US20060006144A1 - Arc-extinguishing composition and articles manufactured therefrom - Google Patents
Arc-extinguishing composition and articles manufactured therefrom Download PDFInfo
- Publication number
- US20060006144A1 US20060006144A1 US10/887,937 US88793704A US2006006144A1 US 20060006144 A1 US20060006144 A1 US 20060006144A1 US 88793704 A US88793704 A US 88793704A US 2006006144 A1 US2006006144 A1 US 2006006144A1
- Authority
- US
- United States
- Prior art keywords
- arc
- composition
- melamine
- extinguishing
- nylon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 146
- 239000011230 binding agent Substances 0.000 claims abstract description 122
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 78
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 76
- 150000001875 compounds Chemical class 0.000 claims abstract description 72
- 239000007822 coupling agent Substances 0.000 claims abstract description 50
- -1 melamine Chemical class 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims description 72
- 239000002245 particle Substances 0.000 claims description 29
- 229920001778 nylon Polymers 0.000 claims description 21
- 239000004677 Nylon Substances 0.000 claims description 20
- 239000004014 plasticizer Substances 0.000 claims description 19
- 229920002292 Nylon 6 Polymers 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 150000008064 anhydrides Chemical class 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 10
- 239000004952 Polyamide Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- QQLZTRHXUSFZOM-UHFFFAOYSA-N 6-amino-1h-1,3,5-triazine-2,4-dithione Chemical compound NC1=NC(=S)NC(=S)N1 QQLZTRHXUSFZOM-UHFFFAOYSA-N 0.000 claims description 7
- MASBWURJQFFLOO-UHFFFAOYSA-N ammeline Chemical compound NC1=NC(N)=NC(O)=N1 MASBWURJQFFLOO-UHFFFAOYSA-N 0.000 claims description 7
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 6
- POJWUDADGALRAB-UHFFFAOYSA-N allantoin Chemical compound NC(=O)NC1NC(=O)NC1=O POJWUDADGALRAB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001408 amides Chemical class 0.000 claims description 6
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 229920000571 Nylon 11 Polymers 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 3
- POJWUDADGALRAB-PVQJCKRUSA-N Allantoin Natural products NC(=O)N[C@@H]1NC(=O)NC1=O POJWUDADGALRAB-PVQJCKRUSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 3
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 3
- 229920000572 Nylon 6/12 Polymers 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- DZHMRSPXDUUJER-UHFFFAOYSA-N [amino(hydroxy)methylidene]azanium;dihydrogen phosphate Chemical compound NC(N)=O.OP(O)(O)=O DZHMRSPXDUUJER-UHFFFAOYSA-N 0.000 claims description 3
- 229960000458 allantoin Drugs 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 claims description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 3
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 claims description 3
- DXTIKTAIYCJTII-UHFFFAOYSA-N guanidine acetate Chemical compound CC([O-])=O.NC([NH3+])=N DXTIKTAIYCJTII-UHFFFAOYSA-N 0.000 claims description 3
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 claims description 3
- 229940091173 hydantoin Drugs 0.000 claims description 3
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 claims description 3
- 150000003951 lactams Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 229940045136 urea Drugs 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims 2
- 125000000524 functional group Chemical group 0.000 abstract description 23
- 229920000642 polymer Polymers 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 12
- 238000010791 quenching Methods 0.000 description 31
- 229920001577 copolymer Polymers 0.000 description 17
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 16
- 230000008878 coupling Effects 0.000 description 15
- 238000010168 coupling process Methods 0.000 description 15
- 238000005859 coupling reaction Methods 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 239000004698 Polyethylene Substances 0.000 description 14
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 230000007613 environmental effect Effects 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 238000005382 thermal cycling Methods 0.000 description 10
- 229920004943 Delrin® Polymers 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 239000004743 Polypropylene Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 229920001169 thermoplastic Polymers 0.000 description 7
- 239000004416 thermosoftening plastic Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 239000002491 polymer binding agent Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010891 electric arc Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- YYXLGGIKSIZHSF-UHFFFAOYSA-N ethene;furan-2,5-dione Chemical compound C=C.O=C1OC(=O)C=C1 YYXLGGIKSIZHSF-UHFFFAOYSA-N 0.000 description 3
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920005596 polymer binder Polymers 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 229920005822 acrylic binder Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
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- 230000000704 physical effect Effects 0.000 description 2
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
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- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 description 1
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- UPRXAOPZPSAYHF-UHFFFAOYSA-N lithium;cyclohexyl(propan-2-yl)azanide Chemical compound CC(C)N([Li])C1CCCCC1 UPRXAOPZPSAYHF-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H85/00—Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
