WO2022204398A1 - Dispersions for additive manufacturing comprising discrete carbon nanotubes - Google Patents
Dispersions for additive manufacturing comprising discrete carbon nanotubes Download PDFInfo
- Publication number
- WO2022204398A1 WO2022204398A1 PCT/US2022/021737 US2022021737W WO2022204398A1 WO 2022204398 A1 WO2022204398 A1 WO 2022204398A1 US 2022021737 W US2022021737 W US 2022021737W WO 2022204398 A1 WO2022204398 A1 WO 2022204398A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon nanotubes
- dispersion
- oxidized
- discrete carbon
- discrete
- Prior art date
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 314
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 286
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 285
- 239000006185 dispersion Substances 0.000 title claims abstract description 180
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 34
- 239000000654 additive Substances 0.000 title claims abstract description 29
- 230000000996 additive effect Effects 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000002270 dispersing agent Substances 0.000 claims description 109
- 239000002245 particle Substances 0.000 claims description 53
- -1 metallic and Substances 0.000 claims description 39
- 241000894007 species Species 0.000 claims description 39
- 229920001971 elastomer Polymers 0.000 claims description 37
- 239000000806 elastomer Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 33
- 239000000945 filler Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 25
- 229920001577 copolymer Polymers 0.000 claims description 22
- 238000009826 distribution Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910021389 graphene Inorganic materials 0.000 claims description 18
- 239000000919 ceramic Substances 0.000 claims description 16
- 239000011258 core-shell material Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 14
- 229920001169 thermoplastic Polymers 0.000 claims description 13
- 239000004416 thermosoftening plastic Substances 0.000 claims description 13
- 239000002048 multi walled nanotube Substances 0.000 claims description 12
- 229920000570 polyether Polymers 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 9
- 230000002902 bimodal effect Effects 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002835 absorbance Methods 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000003063 flame retardant Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 5
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 150000002170 ethers Chemical class 0.000 claims description 5
- 229910052621 halloysite Inorganic materials 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 150000004760 silicates Chemical class 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000000454 talc Substances 0.000 claims description 5
- 229910052623 talc Inorganic materials 0.000 claims description 5
- 239000010456 wollastonite Substances 0.000 claims description 5
- 229910052882 wollastonite Inorganic materials 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 4
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 4
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 4
- 239000003093 cationic surfactant Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 229910003460 diamond Inorganic materials 0.000 claims description 4
- 239000010432 diamond Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 241000894006 Bacteria Species 0.000 claims description 2
- 241000233866 Fungi Species 0.000 claims description 2
- 241000700605 Viruses Species 0.000 claims description 2
- 239000003124 biologic agent Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 21
- 230000005855 radiation Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 16
- 239000002131 composite material Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 description 22
- 239000011347 resin Substances 0.000 description 22
- 239000004609 Impact Modifier Substances 0.000 description 21
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 17
- 239000011257 shell material Substances 0.000 description 16
- 239000011230 binding agent Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 239000002071 nanotube Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000002109 single walled nanotube Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000011162 core material Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 229920005604 random copolymer Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000019241 carbon black Nutrition 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 229920000571 Nylon 11 Polymers 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- 230000005291 magnetic effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000003921 particle size analysis Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 4
- 229920000058 polyacrylate Polymers 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical group C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229940071826 hydroxyethyl cellulose Drugs 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229920000491 Polyphenylsulfone Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 229920004482 WACKER® Polymers 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 229920000800 acrylic rubber Polymers 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 206010061592 cardiac fibrillation Diseases 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000002079 double walled nanotube Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000002600 fibrillogenic effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229920000554 ionomer Polymers 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000000399 optical microscopy Methods 0.000 description 2
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical group 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000011417 postcuring Methods 0.000 description 2
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 2
- CIBMHJPPKCXONB-UHFFFAOYSA-N propane-2,2-diol Chemical compound CC(C)(O)O CIBMHJPPKCXONB-UHFFFAOYSA-N 0.000 description 2
- 239000011369 resultant mixture Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010146 3D printing Methods 0.000 description 1
- UFERIGCCDYCZLN-UHFFFAOYSA-N 3a,4,7,7a-tetrahydro-1h-indene Chemical compound C1C=CCC2CC=CC21 UFERIGCCDYCZLN-UHFFFAOYSA-N 0.000 description 1
- IRLPACMLTUPBCL-KQYNXXCUSA-N 5'-adenylyl sulfate Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](COP(O)(=O)OS(O)(=O)=O)[C@@H](O)[C@H]1O IRLPACMLTUPBCL-KQYNXXCUSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- 229920001081 Commodity plastic Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 108020004414 DNA Proteins 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 241000183290 Scleropages leichardti Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000560 biocompatible material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000002051 biphasic effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical group CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000003302 ferromagnetic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 102000040430 polynucleotide Human genes 0.000 description 1
- 108091033319 polynucleotide Proteins 0.000 description 1
- 239000002157 polynucleotide Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/324—Inkjet printing inks characterised by colouring agents containing carbon black
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Definitions
- the present invention is directed to additive manufacturing compositions and methods for producing additive manufacturing composite blends with oxidized discrete carbon nanotubes with dispersion agents bonded to at least one sidewall of the oxidized discrete carbon nanotubes.
- Such compositions are especially useful when radiation cured, sintered or melt fused.
- AM additive Manufacturing
- CAD Computer Aided Design
- Liquid radiation curable resins are selectively cross-linked (or cured) by an energy source such as lasers.
- Photocurable resin formulation efforts have focused on mechanical performance enhancement to simulate properties of commodity plastics and engineered polymers. Improving mechanical performance of photo-curable resins can be accomplished through development of special monomers and curing agents, altering chain growth mechanisms, utilization of mixed modes of polymerization and inclusion of additives and fillers.
- fillers have been utilized to meet specific performance requirements for select AM applications, such as stiffness.
- Inorganic fillers such as Si02 and A1203 have shown to improve the strength and stiffness of the components fabricated via vat photopolymerization, but often with much longer undesirable cure times.
- these fillers often cause high initial resin viscosity, poor viscosity stability, and exhibit a tendency of filler to separate from the base resin.
- Binder selection is considered essential for successful part fabrication.
- the binder must be jettable.
- An ideal binder has low viscosity, is stable under shear stresses, has good interaction with powdered feedstock, has a clean bum-out, has long shelf-life.
- Common in-liquid binding agents are butyral resins, polyvinyls, polysiloxanes, polyacrylic acids, and polyether-urethanes. It is desirable in some cases for a higher strength polymeric binder particularly where the sintering is occurring at higher temperatures.
- Binders for metallic and ceramic powders are typically aqueous or non-aqueous dispersions of inorganic particles such as silica, aluminum nitrate or film forming polymer dispersions.
- inorganic particles such as silica, aluminum nitrate or film forming polymer dispersions.
- the incorporation of nanoparticles into the binder system fills the voids in the packed powder bed and therefore improves sinterability, increases part density and reduces shrinkage.
- the melting point of nanoparticles decreases exponentially with a decrease in nanoparticle size. Therefore, nanoparticles in the binder will sinter at lower temperature than the feedstock powder and can fuse the large particles, thus improving green strength of the component.
- Binder for polymeric powders typically consist of the solvent or a solvent mixture that promote swelling of the polymeric feedstock leading to particle coalescence by interdiffusion and entanglement. Solutions of film forming polymeric dispersions can be used as binders as well. Processing hydrophilic powders such as starch plaster, and cement require aqueous binders. Hydrophobic polymer powders (e.g., polylactic acid or PLA) can be processed using organic solvents. These types of binders for polymeric powders can also be used to coat thermoplastic filaments for fusion into parts.
- Carbon nanotubes can be classified by the number of walls in the tube, single wall, double wall and multiwall. Each wall of a carbon nanotube can be further classified into chiral or non-chiral forms. Some of the carbon atoms of the carbon nanotube may be substituted by nitrogen atoms.
- Carbon nanotubes are currently manufactured as agglomerated carbon nanotube balls or bundles which have very limited commercial use. Use of carbon nanotubes as a reinforcing agent in polymer composites is an area in which carbon nanotubes are predicted to have significant utility. However, utilization of carbon nanotubes in these applications has been hampered due to the general inability to reliably produce individualized carbon nanotubes.
- the aspect ratio that is length to diameter ratio
- the maximum aspect ratio for a given tube length is taken to be reached when each tube is fully separated from another.
- a bundle of carbon nanotubes for example, has an effective aspect ratio in composites of the average length of the bundle divided by the bundle diameter.
- carbon nanotubes may be shortened extensively by aggressive oxidative means and then dispersed as individual nanotubes in dilute solution. These tubes have low aspect ratios not suitable for high strength composite materials.
- Carbon nanotubes may also be dispersed in very dilute solution as individuals by sonication in the presence of a surfactant.
- Illustrative surfactants used for dispersing carbon nanotubes in aqueous solution include, for example, sodium dodecyl sulfate, or cetyltrimethyl ammonium bromide.
