method thereof | |
CN104011141A (en) | Resin molded body for electrostatic coating | |
CN101585947A (en) | The preparation of low-cost fireresistant parting plastic complex film |