- H01H85/02—Details
- H01H85/38—Means for extinguishing or suppressing arc
- H01H85/42—Means for extinguishing or suppressing arc using an arc-extinguishing gas
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H33/00—High-tension or heavy-current switches with arc-extinguishing or arc-preventing means
- H01H33/70—Switches with separate means for directing, obtaining, or increasing flow of arc-extinguishing fluid
- H01H33/76—Switches with separate means for directing, obtaining, or increasing flow of arc-extinguishing fluid wherein arc-extinguishing gas is evolved from stationary parts; Selection of material therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H9/00—Details of switching devices, not covered by groups H01H1/00 - H01H7/00
- H01H9/30—Means for extinguishing or preventing arc between current-carrying parts
- H01H9/302—Means for extinguishing or preventing arc between current-carrying parts wherein arc-extinguishing gas is evolved from stationary parts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H85/00—Protective devices in which the current flows through a part of fusible material and this current is interrupted by displacement of the fusible material when this current becomes excessive
- H01H85/02—Details
- H01H85/38—Means for extinguishing or suppressing arc
- H01H2085/388—Means for extinguishing or suppressing arc using special materials
Definitions
- the present invention relates to arc-quenching materials and articles fabricated therefrom for high-voltage electrical devices and equipment such as circuit interrupters wherein, under certain conditions of operation, a high-voltage electrical arc is produced that is either desirably, or by necessity, quenched. More particularly, the present invention relates to a composition to achieve arc-quenching and structural properties in devices such as circuit interrupters, high-voltage fuses, circuit breakers, and separable cable connectors.
- the arc-quenching materials should include characteristics and properties sufficient for the particular application so as to be effective in quenching arcs via the rapid evolution of quenching gases.
- the evolved quenching gases should also be relatively nonconductive.
- the arc-quenching materials are capable of being molded or otherwise fabricated into suitable articles and shapes having desirable structural properties, thermal stability, and environmental resistance to thermal cycling.
- a sleeve or liner surrounds the path of the arc during fuse operation with the sleeve or liner being fabricated from an arc-extinguishing material.
- U.S. Pat. Nos. 3,629,767 and 4,307,369 for an example of fuses of this type surrounded by arc-extinguishing sleeves or liners.
- Typical arc-extinguishing materials and their properties are disclosed in the following U.S. Pat. Nos. 3,582,586; 3,761,669; 4,251,699; and 4,444,671.
- One composition in U.S. Pat. No. 3,582,586 includes melamine and polyethylene. While this composition is generally suitable for various applications and exhibits desirable arc-quenching properties, for many applications, it would be desirable to achieve a composition with improved mechanical characteristics and environmental resistance to thermal cycling while maintaining the desirable arc-quenching characteristics.
- melamine C 3 N 6 H 6
- Other, related nitrogen-containing compounds are also recognized in the prior art as arc-quenching or arc-interrupting compounds and are disclosed in Amundson et al U.S. Pat. No. 2,526,448.
- Melamine and its related compounds have excellent arc-interrupting characteristics but suffer from extreme structural weakness, so that they cannot be molded or pressed into satisfactory structural shapes except in combination with a suitable binder.
- a binder For a binder to be most effective in an arc-quenching or arc-interrupting composition it should volatilize or decompose in the presence of an electric arc, as does melamine.
- the binder does not necessarily have to provide any arc-interrupting or arc-extinguishing characteristics to the composition, since, in some cases, the arc-interrupting characteristics of the melamine included in the composition is sufficient for arc-interrupting purposes.
- the binder therefore, is primarily included for purposes of providing the melamine-containing composition with sufficient moldability and to provide a molded structure of sufficient physical strength, physical and chemical stability, and electrical insulating properties to provide a structurally sound, molded product.
- the physical strength of the molded product is most evident in its tensile strength, its percent elongation, and the amount of energy required to break the molded structure, or impact strength.
- Structural damage i.e., cracks have been found in prior art devices containing polyethylene as its primary binder material, and such damage is unacceptable in this art, since the break point allows another air space for the gases and arc to fill, thereby significantly lessening the arc-interrupting properties of the arc-interrupting device.
- failed arc extinguishing compositions that contain melamine usually fail because the pressure wave associated with the arc causes the composition to physically break before it has an opportunity to extinguish the arc.
- the arc-extinguishing compositions described herein extinguish the arc without physically breaking.