- solutions of individualized carbon nanotubes may be prepared from polymer- wrapped carbon nanotubes.
- Individualized single-wall carbon nanotube solutions have also been prepared in very dilute solutions using polysaccharides, polypeptides, water-soluble polymers, nucleic acids, DNA, polynucleotides, polyimides, and polyvinylpyrrolidone, but these dilute solutions are unsuitable for additive manufacturing.
- the present invention relates to novel compositions and methods for producing additive manufacturing dispersions and parts thereof.
- the composition of this invention comprises an Additive Manufacturing dispersion, wherein the dispersion comprises at least one portion of a cross- linkable moiety, and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes wherein the oxidized, discrete carbon nanotubes are present in the range of greater than zero and up to about 30% by weight based on the total weight of the dispersion and a plurality of the carbon nanotubes present in the dispersion are discrete.
- the oxidized, discrete carbon nanotubes comprise an interior and exterior surface, each surface comprising an interior surface oxidized species content and an exterior surface oxidized species content, wherein the interior surface oxidized species content differs from the exterior surface oxidized species content by at least about 20%, and as high as 100%.
- the oxidized discrete carbon nanotubes can comprise a mixture of oxidized discrete carbon nanotubes with a bimodal or trimodal distribution of the diameters of the oxidized discrete carbon nanotubes formed from combinations of oxidized discrete single wall, oxidized discrete double wall and oxidized discrete multi wall carbon nanotubes.
- the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is preferably covalently bonded.
- the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes preferably comprises an average molecular weight in the range of about 50 to about 20,000 daltons and the weight fraction of bonded dispersing agent on the sidewall of the discrete carbon nanotubes relative to the oxidized discrete carbon nanotubes is greater than about 0.02 and less than about 0 8
- the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is preferably miscible with a material in contact with the bonded dispersing agent.
- a second embodiment of the invention is an Additive Manufacturing dispersion, wherein the dispersion comprises at least one portion of a cross-linkable acrylate moiety and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes wherein the bonded dispersing agent on the sidewall of the discrete carbon nanotubes comprises molecular units selected from the group of ethers.
- the molecular units of the second embodiment preferably comprise ethylene oxide.
- the first or second embodiments can further comprise fillers in the % weight from about 0.1% to about 30% by weight of the dispersion, preferably wherein the fillers are selected from the group consisting of carbon black, graphene, oxidized graphene, reduced graphene, carbon fibers, silicas, silicates, halloysite, clays, calcium carbonate, wollastonite, glass, fire-retardants and talc.
- the first or second embodiments can further comprise a member of the group consisting of thermoplastics, thermosets, and elastomers.
- the first or second embodiments can further comprise a core shell elastomer, wherein the elastomer preferably comprises particles having diameters from about 0.01 to about 1 micrometer.
- the first or second embodiments can further comprise semi-conductor, metallic, or ceramic powders, wherein the powders comprise particle diameters from about 1 nm to about 20 micrometers.
- the first or second embodiments can further compnse at least one additional dispersing agent attached to the sidewall of the oxidized discrete carbon nanotubes selected from the group consisting of anionic, cationic, nonionic and zwitterionic surfactants, polyvinyl alcohols, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones and their copolymers, carboxymethyl cellulose, carboxypropyl cellulose, carboxymethyl propyl cellulose, hydroxy ethyl cellulose, polyetherimines, poly ethers, starch, and mixtures thereof.
- anionic, cationic, nonionic and zwitterionic surfactants polyvinyl alcohols, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones and their copolymers, carboxymethyl cellulose, carboxypropyl cellulose, carboxymethyl propyl cellulose, hydroxy ethy
- the first or second embodiments wherein the oxidized discrete carbon nanotubes comprise about 0.1% to about 20% by weight of nitrogen atoms.
- a third embodiment of the Invention is an Additive Manufacturing dispersion wherein the dispersion comprises at least one portion of a thermoplastic moiety and discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the discrete carbon nanotubes wherein the discrete carbon nanotubes are present in an amount greater than zero and up to about 30% by weight based on the total weight of the dispersion.
- the third embodiment can comprise a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes at least partially thermally decomposes at less than about 500 °C in nitrogen with less than about 5% weight ash content.
- the third embodiment can comprise a plurality of discrete carbon nanotubes.
- Any of the three embodiments can comprise a part made by Additive Manufacturing having an electrical resistance less than about 10 billion ohms per square.
- Any of the three embodiments can comprise a dispersion having a UV-visible absorption at 500 nm greater than about 0.5 units of absorbance for a concentration of oxidized discrete carbon nanotubes in the dispersion of 2.5 xl0-5 g/ml.
- any of the three embodiments can further comprise a filler selected from the group of thermally conducting materials, such as but not limited to metals and metal alloys, boron nitride, aluminum oxide, silicon nitride, aluminum nitride, diamond, graphite and graphene.
- a filler selected from the group of thermally conducting materials, such as but not limited to metals and metal alloys, boron nitride, aluminum oxide, silicon nitride, aluminum nitride, diamond, graphite and graphene.
- Any of the three embodiments can further comprise a biologically reactive species selected from the group consisting of species that can interact with bacteria, virus, fungi, and biological agents.
- Oxidized carbon nanotubes are those carbon nanotubes that have been subj ected to oxidizing media, such as but not limited to, concentrated nitric acid, peroxides and persulfates, that introduces chemical units such as carboxylic acids, hydroxyls, ketones and lactones.
- the oxidized discrete carbon nanotubes are selected from the group consisting of oxidized discrete single wall, oxidized discrete double wall, or oxidized discrete multiwall carbon nanotubes.
- the oxidized, discrete carbon nanotubes can also comprise an interior and exterior surface, each surface comprising an interior surface oxidized species content (also called interior oxygen containing species content because the interior oxygen species may differ from the exterior oxygen species) and an exterior surface oxidized species content (also called exterior oxygen containing species content because the interior oxygen species may differ from the exterior oxygen species), wherein the interior surface oxidized species content differs from the exterior surface oxidized species content by at least 20%, and as high as 100%, preferably wherein the interior surface oxidized species content is less than the exterior surface oxidized species content.
- an interior surface oxidized species content also called interior oxygen containing species content because the interior oxygen species may differ from the exterior oxygen species
- an exterior surface oxidized species content also called exterior oxygen containing species content because the interior oxygen species may differ from the exterior oxygen species
- the interior surface oxidized species content can be up to 3 weight percent relative to carbon nanotube weight, preferably from about 0.01 to about 3 weight percent relative to carbon nanotube weight, more preferably from about 0.01 to about 2, most preferably from about 0.01 to about 1. Especially preferred interior surface oxidized species content is from zero to about 0.01 weight percent relative to carbon nanotube weight.
- the exterior surface oxidized species content can be from about 0.1 to about 65 weight percent relative to carbon nanotube weight, preferably from about 1 to about 40, more preferably from about 1 to about 20 weight percent relative to carbon nanotube weight. This is determined by comparing the exterior oxidized species content for a given plurality of nanotubes against the total weight of that plurality of nanotubes.
- the oxidized, discrete carbon nanotubes can further comprise a mixture of oxidized discrete carbon nanotubes with a bimodal or trimodal distribution of the diameters of the oxidized discrete carbon nanotube formed from combinations of oxidized discrete single wall, oxidized discrete double wall and oxidized discrete multiwall carbon nanotubes.
- the dispersion of oxidized discrete carbon nanotubes comprises a majority of oxidized discrete multi wall carbon nanotubes, more preferably a majority of oxidized discrete double wall carbon nanotubes and even more preferably a majority of oxidized discrete single wall carbon nanotubes. The meaning of majority is more than 50% by weight of all the carbon nanotubes present in the dispersion.
- the Additive Manufacturing dispersion the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is hydrogen bonded, preferably ionically bonded and more preferably covalently bonded.
- the oxidized discrete carbon nanotubes further have a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes consisting of a molecular weight in the range of about 50 to about 20,000 daltons.
- the molecular weight range of the bonded dispersing agent is from about 60 to about 5000 daltons and more preferably from about 70 to about 1000 daltons.
- the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes consists of chemical units selected from the group of carbon-carbon bonds, carbon-nitrogen bonds, carbon-oxygen bonds, carbon-sulfur bonds and silicon-oxygen bonds.
- the chemical units of the bonded dispersing agent are preferred to be able to be crosslinked into the matrices.
- the weight fraction of bonded dispersing agent on the sidewall of the discrete carbon nanotubes relative to the oxidized discrete carbon nanotubes is greater than about 0.02 and less than about 0.8.
- the weight fraction of bonded dispersing agent from about 0.03 to about 0.6, more preferably from about 0.05 to about 0.5 and most preferably from about 0.06 to about 0.4.
- the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is selected such that it has good compatibility with a material in contact with the dispersing agent.
- Good compatibility here is to mean a sufficient amount of electronic, van der Waals, ionic or dipole interactions such that the oxidized carbon nanotube can be dispersed as individual or discrete carbon nanotubes.
- the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is selected such that it is thermodynamically miscible, i.e., forms a homogeneous mixture with a material in contact with the dispersing agent.
- the bonded dispersing agent on the sidewall of the discrete carbon nanotubes can further comprise ethylene oxide molecular units. More preferred is the bonded dispersion agent comprise a mixture of propylene oxide and ethylene oxide molecular units. There may be a mixture of bonded dispersing agents on the sidewall of the discrete carbon nanotubes or a mixture of oxidized discrete carbon nanotubes with different types of bonded dispersion agents. [0042] In another embodiment of this invention the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes may be further selected to have a thermal decomposition such that at less than 500 °C in nitrogen there is less than about 5% weight ash content of the dispersing agent.
- the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes has a thermal decomposition such that at less than about 500 °C in nitrogen there is less than about 1% weight ash content of the dispersing agent and more preferably the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes has a thermal decomposition such that at less than about 400 °C in nitrogen there is less than about 1% weight ash content of the dispersing agent.
- the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes consist of an aspect ratio, known as the ratio of the length to diameter of the oxidized discrete carbon nanotube, from about 10 to about 10000.
- the aspect ratio is preferred to be from about 300 to about 10000, for oxidized discrete double wall carbon nanotubes the aspect ratio is preferred to be from about 150 to about 5000 and for oxidized discrete multiwall carbon nanotubes the aspect ratio is preferred from about 40 to about 500.
- the aspect ratio of the oxidized discrete carbon nanotubes can be a unimodal distribution, or a multimodal distribution (such as a bimodal or trimodal distribution).
- the multimodal distributions can have evenly distributed ranges of aspect ratios (such as 50% of one L/D range and about 50% of another L/D range).
- the distributions can also be asymmetrical - meaning that a relatively small percent of discrete nanotubes can have a specific L/D while a greater amount can comprise another aspect ratio distribution.
- an embodiment of this invention is that the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes are present in the weight range greater than zero and up to about 30% by weight based on the total weight of the dispersion.
- the weight range of oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes present in the dispersion is from about 0.01 to about 10% by weight and more preferably from about 0.01 to about 5% by weight based on the total weight of the dispersion.
- a plurality of the carbon nanotubes present in the dispersion are discrete.
- at least about 51% by weight of oxidized carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized carbon nanotubes present in the dispersion are discrete, preferably at least about 65% by weight of oxidized carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized carbon nanotubes present in the dispersion are discrete, more preferably at least about 75% by weight of oxidized carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized carbon nanotubes present in the dispersion are discrete and most preferably at least about 85% by weight of carbon nanotubes present in the dispersion are discrete.
- the dispersion of oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes comprises fillers in the % weight from about 0.05% to about 80% relative to the total weight of the dispersion.
- the % weight of fillers is from about 0.05% to about 30% and most preferably from about 0.1% to about 10% relative to the total weight of the dispersion.
- the fillers are selected from the group consisting of carbon black, graphene, oxidized graphene, reduced graphene, carbon fibers, silicas, silicates, halloysite, clays, calcium carbonate, wollastonite, glass, flame retardants and talc.
- the fillers may be in the shapes of roughly spherical particles, rods, fibers or plates.
- the fillers have at least one scale of dimension greater than about 1 nm and less than about 10 micrometers, more preferably have at least one scale of dimension greater than about 5 nm and less than about 2 micrometers and most preferably have at least one scale of dimension greater than about 10 nm and less than about 1 micrometer.
- the dispersion comprising of oxidized discrete carbon nanotubes further comprises a mixture of at least two different fillers. In some embodiments the dispersion comprising oxidized discrete carbon nanotubes further comprises a mixture of a different species of a single filler which may vary by particles size, thermal conductivity, packing, or molecular weight.
- the dispersion further comprises photo- crosslinkable monomers, oligomers or polymers.
- the cross-linkable monomers, oligomers or polymers contain molecular units selected from the group of carbon-carbon double bonds, carbon-carbon triple bonds, urethanes, acrylates, alkylacrylates, cyanonitriles, cyanoacrylates, nitriles, epoxies, amides, amines, alcohols, ethers and esters.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises a thermoplastic.
- the dispersion of oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes may coat the thermoplastic or oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes may be dispersed within the thermoplastic.
- a preferred thermoplastic is selected from the group of amorphous and semi-crystalline thermoplastics, including, but not limited to, Polylactic acid (PLA), Acrylonitrile butadiene styrene (ABS), Polycarbonate (PC), Polycarbonate - Acrylonitrile butadiene styrene blend (PC- ABS), Polyetherimide (PEI), Polyphenylsulfone (PPSF), Polyethylene terephthalate (PET), Polyethylene terephthalate glycol (PETG), Polyether ether ketone (PEEK), Polyamides, such as but not limited to Nylon 12, Nylon 11, Nylon 6, and Nylon 6,6, polyvinyl alcohol and copolymers, polyvinylbutyrate and copolymers, polyvinylpyrrolidone and copolymers, polyether and copolymers.
- the thermoplastic may be a linear, grafted, comb or block polymer.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises elastomers.
- the elastomers can be selected from the group consisting of, but not limited to, natural rubber, polyisobutylene, polybutadiene, styrene-butadiene hydrogenated styrene-butadiene, butyl rubber, polyisoprene, styrene- isoprene rubber, ethylene propylene diene, silicones, polyurethanes, polyester, polyether, polyacrylates, hydrogenated and non-hydrogenated nitrile rubbers, halogen modified elastomers, polyolefin elastomers fluoroelastomers, and combinations thereof.
- the elastomers may be non-crosslinked or crosslmked, grafted or copolymers.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises polymeric impact modifiers with a glass transition temperature of less than about 25 °C.
- the impact modifiers are selected from the group of polyethers, polyesters, vinylpolymers, polyvinylcopolymers, polyolefins polyacrylates, polyurethanes, polyamides and polysiloxanes, blends and copolymers thereof. They may be further functionalized with reactive groups, such as but not limited to epoxy, hydroxyl, isocyanate, and carboxylic groups.
- the impact modifiers are preferred to be phase-separated from the main matrix material of the dispersion yet have good cohesion or thermodynamic interaction. More preferred is that the composition of the impact modifiers that are block copolymers or core shell polymers. Examples of core shell polymers are PARALOIDTM Impact Modifiers which are acrylate or butadiene based. More preferred is that the impact modifiers have a refractive index value at least within 0.03 units of the refractive index value of the matrix, more preferably within 0.02 units, so as to minimize the scattering of radiation in the UV -visible wavelength range.
- the core-shell particles can include more than one core and/or more than one shell.
- mixtures of core-shell particles with elastomer particles can be used.
- two different diameters of impact modifiers are used in a certain ratio. The use of two different impact modifiers with different diameters has the effect of lowering the viscosity of the liquid radiation curable resin.
- the composition of impact modifiers is about a 7 to 1 ratio of diameter (e.g. 140 nm particles vs. a 20 nm particles) and about a 4 to 1 ratio of wt%.
- the composition of impact modifiers is about a 5 to 1 ratio of diameter and about a 4 to 1 ratio of wt%.
- the composition of impact modifiers is about a 5 to 1 ratio of diameter and about a 6 to 1 ratio of wt%.
- the phase-separated domain size of the impact modifier in the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes can be greater than about 0.005 micrometers and less than about 1 micrometer in diameter, preferably greater than 0.01 micrometers and less than about 0.8 micrometer in diameter and most preferably greater than about 0.05 micrometers and less than about 0.6 micrometer in diameter.
- the impact modifier may be present in the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes from at least about 0.1% to less than about 30% by weight of the dispersion, preferably at least greater than about 0.5% to less than about 15% and most preferably at least about 2% to less than about 10%.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises metallic powders.
- the metallic powders can contain any of those metal elements listed in the Periodic Table of Elements.
- the metals may also be in the form of metal oxides, carbides, silicides or nitrides, or alloys with other elements.
- Preferred metallic powders can be selected, but not limited to, the class of stainless steel, Inconel, bronze, copper, silver, platinum, tungsten, Aluminum, cobalt, platinum, and tungsten carbide. More preferred is that the metallic powders have a particle diameter greater than about 1 nm and less than about 20 micrometers. For more effective sintering it may be further preferred to have a bimodal metallic powder particle diameter distribution. Yet further preferred is that in the metallic powder particle distribution the number of larger particle size be in the majority.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises ceramic powders.
- the ceramic powders can be selected from, but not limited to, the class of aluminum oxide, zirconium oxide, silica, boron nitride and silicon carbide and blends thereof. Preferred is that the ceramic powders have a particle diameter greater than about 1 nm and less than about 20 micrometers. For more effective sintering of the ceramic it may be further preferred to have a bimodal ceramic powder particle diameter distribution. Yet further preferred that in the ceramic powder particle distribution that the number of larger particle size be in the majority.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises a mixture of ceramic powders and metallic powders which when sintered form cermets.