- thermoplastic polymeric binders have been found to be the most useful in arc-interrupting compositions based upon melamine or similar compounds, since the thermoplastic binders volatilize or decompose in the presence of an electric arc at lower power conditions than necessary to sublime melamine thereby producing large volumes of gas to drive the melamine into the core of the arc and to extinguish the arc under a wide range of power conditions. Further, the thermoplastic binders provide compositions with good molding characteristics, stability and electrical insulating properties.
- thermoplastic polymeric resins known to be useful as binders in melamine-based arc-interrupting compositions include polyethylene, polypropylene, polytetrafluoroethylene, acrylics, polystyrene, cellulosics polyamides (nylons), polyacetals (DELRIN), polyphenylene oxides, blends such as ABS, and polyimides.
- elastomeric, rubber-like materials as a portion of the binder in melamine-based arc-interrupting compositions such as butyl compounds, isoprene-based compounds, neoprene-based compounds and other synthetic elastomers.
- a binder comprising a carboxylic acid group-containing polymer, particularly a copolymer of two different monomers, at least one of which contains a carboxylic acid moiety, such as an ethylene acrylic acid copolymer.
- the carboxylic acid functionalities of the binder interact with arc-extinguishing compounds having carboxylic acid-active sites, such as amine, thiol, alcohol, halogen, and the like sites, to provide added physical strength and stability to the composition.
- the molded composition including the arc-interrupting compound and the binder, maintains excellent arc-interrupting capability, chemical stability and electrical insulating properties as well as increased physical strength.
- the present invention is directed to a new and improved arc extinguishing composition
- a new and improved binder for compositions containing an arc-interrupting compound, such as melamine, and to a method of extinguishing an arc by disposing the composition along the path of the arc, for contacting the arc.
- the binder or at least a portion of the binder, is a polymer that contains a functional group that binds to a coupling agent that is included in the arc-extinguishing composition.
- the coupling agent which may be a polymer that is compatible with the binder, contains a functional group that binds to the arc-extinguishing compound to tie the polymeric binder to the arc-extinguishing compound, e.g., melamine, to provide new and unexpected physical strength and stability to the composition.
- the molded composition including the arc-interrupting compound coupled to the binder, maintains excellent arc-interrupting capability, while providing chemical stability and electrical insulating properties as well as unexpected physical strength.
- the melamine or other arc-extinguishing compound provides unexpectedly better results when incorporated into the composition in finely divided form; and improved results are provided by combining a plasticizer for the polymeric binder.
- At least three embodiments of the arc-quenching materials and articles are described herein—each embodiment providing improved mechanical properties and/or arc-extinguishing results either alone or in combination with one or both of the other embodiments.
- Each of these three individual embodiments can be included alone in the materials and articles described herein or any two or three of these embodiments can be combined to further improve the materials and articles described herein.
- compositions described herein are suitable for deionizing and extinguishing a high-voltage electrical arc.
- the compositions include effective amounts of an arc-extinguishing material, such as melamine, and sufficient binding polymer to achieve the desired combination of arc-extinguishing properties and structural characteristics, such as tensile strength, elongation, environmental resistance to thermal cycling, and the like. Additionally, the composition for various applications and uses may include additives, fillers or fibrous materials.
- the composition is homogenized by compounding the constituents using dry blending, roll mill, extrusion and/or other plastic compounding techniques to obtain the molding resin compositions.
- the molding resin then is molded into articles of the desired shape using plastic processing techniques, such as injection molding, extrusion, and the like.
- plastic processing techniques such as injection molding, extrusion, and the like.
- a nylon base polymer binder is combined with melamine and an anhydride-functional coupling agent to achieve the desired arc-extinguishing and mechanical characteristics by virtue of the bonding and/or miscibility between the melamine, nylon, and the anhydride-functional coupling agent.
- the composition includes non-functionalized base polymeric binder(s) with or without the coupling agent and contains a finely divided arc-extinguishing material and/or a plasticizer for the base polymeric binder(s).
- compositions, articles and methods described herein is to provide a new and improved arc-quenching composition
- a new and improved arc-quenching composition comprising effective proportions of an arc-extinguishing compound, such as melamine, and a polymeric binder containing coupling agent-interactive moieties, such as an ethylene maleic anhydride polymer, and a suitable coupling agent capable of chemically and/or mechanically attaching the arc-extinguishing compound to the coupling agent and coupling the arc-extinguishing compound to the polymeric binder to achieve improved strength and desirable environmental resistance to thermal cycling.