- the preferred cermets which are based on carbides, nitrides, borides, and silicides of the fourth to sixth element groups of the Periodic Table of Elements.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprising at least one additional dispersing agent attached to the sidewall of the oxidized discrete carbon nanotubes selected from the group consisting of anionic, cationic, nonionic and zwitterionic surfactants, polyvinyl alcohols, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones and their copolymers, carboxymethyl cellulose, carboxypropyl cellulose, carboxymethyl propyl cellulose, hydroxyethyl cellulose, polyetherimines, polyethers, starch, and mixtures thereof.
- the non-covalently attached polymeric dispersion agents be selected from the group of amphiphilic polymers.
- the molecular weight of the additional dispersing agent attached to the sidewall of the oxidized discrete carbon nanotubes is preferred to be in the range of about 100 to about 400,000 daltons, more preferably in the range of about 1000 to about 200,000 daltons and most preferably in the range of about 10,000 to about 100,000 daltons.
- the additional dispersing agents attached to the sidewall of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes can be present in the dispersion in the weight ratio of attached additional dispersing agent to oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes from about 0.01 to about 2.
- the weight ratio is from about 0.1 to about 1 and most preferably from about 0.2 to about 0.75.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further compnses an organic solvent.
- a preferred organic solvent is selected from the group of alcohols, ethers, ketones, dioxolane, acetates, glycols, and mixtures thereof.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises water.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is electrostatic-dissipative.
- the dispersion has a surface resistivity of less than 10 billion ohms per square, more preferably less than 10 million ohms per square.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes further comprises about 0.1% to about 20% by weight of nitrogen atoms.
- the UV-visible absorption at 500 nm for the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is above 0.5 units of absorbance for a concentration of oxidized discrete carbon nanotubes with a bonded dispersing agent in the dispersion of 2.5 xlO 5 g/ml.
- the unit of absorption is above 0.75 at the same concentration of oxidized carbon nanotubes and wavelength of measurement, most preferably above 1 unit of absorbance at the same concentration of oxidized carbon nanotubes and wavelength of measurement.
- the filler can be selected from the group of fire retardants consisting of char formation agents, intumescent agents, and reactions in the gas phase such but not limited to organic halides (haloalkanes).
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes comprises a filler selected from the group of thermally conducting materials such as but not limited to metals and metal alloys, boron nitride, aluminum oxide, silicon nitride, aluminum nitride, diamond, graphite.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes comprises a filler selected from the group of magnetic and ferromagnetic materials, such as but not limited to those materials containing atoms of nickel, iron, cobalt and their alloys and oxides.
- An embodiment of this invention is the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent further comprising magnetic or ferromagnetic particles provide electromagnetic absorbance or shielding at frequencies greater than about 1 MHz, preferably at frequencies greater than about 1GHz.
- the dispersion of the oxidized discrete carbon nanotubes with a bonded dispersing agent further comprising electron conducting filler particles are also desirable for shielding of radio frequencies.
- the dispersion comprising at least one portion of a cross-linkable moiety, and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes is crosslinked at least partially by radiation followed by post-curing comprises at least one portion of a cross-linkable moiety, and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes to achieve final desired part performance by thermal or irradiative methods wherein the time to post cure to achieve the final desired part performance is 10% less than the dispersion without oxidized discrete carbon nanotubes, preferably 25% less time and more preferably 50% less time.
- the dispersion comprising at least one portion of a cross- linkable moiety, and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes is jettable.
- the dispersion comprising at least one portion of a cross- linkable moiety, and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes further comprising materials which can be sintered using about 10% less radiation power than a similar dispersion not containing oxidized discrete carbon nanotubes, preferably using about 25% less radiation power, more preferably using about 50% less radiation power than a similar dispersion not containing oxidized discrete carbon nanotubes.
- the dispersion of oxidized discrete carbon nanotubes with bonded dispersion agent further comprises an elastomer wherein the final part exhibits at least about 20% higher resistance to fracture under cyclic fatigue, preferably at least about 50% and most preferably at least about 100% higher resistance to fracture than a similar dispersion without the oxidized discrete carbon nanotubes with bonded dispersion agent.
- Embodiment 1 An Additive Manufacturing dispersion wherein the dispersion comprises at least one portion of a cross-linkable moiety, and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes wherein the oxidized, discrete carbon nanotubes are present in the range of greater than zero and up to about 30% by weight based on the total weight of the dispersion and a plurality of the carbon nanotubes present in the dispersion are discrete.
- Embodiment 2 The dispersion of Embodiment 1 wherein the oxidized, discrete carbon nanotubes comprise an interior and exterior surface, each surface comprising an interior surface oxidized species content and an exterior surface oxidized species content, wherein the interior surface oxidized species content differs from the exterior surface oxidized species content by at least about 20%, and as high as 100%.
- Embodiment 1 wherein the oxidized discrete carbon nanotubes comprise a mixture of oxidized discrete carbon nanotubes with a bimodal or trimodal distribution of the diameters of the oxidized discrete carbon nanotubes formed from combinations of oxidized discrete single wall, oxidized discrete double wall and oxidized discrete multi wall carbon nanotubes.
- Embodiment 4 The dispersion of Embodiment 1 wherein the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is covalently bonded.
- Embodiment 5 The dispersion of Embodiment 1 wherein the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes comprises an average molecular weight m the range of about 50 to about 20,000 daltons and the weight fraction of bonded dispersing agent on the sidewall of the discrete carbon nanotubes relative to the oxidized discrete carbon nanotubes is greater than about 0.02 and less than about 0.8.
- Embodiment 6 The dispersion of Embodiment 1 wherein the bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes is miscible with a material in contact with the bonded dispersing agent.
- Embodiment 7 An Additive Manufacturing dispersion wherein the dispersion comprises at least one portion of a cross-linkable acrylate moiety and oxidized, discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the oxidized discrete carbon nanotubes wherein the bonded dispersing agent on the sidewall of the discrete carbon nanotubes comprises molecular units selected from the group of ethers.
- Embodiment 8 The dispersion of Embodiment 7 wherein the molecular units comprise ethylene oxide.
- Embodiment 9 The dispersion of Embodiment 1 further comprising fillers in the % weight from about 0.1% to about 30% by weight of the dispersion selected from the group consisting of carbon black, graphene, oxidized graphene, reduced graphene, carbon fibers, silicas, silicates, halloysite, clays, calcium carbonate, wollastonite, glass, fire-retardants and talc.
- fillers in the % weight from about 0.1% to about 30% by weight of the dispersion selected from the group consisting of carbon black, graphene, oxidized graphene, reduced graphene, carbon fibers, silicas, silicates, halloysite, clays, calcium carbonate, wollastonite, glass, fire-retardants and talc.
- Embodiment 10 The dispersion of Embodiment 1 further comprising a member of the group consisting of thermoplastics, thermosets, and elastomers.
- Embodiment 11 The dispersion of Embodiment 1 further comprising a core shell elastomer further comprising particles diameters from about 0.01 to about 1 micrometer.
- Embodiment 12 The dispersion of Embodiment 1 further comprising semi conductor, metallic and, or ceramic powders with particle diameters from about 1 nm to about 20 micrometers.
- Embodiment 13 The dispersion of Embodiment 1 further comprising at least one additional dispersing agent attached to the sidewall of the oxidized discrete carbon nanotubes selected from the group consisting of anionic, cationic, nonionic and zwitterionic surfactants, polyvinyl alcohols, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones and their copolymers, carboxymethyl cellulose, carboxypropyl cellulose, carboxymethyl propyl cellulose, hydroxyethyl cellulose, polyetherimines, polyethers, starch, and mixtures thereof.
- additional dispersing agent attached to the sidewall of the oxidized discrete carbon nanotubes selected from the group consisting of anionic, cationic, nonionic and zwitterionic surfactants, polyvinyl alcohols, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones and their cop
- Embodiment 14 The composition of Embodiment 1 wherein the oxidized discrete carbon nanotubes comprise about 0.1% to about 20% by weight of nitrogen atoms.
- Embodiment 15 An Additive Manufacturing dispersion wherein the dispersion comprises at least one portion of a thermoplastic moiety and discrete carbon nanotubes with a bonded dispersing agent on at least one sidewall of the discrete carbon nanotubes wherein the discrete carbon nanotubes are present in an amount greater than zero and up to about 30% by weight based on the total weight of the dispersion.
- Embodiment 16 The dispersion of Embodiment 15 wherein a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes at least partially thermally decomposes at less than about 500 °C in nitrogen with less than about 5% weight ash content.