- an arc-extinguishing compound such as melamine
- a polymeric binder containing coupling agent-interactive moieties such as an ethylene maleic anhydride polymer
- suitable coupling agent capable of chemically and/or mechanically attaching the arc-extinguishing compound to the coupling agent and coupling the arc-extinguishing compound to the polymeric
- compositions, articles, and methods described herein is to provide a new and improved arc-extinguishing composition with improved mechanical characteristics, when molded, while exhibiting at least the same desirable electrical arc-extinguishing characteristics of previously available arc-extinguishing compositions and articles.
- compositions, articles and methods described herein are to provide a new and improved arc-extinguishing composition including an arc-interrupting compound and a polymeric binder wherein the binder is a polymer, or copolymer formed from two different monomers, including coupling agent reactive groups or moieties for coupling the binder to the arc-interrupting compound through a coupling agent.
- compositions, articles and methods described herein are to provide a new and improved arc-extinguishing composition including an arc-extinguishing compound having at least one site reactive with a coupling agent-contained functional group; or a polymeric binder material including a plurality of reactive coupling agent contained functional moieties, such that when the composition is molded under heat and pressure, the arc-extinguishing compound and the polymeric binder will chemically bond (including ionic and/or covalent bonds) to the coupling agent to provide new and unexpected physical strength in the molded composition.
- Still another aspect of the compositions, articles and methods described herein, is to provide a new and improved arc-interrupting composition including an arc-interrupting compound having at least one reactive amine site in its molecule, such as melamine, and a thermoplastic resin binder material containing an amine-reactive site and a binder-reactive site; together with a suitable coupling agent for coupling the arc-interrupting compound to the polymeric binder through the coupling agent.
- an arc-interrupting compound having at least one reactive amine site in its molecule, such as melamine, and a thermoplastic resin binder material containing an amine-reactive site and a binder-reactive site
- compositions, articles and methods described herein are to provide a new and improved arc-interrupting composition that provides sufficient and excellent arc-interrupting characteristics as well as new and unexpected molding and physical strength properties such as tensile strength, elongation and ability to withstand thermal cycling and resist cracking.
- FIG. 1 is a bar graph showing mechanical toughness properties for the arc-extinguishing compositions of Table 1 in comparison to DELRIN 500;
- FIG. 2 and 3 are bar graphs showing weight changes due to water and nitric acid attack on the arc-extinguishing compositions of Table 1 in comparison to DELRIN 500;
- FIG. 4 is a bar graph showing the particle size distribution of standard grade and fine grade melamine
- FIG. 5 is a perspective view of a fuse sleeve or liner formed from the arc-extinguishing compositions described herein;
- FIG. 6 is a partially broken-away side view showing the sleeve or liner of FIG. 1 surrounding a fuse.
- the physical and thermal properties of an arc-extinguishing composition can be unexpectedly improved when the arc-extinguishing composition includes a binder that contains a coupling agent-reactive functional group, such as an anhydride group, that bonds to coupling agent.
- binders are particularly effective when used with arc-extinguishing compounds that have available reactive sites, such as amine groups; compounds containing one or more available hydroxyl groups, epoxy groups and/or aziridine groups; or compounds containing one or more available thiol groups having available carboxylic acid-reactive sulphur atoms, but are also effective with other arc-extinguishing compounds.
- polymeric binders having one or more coupling agent-reactive functional groups, and the reactive coupling agents, described herein have been found to be particularly effective with melamine or other similar arc-extinguishing compounds, such as benzoguanamine, dithioammelide, ammeline, and a cyanuric halide.
- the functionalized, coupling agent-reactive polymeric binder need not form 100% of the binder material used in the arc-extinguishing compositions and excellent results have been found in improvement of known arc-extinguishing compositions when the functionalized binder is included in only a small portion, e.g., 0.5 to 20% by weight, of the binder material used.
- the non-reacted (non-functional) portion of the coupling agent and polymeric binder should be sufficiently compatible such that the composition, when melted, forms a homogenous composition.
- Suitable polymeric binders having one or more coupling agent-reactive functional groups include thermoplastic and thermosetting polymers having one or more functional groups selected from anhydride, carbonyl, hydroxyl, carboxyl, amine, amide, ether, lactam, lactone, epoxy, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate, and/or phosphinate; or an aromatic ring capable of covalently or ionically bonding to the coupling agent.
- the binder has a functional group selected from anhydride, carbonyl, carboxyl, hydroxyl, amine, amide (particularly any nylon), ether, and/or an aromatic ring having a reactive group as part of the ring structure or as an extending coupling agent-reactive functional group.
- a functional group selected from anhydride, carbonyl, carboxyl, hydroxyl, amine, amide (particularly any nylon), ether, and/or an aromatic ring having a reactive group as part of the ring structure or as an extending coupling agent-reactive functional group.