- Embodiment 17 The Additive Manufacturing dispersion of Embodiment 15 wherein a plurality of carbon nanotubes is discrete.
- Embodiment 18 The dispersion of Embodiment 1 wherein a part made by Additive Manufacturing has an electrical resistance less than 10 billion ohms per square.
- Embodiment 19 The dispersion of Embodiment 1 wherein the dispersion has a UV -visible absorption at 500 nm greater than about 0.5 units of absorbance for a concentration of oxidized discrete carbon nanotubes in the dispersion of 2.5 xl0-5 g/ml.
- Embodiment 20 The dispersion of Embodiment 1 further comprises a filler selected from the group of thermally conducting materials, such as but not limited to metals and metal alloys, boron nitride, aluminum oxide, silicon nitride, aluminum nitride, diamond, graphite and graphene.
- a filler selected from the group of thermally conducting materials, such as but not limited to metals and metal alloys, boron nitride, aluminum oxide, silicon nitride, aluminum nitride, diamond, graphite and graphene.
- Embodiment 21 An additive manufacturing dispersion for at least partially encapsulating electronic components, wherein the dispersion comprises: at least one portion of a cross-linkable moiety; and oxidized, discrete carbon nanotubes; wherein the oxidized, discrete carbon nanotubes comprise a dispersing agent bonded on a sidewall of the oxidized, discrete carbon nanotubes; and wherein the oxidized, discrete carbon nanotubes are present in the range of greater than zero and up to about 30% by weight based on the total weight of the dispersion; and wherein a plurality of the carbon nanotubes present in the dispersion are discrete.
- a dispersion comprising oxidized, discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes wherein the oxidized, discrete carbon nanotubes are present in an amount greater than zero and up to about 30% by weight based on the total weight of the dispersion and a plurality of the oxidized carbon nanotubes present in the dispersion are discrete.
- As-made carbon nanotubes using metal catalysts such as iron, aluminum or cobalt can retain a significant amount of the catalyst associated or entrapped within the carbon nanotube, as much as five weight percent or more. These residual metals can be deleterious in such applications as electronic devices because of enhanced corrosion or can interfere with the vulcanization process in curing elastomer composites. Furthermore, these divalent or multivalent metal ions can associate with carboxylic acid groups on the carbon nanotube and interfere with the discretization of the carbon nanotubes in subsequent dispersion processes.
- metal catalysts such as iron, aluminum or cobalt
- a dispersion comprising oxidized, discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes comprising a residual metal concentration of less than about 50,000 parts per million, ppm, and preferably less than about 10,000 parts per million.
- the residual catalyst concentration can be conveniently determined by using thermogravimetry by heating at 5 °C/min in nitrogen from 25 °C to 800 °C then switching the gas to air and holding at 800 °C for 30 minutes.
- the % residual ash is determined by the weight of material remaining compared to the weight of the starting material. The ash can then be analyzed for metal type using energy dispersive X-ray and a scanning electron microscope.
- the oxidized discrete carbon nanotubes can be separation from the dispersion medium and analyzed using atomic absorption techniques.
- the oxidation level of the oxidized discrete carbon nanotubes is defined as the amount by weight of oxygenated species covalently bound to the carbon nanotube.
- the thermogravimetric method for the determination of the percent weight of oxygenated species on the carbon nanotube involves taking about 5 mg of the dried oxidized carbon nanotube and heating at 5 °C/minute from room temperature to 800 degrees centigrade in a dry nitrogen atmosphere. The percentage weight loss from 200 to 600 degrees centigrade is taken as the percent weight loss of oxygenated species.
- the oxygenated species can also be quantified using Fourier transform infra-red spectroscopy, FTIR, particularly in the wavelength range from 1680 to 1730 cm 1 .
- the oxidized carbon nanotubes can have oxidation species comprising of carboxylic acid or derivative carbonyl containing species.
- the derivative carbonyl species can include ketones, quaternary amines, amides, esters, acyl halogens, monovalent metal salts and the like.
- the carbon nanotubes may comprise an oxidation species selected from hydroxyl or derived from hydroxyl containing species, ketones and lactones.
- the term discrete is taken here to mean individual carbon nanotubes separated substantially along their length, i.e., not bundled. Aspect ratio is defined as the length to diameter ratio of the carbon nanotube. If a bundle of carbon nanotubes are present the aspect ratio is taken as the length to diameter ratio of the bundle. For a spherical ball of entangled carbon nanotubes the aspect ratio is taken as 1.
- the aspect ratio of the oxidized discrete carbon nanotubes can be a unimodal distribution, or a multimodal distribution (such as a bimodal or trimodal distribution).
- the multimodal distributions can have evenly distributed ranges of aspect ratios (such as 50% of one L/D range and about 50% of another L/D range).
- the distributions can also be asymmetrical - meaning that a relatively small percent of discrete nanotubes can have a specific L/D while a greater amount can comprise another aspect ratio distribution.
- the aspect ratio of the oxidized discrete carbon nanotubes can be determined, for example, using dilutions of the dispersion in organic solvent and scanning electron microscopy.
- Manufacturers of carbon nanotubes that may be suitable for use in the applications described herein include, for example, Southwest Nanotechnologies, Zeonano or Zeon, CNano Technology, Nanocyl, ACS Materials, American Elements, Chasm Technologies, Haoxin Technology, Hanwha Nanotech Group, Hyperion Catalysis, KH Chemical, Klean Commodities, LG Chem, Nano-C, NTP Shenzhen Nanotech Port, Nikkiso, Raymor, Saratoga Energy , SK Global, Solid Carbon Products, Sigma Aldrich, Sun Nanotech, Thomas Swan, TimesNano, Tokyo Chemical Industry, XF Nano, and OCSiAl.
- a method to obtain discrete carbon nanotubes is to subject the carbon nanotubes to high mechanical forces.
- samples may be subjected to intensely disruptive forces generated by shear (turbulent) and/or cavitation with process equipment capable of producing energy densities as high as of 10 6 to 10 s Joules/m 3 .
- Equipment that meets this specification includes but is not limited to ultrasonicators, cavitators, mechanical homogenizers, pressure homogenizers and microfluidizers.
- One such homogenizer is shown in U.S. Patent 756,953, the disclosure of which is incorporated herein by reference.
- Additional shearing equipment includes, but is not limited to, HAAKETM mixers, Brabender mixers, Omni mixers, Silverson mixers, Colloidal mills, Gaullin homogenizers, and/or twin-screw extruders.
- HAAKETM mixers Brabender mixers
- Omni mixers Omni mixers
- Silverson mixers Colloidal mills
- Gaullin homogenizers and/or twin-screw extruders.
- a plurality of high-surface area oxidized carbon nanotubes results from this process, preferably at least about 60%, more preferably at least about 75%, most preferably at least about 95% and as high as 100%, with the minority of the tubes, usually the vast minority of the tubes remaining tightly bundled and with the surface of such tightly bundled nanotubes substantially inaccessible.
- Bosnyak et al. in various patent applications (e.g., US 2012-0183770 A1 and US 2011-0294013 Al), have made discrete carbon nanotubes through judicious and substantially simultaneous use of oxidation and shear forces, thereby oxidizing both the inner and outer surface of the nanotubes, ty pically to approximately the same oxidation level on the inner and outer surfaces, resulting in individual or discrete tubes.
- the present inventions differ from those earlier Bosnyak et al. applications and disclosures.
- the degree of fibrillation of the carbon nanotubes can influence the population of carbon nanotubes that differ by extent or type of oxygen containing species and also the bonded dispersing agent on the sidewall of the oxidized carbon nanotubes. For example, if many of the tubes are aligned as trunks then the tubes within the core of the trunk are less likely to contain oxygenated species on reaction with say nitric acid than the tubes on the outermost portion of the trunk.
- modified carbon nanotubes For a more homogeneous population of modified carbon nanotubes it is desired to have discrete or open structure of carbon nanotubes during the reaction to modify the carbon nanotube. For some applications such as, but not limited to electrical conductivity in biphasic materials it may be desirable to control the degree of fibrillation of the carbon nanotube bundle to obtain a distribution of bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes.
- the dispersion comprising oxidized discrete carbon nanotubes with a bonded dispersing agent on the sidewall of the oxidized discrete carbon nanotubes can be made by first making oxidized discrete carbon nanotubes then bonding the dispersing agent on the sidewall or ends of the oxidized discrete carbon nanotubes, or alternatively making oxidized carbon nanotubes, then bonding the dispersing agent on the sidewall or ends of the oxidized carbon nanotubes, then making the carbon nanotubes with bonded dispersion agent discrete.
- the dispersion of oxidized discrete carbon nanotubes with bonded dispersion agent can be used advantageously in Additive Manufacturing to improve the processing and part performance by employing near infra-red to radio frequency radiation up to 1 Terahertz which is absorbed rapidly by the carbon nanotubes to create heat. This effect can be used to improve the time required to fully cure cross-linkable molecules, improve the sintering of materials and reduced part warpage.
- Suitable impact modifiers are elastomers and, more preferably, prefabricated elastomer particles. These elastomers have a glass transition temperature (Tg) lower than 0 °C, preferably lower than -20 °C.
- Particle size of the impact modifying component can be accomplished by using, for example, a dynamic light scattering nanoparticle size analysis system.
- a dynamic light scattering nanoparticle size analysis system is the LB-550 machine, available from Honba Instruments, Inc.
- a preferred method of measuring particle size is laser diffraction particle size analysis in accordance with IS013320:2009. Information regarding such analysis can be found in Setting New Standards for Laser Diffraction Particle Size Analysis. Alan Rawle and Paul Kippax, Laboratory Instrumentation News, January 21, 2010.
- Monomers from a liquid radiation curable resin or solvents used in analysis can affect the measured average particle size. Additionally, analysis by laser diffraction may require the use of a solvent or other low viscosity dispersant. These solvents may affect measured average particle size.
- dispersed average particle size refers to those particles that have been exposed to the listed monomers of a given formulation, dispersed, and then analyzed using propylene carbonate as solvent for laser diffraction particle size analysis. Dispersions of impact modifier particles were subjected to particle size analysis while in dilute propylene carbonate solution, typically used was a concentration of 0.1-0.4g dispersion in lOg propylene carbonate.
- Suitable impact modifying components which can be mixed into the dispersion of oxidized discrete carbon nanotubes with bonded dispersion agent are elastomers based on copolymers of ethylene or propylene and one or more C2 to C12 olefin monomers.
- Examples of such are ethylene/propylene copolymers or ethylene/propylene copolymers, optionally containing a third copolymerizable diene monomer (EPDM), such as 1 ,4-hexadiene, dicyclopentadiene, di-cyclooctadiene, methylene norbomene, ethylidene norbomene and tetrahydroindene; ethylene/a-olefm copolymers, such as ethylene-octene copolymers and ethylene/a- olefm/polyene copolymers.
- EPDM copolymerizable diene monomer
- Suitable elastomers are polybutadiene, polyisoprene, styrene/butadiene random copolymer, styrene/isoprene random copolymer, acrylic rubbers (e.g., polybutylacr late), poly(hexamethylene carbonate), ethylene/acr late random copolymers and acrylic block copolymers, styrene/butadiene/(meth)acrylate (SBM) block-copolymers, styrene/butadiene block copolymer (styrene- butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS) and their hydrogenated versions, SEBS, SEPS), and (SIS) and ionomers.
- SBM styrene/butadiene/(meth)acrylate
- SBS styrene/
- Suitable commercial elastomers are Kraton (SBS, SEBS, SIS, SEBS and SEPS) block copolymers produced by Shell, Nanostrength block copolymers E20, E40 (SBM type) and M22 (full- acrylic) as produced by Arkema, Lotryl ethyl/acrylate random copolymer (Arkema) and Surlyn ionomers (Dupont).
- the elastomer may be modified to contain reactive groups such as e.g. epoxy, oxetane, carboxyl or alcohol.
- This modification can e.g. be introduced by reactive grafting or by copolymerization.
- Commercial examples of the latter are the Lotader random ethylene/acrylate copolymers AX8840 (glycidyl methacrylate/GMA modified), AX8900 and AX8930 (GMA and maleic anhydride modified/MA) produced by Arkema.
- the elastomer may be crosslinked after mixing into a dispersion of oxidized discrete carbon nanotubes with bonded dispersion agent.
- the crosslinking structure may be introduced via a conventional method.
- crosslinking agents used in such a materials peroxide, sulfur, cresol and the like, optionally in combination with multifunctional monomers like divinylbenzene, ethylene glycol di(meth)acrylate, diallylmaleate, triallylcyanurate, triallylisocyanurate, diallylphthalate, trimethylolpropane triacrylate, allyl methacrylate and the like can be given.
- the impact modifiers that can be mixed into the dispersion of oxidized discrete carbon nanotubes with bonded dispersion agent are pre-fabricated elastomer particles.
- Elastomer particles may be prepared by a variety of means, including those obtained by isolation from latex made via emulsion polymerization, or preparation in-situ in another component of the composition.
- Suitable commercial sources of such pre-fabricated elastomer particles are PB (polybutadiene) or PBA (polybutylacrylate) lattices available with varying average particle size from various producers, or lattices obtained by emulsification of EPDM, SBS, SIS or any other rubber.
- PB polybutadiene
- PBA polybutylacrylate
- the elastomer may contain a crosslinking structure.
- the crosslinking structure may be introduced by a conventional method.
- crosslinking agents used in such a material peroxide, sulfur, cresol and the like, optionally in combination with multifunctional monomers like divinylbenzene, ethylene glycol di(meth)acrylate, diallylmaleate, triallylcyanurate, triallylisocyanurate, diallylphthalate, trimethylolpropane triacrylate, allyl methacrylate, and the like can be given.
- a shell may be present on the particles that can e.g. be introduced via grafting or during a second stage of emulsion polymenzation.
- Examples of such particles are core-shell impact modifier particles that contain a rubber core and a glassy shell.
- core materials are polybutadiene, polyisoprene, acrylic rubber (e.g. polybutylacrylate rubber), styrene/butadiene random copolymer, styrene/isoprene random copolymer, or polysiloxane.
- shell materials or graft copolymers are (co)polymers of vinyl aromatic compounds (e.g. styrene) and vinyl cyanides (e.g. acrylonitrile) or (meth)acrylates, (e.g. methylmethacrylate).
- reactive groups can be incorporated into the shell by copolymerization, such as copolymerization with glycidyl methacrylate, or by treatment of the shell to form reactive functional groups.
- Suitable reactive functional groups include, but are not limited to, epoxy groups, oxetane groups, hydroxyl groups, carboxyl groups, vinyl ether groups, and/or acrylate groups.
- Suitable commercially available products of these core-shell type elastomer particles are, for example but not limited to, Resinous Bond RKB (dispersions of core-shell particles in epoxy manufactured by Resinous Chemical Industries Co., Ltd.), Durastrength D400, Durastrength 400R (manufactured by Arkema Group), Paraloid EXL-2300 (non functional shell), Paraloid EXL-2314 (epoxy functional shell), Paraloid EXL-2600, Paraloid KM 334, and Paraloid EXL 2300G.
- Paraloid core shell elastomers are manufactured by Dow Chemical Co.
- Genioperl P53, Genioperl P23, Genioperl P22 are manufactured by Wacker Chemical, Kane Ace MX products (manufactured by Kaneka).
- elastomer particles are crosslinked polyorganosiloxane rubbers that may include dialkylsiloxane repeating units, where "alkyl” is Ci to Ce alkyl.
- Such particles may be made by the method disclosed in U.S. Pat. No. 4,853,434 to Block, incorporated in its entirety herein by reference.
- the particles may be modified to include reactive groups such as oxirane, glycidyl, oxetane, hydroxyl, vinyl ester, vinyl ether, or (meth)acrylate groups, or combinations thereof, preferably on the surface of the particles.
- reactive groups such as oxirane, glycidyl, oxetane, hydroxyl, vinyl ester, vinyl ether, or (meth)acrylate groups, or combinations thereof, preferably on the surface of the particles.
- polyorganosiloxane elastomer particles that are commercially available are Albidur.
- EP 2240(A), Albidur EP 2640, Albidur VE 3320, Albidur EP 5340, Albidur EP 5640, and Albiflex 296 (dispersions of particles in epoxy or vinyl ether resins, Hanse Chemie, Germany), Genioperl M41C (dispersion in epoxy, Wacker Chemical), Chemisnow MX Series and MP Series (Soken Chemical and Engineering Co.).
- Genioperl M41C disersion in epoxy, Wacker Chemical
- Chemisnow MX Series and MP Series Soken Chemical and Engineering Co.
- Other materials that can be used to make the core-shell particles for use in the present invention can be found in for example: Nakamura et al, J Appl. Polym. Sci. v 33 n 3 Feb.
- the core-shell particles can include more than one core and/or more than one shell.
- mixtures of core-shell particles with elastomer particles can be used.
- Two different diameters of impact modifiers can be used in a certain ratio to lower the viscosity of the dispersion comprising a cross-linkable monomer or oligomer.
- the composition of impact modifiers can be about a 7 to 1 ratio of diameters i.e. 140 nm diameter particles vs 20 nm diameter particles and about a 4 to 1 ratio of wt%.
- Another desirable feature of selection of the elastomer or impact modifier is to select a composition of the elastomer or impact modifier that has a refractive index value at least within 0.03 units of the refractive index value of the material it is dispersed in, more preferably within 0.02 units, so as to minimize the scattering of radiation in the UV-visible wavelength range.
- An example of such a mixture is Paraloid KM 334, refractive index 1.47, and Dymax BR-952- a urethane dimethacrylate, refractive index 1.48.