- suitable polymeric binders containing these coupling agent-reactive functional groups include polypropylene, nylon 4/6, nylon 6/6, nylon 6, nylon 11, nylon 6/12, high-impact nylon, mineral-filled nylon, polycarbonate, polystyrene, acrylonitrile butadiene styrene, polysulfone, polybutylene terphthalate, polyethylene terphthalate, polyphenylene sulfide, polyester thermoplastic elastomer, polyetherimide, styrenic thermoplastic elastomer, olefinic thermoplastic elastomer, polyurethane thermoplastic, polyphenylene oxide, polyetheretherketone, phenylene ether co-polymer, polycarbonate/acrylonitrile butadiene styrene, polyarylether ketone, polyetherketoneetherketoneketone, polyphthalamide, and polyetherketoneketone and blends of any two or more of these polymers.
- Other suitable base resins include perfluoroal
- the functionalized binders used in one embodiment of the arc-interrupting compositions can be used in a widely varying amount, as well known in the art, together with the arc-interrupting or arc-extinguishing compound, such as melamine, and can be a combination of a number of different thermosetting and/or thermoplastic binder materials well known in the art.
- the functionalized binders are usually included in amounts of at least about 10% by weight of the total arc-interrupting composition and preferably in an amount of at least about 20% by weight of the arc-interrupting composition.
- the coupling agents used in the coupling agent embodiment to tie the arc-extinguishing compound to the functionalized polymeric binder preferably is a monomeric or polymeric compound that contains reactive functional groups that provide covalent bonds to both the arc-extinguishing compound and the polymeric binder.
- the attractive interaction between the coupling agent and/or the arc-extinguishing compound and/or the polymeric binder also can be by any mechanism selected from the group consisting of electrostatic complexing, ionic complexing, chelation, hydrogen bonding, ion-dipole, dipole/dipole, Van Der Waals forces, and any combination thereof.
- the preferred coupling agent is a polymer, e.g., terpolymer, that has an anhydride functionality for reaction with the preferred melamine arc-extinguishing compound.
- a polymer e.g., terpolymer
- an ethylene/ethyl acrylate/maleic anhydride terpolymer coupling agent e.g., Lotader 4720 from Atofina Chemicals Corporation
- the non-functional portion of the Lotadur coupling agent is compatible with the nylon, e.g., nylon 6 polymeric binder.
- suitable coupling agents include organosilanes, organofunctional silylating agents, particularly the organosilanes having an amino, epoxy, acrylate, n-mercapto and/or vinyl functionality including (3-Acryloxypropyl)trimethoxysilane; N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane; 3-Aminopropyltriethoxysilane; 3-Aminopropyltrimethoxylsilane; 3-Isocyanatoproplytriethoxysilane; (3-Glycidoxypropyl)trimethoxysilane; 3-Mercaptopropyltrimethoxysilane; 3-Methacryloxypropyltrimethoxysilane; and Vinyltrimethoxysilane.
- organosilanes organofunctional silylating agents, particularly the organosilanes having an amino, epoxy, acrylate, n-mercapto and/or vinyl functionality including (3-A
- the preferred coupling agents are functionalized polyolefins, e.g., polyethylene or polypropylene that is functionalized with one or more reactive functionalities that provide reactivity or electrostatic association with the arc-extinguishing material and with the polymeric binder.
- the coupling agent preferably includes glycidylmethacrylate (GMA) and/or maleic anhydride (MAH) functional groups for better compatibility with polyester, polyamide and/or polyolefin polymeric binders.
- the most preferred coupling agents are functionalized polyolefins, particularly terpolymers of ethylene or propylene (PE or PP) with ethylacrylate (EA) and maleic anhydride (MAH) or glycidylmethacrylate having 6.5-30 wt. % EA; 0.3-3.1 wt. % MAH or GMA with the remaining 66.9 wt. % to 93.2 wt. % being PE or PP, preferably polyethylene.
- EA ethylacrylate
- MAH maleic anhydride
- GMAH glycidylmethacrylate
- the terpolymer containing MAH is sold under the trade name Lotader, from Atofina Chemicals.
- Suitable coupling agents include terpolymers of PE or PP with MAH and n-butyl acrylate (Lotader grades 2210, 3210, 4210 and 3410); MAH grafted ethylene/butane copolymers (elastomers), having about 0.25 wt. % to 1 wt.