- the dispersion of oxidized discrete carbon nanotubes with bonded dispersion agent further comprises fillers in the % weight from about 0.1% to about 30% by weight of the dispersion selected from the group consisting of carbon black, graphene, oxidized graphene, reduced graphene, carbon fibers, silicas, silicates, halloysite, clays, calcium carbonate, wollastonite, glass, fire-retardants and talc.
- the fillers can also be surface modified to improve their bonding and distribution within the dispersion.
- An example of a surface treatment is the use of a silane coupling agent to silica particles.
- a general method to determine the thermal conductivity of the dispersion is to apply a known heat flux to a sample and once the sample's steady-state temperature is reached, the difference in temperature across the thickness of the sample is measured. After assuming one-dimensional heat flow and an isotropic medium, Fourier's Law is then used to calculate the measured thermal conductivity,
- Example 2 Oxidizing multiwall carbon nanotubes, CNano Flotube 9000
- the filter cake is washed one time with four liters of deionized water followed by one wash of four liters of an ammonium hydroxide solution at pH greater than 9 and then two more washes with four liters of deionized water.
- the resultant pH of the final wash is 4.5.
- a small sample of the filter cake is dried in vacuum at 100°C for four hours and a thermogravimetric analysis taken as described previously .
- the amount of oxidized species on the fiber is 2.4 percent weight and the average aspect ratio as determined by scanning electron microscopy to be 60.
- the residual catalyst content is determined as 2,500 ppm.
- Example 3 Covalently attaching a dispersing agent to oxidized single wall carbon nanotube.
- the slurry is then passed through a laboratory scale homogenizer keeping the temperature below 45 °C until no large structures > 20 micrometers in scale are observed by optical microscopy.
- the resultant mixture is then filtered using a Buchner filter and number 2 Whatman filter paper at 13 and washed 4 times with 100 cm 3 of 35% wt aqueous isopropyl alcohol.
- the washed wet cake is then dried first in a convection oven at 120 °C to 95% solids, then in a vacuum oven at 150 °C for 1 hour. This is termed SWNT MB in Table 1.
- Example 4 Covalently attaching a dispersing agent to oxidized multiwall carbon nanotube.
- oxidized multiwall carbon nanotubes from example 2 in the form of a wet cake with water of solids content 5% weight.
- 40 g of wet cake is mixed with 30g of isopropanol then 2g of Jeffamine M2005 monoamine terminated polyether dissolved in 350g of isopropanol and 622g water is added with stirring. Stirring is continued for 10 minutes.
- the slurry is transferred to a Waring Blender and blended at high speed for 10 minutes.
- the slurry is then passed through a laboratory scale homogenizer keeping the temperature below 45 °C until no large structures > 20 micrometers in scale are observed by optical microscopy.
- the resultant mixture is then filtered using a Buchner filter and number 2 Whatman filter paper at 13 and washed 4 times with 100 cm 3 of 35% wt. aqueous isopropyl alcohol.
- the washed wet cake is then dried first in a convection oven at 120 °C to 95% solids, then in a vacuum oven at 150 °C for 1 hour.
- the TGA analysis run in nitrogen at 5 °C/min in the range 200-600 °C gave 18% covalently bound polyether.
- Example 5 Coating a Nylon powder
- Nylon 11 is ground into small powder granules less than 10 micrometers in diameter.
- a dispersion is made by taking lg of the carbon nanotubes of Example 4 in 200g aqueous isopropanol alcohol (50/50) together with lg of polyvinylpyrrolidone, Molecular weight about 24,000 daltons (Sigma Aldrich).
- lOOg of the Nylon 11 powder is stirred into the modified carbon nanotube dispersion and stirred for 1 hour.
- the material is then dried in a convection oven at 110 °C.
- the dried material is placed in a ball mill for 1 hour to give a fine dispersion of Nylon 11 with a coating of the dried dispersion.
- the powder can then be used in an SLS additive manufacturing process to create strong parts with enhanced electrical conductivity with resistance less than 10 billion ohm per square.
- the coating of oxidized discrete carbon nanotubes with covalently attached dispersing agent allows for improved post sinter annealing of parts by infra-red or radio frequency radiation.
- a dispersion is made by taking lg of the carbon nanotubes of Example 4 in 200g isopropanol alcohol together with lg Molecular weight about 24,000 daltons (Sigma Aldrich) and mixing in a Thinky mixer at 2000 rpm for 5 minutes. The dispersion is jetted selectively onto the layer of aluminum oxide powder and the alcohol is removed by drying.
- the powder is bound by the dried dispersion of oxidized discrete carbon nanotubes and can then be sintered to create strong parts.
- the dispersion of oxidized discrete carbon nanotubes with covalently attached dispersing agent significantly improves the green strength of the ceramic part and the during sintering the covalently bound dispersing agent is removed.
- the oxidized discrete carbon nanotubes can be used to induce heating by electric/magnetic fields, or infra-red or radio frequency radiation.
- Radiation curable compositions for vat photopolymerization are prepared by weighing ingredient and loading into a container. The mixture is mechanically stirred at room temperature or elevated temperatures (up to 80°C) until a homogeneous resin mixture is obtained. The prepared compositions are processed in the vat photopolymerization equipment and fabricated specimens are analyzed in accordance with the test methods described below.
- the general procedure used for preparing three-dimensional specimens with vat photopolymerization equipment is as follows.
- the radiation curable resin is poured into a vat.
- the fabrication parameters were set as standard-black resin and 25pm layer thickness. In that mode, the resin is heated to 31°C prior to part fabrication.
- a sufficient number of laser passes were employed to provide the desired polymerization energy.
- the material was exposed to a laser emitting in the range of 405 nm. Initially a “green part” is formed, in which layers are not completely cured. Under curing allows for the successive layers to better adhere by bonding when further cured.
- the fabricated “green part” is removed from the machine, washed with isopropyl alcohol, dried in air and post-cured in a curing chamber equipped with 405 nm multi-directional LED lamps. All specimens were post-cured in the curing chamber at room temperature for 30 minutes unless specified otherwise.
- the resin is prepared to satisfy desired viscosity and wetting behavior requirements. Viscosity and wetting behavior directly affect the recoating depth (layer thickness before radiation exposure), which in turn influences the build resolution in z- direction. Viscosity data was collected on freshly prepared resins using HR20 Discovery Hybrid Rheometer (TA Instruments). The 40 mm 2.002° Stainless Steel Peltier plate was used for the flow sweep experiment. The logarithmic sweep was performed by sweeping the shear rate from l.Oe 3 to 8000 1/s at room temperature. Additional flow temperature ramp testing was conducted at a shear rate of 6 1/s and temperature ramp from 25°C to 80°C at ramp rate of 2°C/min.
- Table 2 shows the viscosity at zero shear rate for three example compositions. Data shows that viscosity increases exponentially with increase in oxidized discrete carbon nanotube with bonded dispersion agent content in the final resin formulation. Temperature ramp results are shown in Table 3 and provide comparison points at 25°C, 50°C, and 80°C. The results show that with increase in temperature the viscosity reduces exponentially at the constant shear rate.
- CONTROL 1 2073 267 50 Table 6 lists the components of each photocurable composition labeled as Examples 7.1,7.2 and Control 7.1. NOTE: TPO and OB amounts do not count towards total composition percentage.
- Tensile data was collected by testing tensile Type IV specimens (ASTM D638) fabricated using vat photopolymerization equipment. All specimens were fabricated vertically. Tensile strength, Young’s modulus, and elongation at break tests were conducted 24 hours or more after post-curing. The tensile tests were conducted in accordance with ASTM D638, which is hereby incorporated in its entirety by reference, except that no provision was made for controlling the room temperature and humidify and the bars were not equilibrated for 2 days. The testing was performed on an Instron testing machine (model 5985). The reported data is an average of three measurements.
- Table 8 shows the Ultimate tensile strength, yield strength, and young’s modulus for example 7.1 and 7.2 compared to control that does not have oxidized discrete carbon nanotubes with bonded dispersing agent added to the composition. These examples show that addition of oxidized discrete carbon nanotubes with bonded dispersing agent increases both tensile and yield strength as well as Young’s modulus compared to resin without the oxidized discrete carbon nanotubes.
- Cured specimens for determining the Izod impact strength were prepared in the same manner as for the tensile bars, except the specimens were designed in accordance with ASTM D-256A standard and had dimensions of 3.2 mm x 12.7 mm x 63.5 mm (thickness x width x length). Specimens were notched using a motorized notching cutter from Ray-Ran. Izod Impact was measured using Universal Pendulum Impact System by Ray-Ran equipped with 2.75 J pendulum. The reported data is the average of three measurements.
- Table 12 lists the components of each photocurable composition labeled as Examples 7.3, 7.4 and Control 2.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP22776650.8A EP4314173A1 (en) | 2021-03-25 | 2022-03-24 | Dispersions for additive manufacturing comprising discrete carbon nanotubes |
KR1020237035626A KR20230160855A (en) | 2021-03-25 | 2022-03-24 | Dispersions for additive manufacturing containing discrete carbon nanotubes |
CA3213250A CA3213250A1 (en) | 2021-03-25 | 2022-03-24 | Dispersions for additive manufacturing comprising discrete carbon nanotubes |
JP2023558445A JP2024512047A (en) | 2021-03-25 | 2022-03-24 | Dispersions for additive manufacturing containing discrete carbon nanotubes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17/212,612 | 2021-03-25 | ||
US17/212,612 US20210237509A1 (en) | 2010-12-14 | 2021-03-25 | Dispersions for additive manufacturing comprising discrete carbon nanotubes |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2022204398A1 true WO2022204398A1 (en) | 2022-09-29 |
Family
ID=83397900
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2022/021737 WO2022204398A1 (en) | 2021-03-25 | 2022-03-24 | Dispersions for additive manufacturing comprising discrete carbon nanotubes |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP4314173A1 (en) |
JP (1) | JP2024512047A (en) |
KR (1) | KR20230160855A (en) |
CA (1) | CA3213250A1 (en) |
TW (1) | TW202244202A (en) |
WO (1) | WO2022204398A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN117383535A (en) * | 2023-11-22 | 2024-01-12 | 广东惠云钛业股份有限公司 | Preparation method of low-cost high-compaction lithium iron phosphate |
CN117410493B (en) * | 2023-12-12 | 2024-04-02 | 成都方大炭炭复合材料股份有限公司 | Sodium vanadium phosphate positive electrode material based on carbon nanotube dispersion stabilization process and preparation method and application thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100267883A1 (en) * | 2006-02-22 | 2010-10-21 | Bhatt Sanjiv M | Nanotube Polymer Composite Composition and Methods of Making |
US20120035309A1 (en) * | 2010-08-06 | 2012-02-09 | Baker Hughes Incorporated | Method to disperse nanoparticles into elastomer and articles produced therefrom |
US20170050158A1 (en) * | 2010-12-14 | 2017-02-23 | Molecular Rebar Design, Llc | Dispersions comprising discrete carbon nanotube fibers |
US20180298221A1 (en) * | 2010-12-14 | 2018-10-18 | Molecular Rebar Design, Llc | Epoxy resin dispersions comprising discrete carbon nanotubes |
US20190161350A1 (en) * | 2016-04-07 | 2019-05-30 | Molecular Rebar Design, Llc | Discrete Carbon Nanotubes with Targeted Oxidation Levels and Formulations Thereof |
WO2020018535A1 (en) * | 2018-07-16 | 2020-01-23 | Molecular Rebar Design, Llc | Dose and time-dependent intracelluar penetration of surface-modified nanotubes for delivery of molecular materials into cells |
US20200198973A1 (en) * | 2016-04-07 | 2020-06-25 | Molecular Rebar Design, Llc | Discrete carbon nanotubes with targeted oxidation levels and stable gel formulations thereof |
US20210237509A1 (en) * | 2010-12-14 | 2021-08-05 | Molecular Rebar Design, Llc | Dispersions for additive manufacturing comprising discrete carbon nanotubes |
-
2022
- 2022-03-24 EP EP22776650.8A patent/EP4314173A1/en active Pending
- 2022-03-24 CA CA3213250A patent/CA3213250A1/en active Pending
- 2022-03-24 TW TW111111127A patent/TW202244202A/en unknown
- 2022-03-24 JP JP2023558445A patent/JP2024512047A/en active Pending
- 2022-03-24 KR KR1020237035626A patent/KR20230160855A/en unknown
- 2022-03-24 WO PCT/US2022/021737 patent/WO2022204398A1/en active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100267883A1 (en) * | 2006-02-22 | 2010-10-21 | Bhatt Sanjiv M | Nanotube Polymer Composite Composition and Methods of Making |
US20120035309A1 (en) * | 2010-08-06 | 2012-02-09 | Baker Hughes Incorporated | Method to disperse nanoparticles into elastomer and articles produced therefrom |
US20170050158A1 (en) * | 2010-12-14 | 2017-02-23 | Molecular Rebar Design, Llc | Dispersions comprising discrete carbon nanotube fibers |
US20180298221A1 (en) * | 2010-12-14 | 2018-10-18 | Molecular Rebar Design, Llc | Epoxy resin dispersions comprising discrete carbon nanotubes |
US20210237509A1 (en) * | 2010-12-14 | 2021-08-05 | Molecular Rebar Design, Llc | Dispersions for additive manufacturing comprising discrete carbon nanotubes |
US20190161350A1 (en) * | 2016-04-07 | 2019-05-30 | Molecular Rebar Design, Llc | Discrete Carbon Nanotubes with Targeted Oxidation Levels and Formulations Thereof |
US20200198973A1 (en) * | 2016-04-07 | 2020-06-25 | Molecular Rebar Design, Llc | Discrete carbon nanotubes with targeted oxidation levels and stable gel formulations thereof |
WO2020018535A1 (en) * | 2018-07-16 | 2020-01-23 | Molecular Rebar Design, Llc | Dose and time-dependent intracelluar penetration of surface-modified nanotubes for delivery of molecular materials into cells |
Also Published As
Publication number | Publication date |
---|---|
KR20230160855A (en) | 2023-11-24 |
CA3213250A1 (en) | 2022-09-29 |
JP2024512047A (en) | 2024-03-18 |
EP4314173A1 (en) | 2024-02-07 |
TW202244202A (en) | 2022-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2022204398A1 (en) | Dispersions for additive manufacturing comprising discrete carbon nanotubes | |
Li et al. | Control of the functionality of graphene oxide for its application in epoxy nanocomposites | |
Albdiry et al. | Toughening of brittle polyester with functionalized halloysite nanocomposites | |
Vijayan et al. | Liquid rubber and silicon carbide nanofiber modified epoxy nanocomposites: Volume shrinkage, cure kinetics and properties | |
US20210237509A1 (en) | Dispersions for additive manufacturing comprising discrete carbon nanotubes | |
Ryu et al. | Characteristics of polystyrene/polyethylene/clay nanocomposites prepared by ultrasound‐assisted mixing process | |
Naeem et al. | Epoxy/graphene nanocomposites prepared by in-situ microwaving | |
Nayak et al. | Novel approach for the selective dispersion of MWCNTs in the Nylon/SAN blend system | |
Park et al. | Selectively distributed graphene in 1, 6-hexanediol diacrylate/epoxy composites via digital light processing 3D printing for enhanced thermal conductivity | |
Nguyen et al. | Study on synergies of fly ash with multiwall carbon nanotubes in manufacturing fire retardant epoxy nanocomposite | |
Puglia et al. | Structure-property relationships of thermoset nanocomposites | |
Hatui et al. | Modification of CNT and its effect on thermo mechanical, morphological as well as rheological properties of Polyether Imide (PEI)/Liquid Crystalline Polymer (LCP) blend system | |
WO2020138496A1 (en) | Production method for lignocellulose fibers, lignocellulose fibers, and composite material | |
Yuan et al. | Effect of ultrasonic on the properties of silicone/montmorillonite nanocomposites by in-situ intercalative polymerization | |
Kim et al. | A novel fabrication method for poly (propylene)/clay nanocomposites by continuous processing | |
KR100998184B1 (en) | The oxyfluorinated carbon nanomaterials and the preparation method of epoxy curing resin using radioactive rays | |
US20230202108A1 (en) | Dispersions and Manufacturing Technologies for Additive Manufacturing Comprising Discrete Carbon Nanotubes | |
Borah et al. | Milled graphitic nanoparticle toughened epoxy composites via increased resistance to in-plane crack propagation | |
EP4313600A1 (en) | Dispersions and manufacturing technologies for additive manufacturing comprising discrete carbon nanotubes | |
Jia et al. | Morphologies and properties of epoxy resin/layered silicate–silica nanocomposites | |
Chen et al. | Preparation of poly (ethylene oxide) brush‐grafted multiwall carbon nanotubes and their effect on morphology and mechanical properties of rigid polyurethane foam | |
Rangari | Polymer nanocomposite materials for structural applications | |
Islam et al. | Thermal stability and kinetics analysis of epoxy composites modified with reactive polyol diluent and multiwalled carbon nanotubes | |
Nayak et al. | Effect of polyphosphazene and modified carbon nanotubes on the morphological and thermo-mechanical properties of polyphenylene sulfide and liquid crystalline polymer blend system | |
Rangari et al. | Synthesis Fabrication and Characterization of Ag/CNT‐Polymer Nanocomposites |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22776650 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2023558445 Country of ref document: JP Ref document number: 3213250 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 20237035626 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020237035626 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022776650 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 2022776650 Country of ref document: EP Effective date: 20231025 |