- % MAH sold by Dow Plastics, as AMPLIFY GR 208 functional polymers; titanate quarternary ammonium compounds, such as those sold by KENRICH petrochemicals as KEN-REACT® Water Soluble Chelate Titanate Quats and KEN-REACT® LICA®; KEN-REACT® NZ® Neoalkoxy Zinconates and Quats; KEN-REACT® KZ® Cycloheteroatom Zinconates; KEN-REACT® KA Reluminates; CAPOW® KR® and L® Series Titanate Coupling Agent Powders; styrene/maleic anhydride copolymers; epoxy modified polyolefins, particularly terpolymers of ethylene/methyl acrylate/glycidylmethacrylate (E-MA-GMA) or copolymers of ethylene and glycidylmethacrylate (E-GMA) having a GMA content of 3-8 wt.
- E-MA-GMA ethylene
- MA methyl acrylate
- the arc-interrupting compound included in the compositions described herein, such as melamine, is included in the compositions in their normal amounts, well-known in the art, and generally in amounts of about 5% to about 90% by total weight of the arc-interrupting composition, preferably about 10% to about 70%, more preferably about 20% to about 50%, based on the total weight of the composition.
- Excellent results are achieved with arc-interrupting compounds and binder materials present in proportions ranging from about four parts by weight of arc-interrupting compound to one part by weight of polymeric binder material by weight to about one part by weight of arc-interrupting compound to one part by weight of polymeric binder material. Best results are achieved when the arc-interrupting compound is included in the composition in an amount of two to three parts by weight of arc-interrupting compound per part by weight of polymeric binder material.
- the functional group-containing polymers or copolymers should be included in an amount sufficient to improve the tensile strength of the molded composition, preferably more than a 10% increase in tensile strength, as a result of the addition of the functional group-containing binder.
- a typical prior art arc-interrupting composition includes melamine in a polyethylene binder in proportions of three parts by weight of melamine to one part by weight of polyethylene binder and has a tensile strength of 1133 psi.
- a coupling agent-interacting functionalized polymeric binder such as ethylene/maleic anhydride
- the tensile strength is increased more than 10%.
- the tensile strength is increased to 1677 psi, or almost 50%.
- the binder material used with the arc-interrupting compound should include the functional group-containing polymers or copolymers described herein in amounts of about 2% by weight to about 100% by weight preferably about 50% to about 100% by weight, based on the total weight of polymeric binders contained in the composition.
- the remaining percentage of binder material can be any binder effective for moldability and arc-extinguishing characteristics, such as the polyolefins, e.g.
- polyethylene and/or polypropylene polyfluorinated resins, such as polytetrafluoroethylene, acrylic resins, polyamides, such as any nylon, and any other suitable binders, including thermosetting resins, such as epoxy resins, polyester resins, phenolic resins, and the like.
- Various elastomeric materials also may be included to improve the elongation properties of the molded compositions, such as butyl-based and/or isoprene-based and/or neoprene-based synthetic elastomers.
- the binders are useful with any arc-interrupting compound(s) to provide an arc-quenching composition that is readily moldable into a desired shape while exhibiting structural properties, thermal stability, and environmental resistance to thermal cycling heretofore impossible with known arc-quenching compositions.
- Very unexpected structural (mechanical) property improvements are achieved for the coupling agent embodiment when the arc-interrupting compound is a material that includes one or more reactive sites that are chemically reactive with one or more reactive moieties of a coupling agent, which is also chemically reactive with the functional binders described herein.
- melamine C 6 N 6 H 6
- melamine includes three equally spaced reactive primary amine moieties that can chemically bond (including ionic and/or covalent bonds) with the extending functional moieties of a vinyl/maleic anhydride binder, wherein the anhydride group acts as a coupling agent for the melamine, thereby achieving new and unexpected tensile strength, elongation and resistance to thermal cycling, while maintaining excellent arc-extinguishing properties.
- the percentage of functional group-containing monomer used in forming a functionalized binder polymer or copolymer can be varied widely to provide sufficient reactive, e.g., anhydride moieties, in the copolymer for chemical bonding (including ionic and/or covalent bonds) at one, two or all three of the reactive amine sites extending from the melamine vinyl structure.
- anhydride moieties in the copolymer for chemical bonding (including ionic and/or covalent bonds) at one, two or all three of the reactive amine sites extending from the melamine vinyl structure.
- different degrees of compound-binder chemical bonding can be provided for different properties when the functional group-containing polymers are used as at least a portion of the binder in the manufacture of arc-quenching compositions.
- the amount of functional group-containing monomer that should be polymerized, or copolymerized with a second monomer in forming copolymers is from about 0.5 percent to about 80%, based on the total weight of the polymerizable monomers, with the second monomer present in an amount of about 20% by weight to about 95% by weight based on the total weight of both monomers.
- Such copolymers are readily available, such as the ethylene/maleic anhydride copolymers manufactured by Atofinacontaining various amounts of maleic anhydride monomer.
- copolymer coupling agent sold by Atofina under the TrademarkLODATER 4720 provides an arc-quenching composition having exceptionally good structural characteristics, thermal stability and environmental resistance to thermal cycling.
- Other functionalized polymers and copolymers can be used having more or less coupling agent-reactive moieties, e.g., an anhydride percentage, and should provide similar structural improvements when used as a coupled binder in arc-quenching compositions.
- a reactive site on the arc-quenching compound chemically bonds (ionically and/or covalently) with the functional moiety of the polymeric binder to achieve new and unexpected tensile strength, elongation and resistance to cracking heretofore unachieved in the prior art.
- other arc-quenching compounds also include reactive sites, such as benzoguanamine having a pair of extending reactive amine groups; thio substituted organic arc-quenching compounds, such as dithioammelide; ammeline; and halogenated compounds such as cyanuric chloride.
- Each of these compounds has the ability to generate large volumes of arc-extinguishing gases under the influence of an electric arc.
- Each of these compounds is useful in accordance with compositions, materials, and articles described herein, in combination with the coupling agent-reactive binders; and/or finely divided form of the arc-extinguishing compounds; and/or the plasticizers for the polymeric binders, to achieve new and unexpected structural, mechanical and physical properties in an arc-extinguishing or arc-interrupting composition.
- a reactive, arc-extinguishing compound such as melamine
- any arc-extinguishing compounds that have reactive epoxy groups, aziridine groups, thiol groups, hydroxyl groups, halogen groups, and like -reactive sites, also can chemically bond (including ionic and/or covalent bonds) with the reactive functional groups from the polymeric binders used in the compositions described herein to provide new and unexpected structural properties, thermal stability, and thermal cycling resistance.
- the molecular weights of the reactive, functionalized polymeric binders vary widely and can range from a low of about 250 weight average molecular weight to a high of about 500,000 or more while achieving exceptionally good physical properties, thermal stability and resistance to thermal cycling in accordance with the compositions, articles, and methods described herein. It is preferred that the weight average molecular weight of the polymeric binders be in the range of about 1,000 to about 100,000 weight average molecular weight, and more preferably in the range of about 1,000 to about 50,000 weight average molecular weight.
- Fibrous additives include glass, inorganic fibers and organic fibers, such as polyacrylonitrile, polyamide and polyester fibers. Fillers that may be included are, for example, cellulosic materials, calcium carbonate, metal oxides, comminuted polymers, carbon black, and natural and synthetic silica materials.
- FIG. 1 shows one example of a specific use of the arc-extinguishing materials in the form of molded or extruded annular fuse sheath or liner 10 , manufactured (molded or extruded) from the arc-extinguishing compositions described herein, that is dimensioned to surround a fuse 12 disposed within a fuse tube 14 .
- Such fuses 12 may be provided to interrupt both low and high level fault currents.
- the sheath 10 does not burst or rupture and remains integral, the arc between terminals is elongated entirely within the fuse tube 14 .
- the elongating arc interacts with the arc-extinguishing material of the sheath 10 , evolving arc-extinguishing gases.
- the fuse 12 may also be called upon to interrupt high fault currents. At high fault currents the sheath usually ruptures and the extinguishment of the arc formed and elongated between terminals of the fuse is primarily due to the evolution of the arc-extinguishing gas from the bore of the fuse tube 14 .
- caprolactam is an effective material in imparting toughness (6.2 vs. 6.6) and the fine melamine also improved toughness (6.1 vs. 6.2). # However, the biggest effect is from the coupling agent/impact modifier. The increase in toughness is dramatically better than that seen going from X-Material to TX-Material. It is also clear a family of materials with a balance of toughness and stiffness can be made. 5. 6.1 material also proved to be a better AEM than Delrin, and to be more resistant to ozone and nitric acid. In addition, it can handle higher temperatures than X or TX.
- the environmental test consisted of immersing flex bars of material (1 ⁇ 2′′ by 1 ⁇ 8′′ by 5′′ long) most of the way into a solution of 10% Nitric Acid in DI water (by volume) for 7 days. Due to a miscalculation, the first 3 days were in a 7% solution. By not immersing the samples completely, an air/solution interface is created that tends to accelerate the chemical attack. Since Nylon 6 is hygroscopic, a control in 100% DI water was also run. The effect on weight and width was documented.
- Composition 6.1 was the first AEM material tested that matched or exceeded the toughness numbers for Delrin. Composition 6.1 also displayed rubber-like properties.
- FIG. 2 Weight Change
- FIG. 3 Size Change
- Both the 6.1 and the F.1 compositions provided much better resistance to nitric acid than the Delrin. They suffer surface attack in the form of yellowing, but no significant material loss.
- the Delrin sample showed severe erosion at the waterline, looking much like Delrin samples from the Swamp.
- Nylon 6 material both gained 1.6% in weight and 1.6% in size due to water absorption.
- the molded arc-extinguishing composition has unexpectedly increased toughness, and especially elongation, thereby preventing breakage of the molded articles.
- the compound should have a particle size distribution such that at least 90% by weight, up to 100%, of the particles have a size less than about 200 microns ( ⁇ m).
- at least 90% by weight of the particles have a particle size less than about 100 ⁇ m and, more preferably, at least 99% by weight of the arc-extinguishing compound particles have a particle size less than 100 ⁇ m.
- at least 90% by weight, up to 100% by weight, of the arc-extinguishing compound particles should have a particle size less than 50 ⁇ m.
- compositions, articles and methods described herein it has been found that by including a plasticizer for the binder polymer into the compositions, the structural properties of the molded articles are increased without sacrificing arc-extinguishing properties.
- compatible plasticizers should have a solubility parameter ( ⁇ ) suitable for the particular polymeric binder, as well known in the art.
- solubility parameters ( ⁇ ) is in accordance with ASTM Designation D-3132-84 (Re-approved 1990).
- the plasticizer for the polymeric binders should have a solubility parameter ( ⁇ ) as close as possible to the solubility parameter of the polymeric binder.
- Polyester polymeric binders have solubility parameters ⁇ in the range of about 9.5 to 12.
- Maleic Anhydride has a ⁇ of about 13.6.
- the adipate plasticizers have relatively low solubility parameters, but are suitable for plasticizing amines.
- Epoxys have ⁇ s of about 9-11 and ethers have ⁇ s of about 7.5-11.
- Ketones have ⁇ s of about 8.4-10; lactones of about 10-14; maleates about 8.5-10; phenols about 9.5-13; phosphates about 7.5-10; phosphonates about 8-10.
- any of the monomers used to form a polymeric binder can be used as a plasticizer for that polymer binder (e.g., ⁇ -caprolactam used to plasticize nylon 6) in accordance with the third (plasticizer) embodiment described herein.
- the plasticizer need only be compatible with the polymeric binder such that a homogeneous mixture is achieved when the arc-extinguishing composition is melted during the article molding process. If the plasticizer is not sufficiently compatible with the polymeric binder, the plasticizer will separate from the binder when melted, or will not form a homogeneous composition when melted together with the arc-extinguishing compound and other components of the composition.
- Table 7 compares the percent elongation achieved in molded articles containing DSM Melamine Grade 003 in comparison to the standard grade melamine. Compositions with and without a plasticizer also are shown in Table 7. A comparison of the finely divided melamine versus standard grade melamine is shown in FIG. 4 .
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Abstract
An arc-interrupting compound, such as melamine, and to a method of extinguishing an arc by disposing the composition along the path of the arc, for contacting the arc. In one embodiment, the binder, or at least a portion of the binder, is a polymer that contains a functional group that binds to a coupling agent that is included in the arc-extinguishing composition. The coupling agent ties the polymeric binder to the arc-extinguishing compound, e.g., melamine, to provide new and unexpected physical strength and stability to the composition. In this embodiment, the molded composition, including the arc-interrupting compound coupled to the binder, maintains excellent arc-interrupting capability, while providing chemical stability and electrical insulating properties as well as unexpected physical strength.
Description
- The present invention relates to arc-quenching materials and articles fabricated therefrom for high-voltage electrical devices and equipment such as circuit interrupters wherein, under certain conditions of operation, a high-voltage electrical arc is produced that is either desirably, or by necessity, quenched. More particularly, the present invention relates to a composition to achieve arc-quenching and structural properties in devices such as circuit interrupters, high-voltage fuses, circuit breakers, and separable cable connectors.
- To provide effective circuit interruption in circuit interrupters, fuses, and the like, it is desirable to utilize an arc-quenching material or composition to quench and suppress arcing during electrical contact separation or fuse operation. Of necessity, the arc-quenching materials should include characteristics and properties sufficient for the particular application so as to be effective in quenching arcs via the rapid evolution of quenching gases. Of course, the evolved quenching gases should also be relatively nonconductive. In addition, it is also important that the arc-quenching materials are capable of being molded or otherwise fabricated into suitable articles and shapes having desirable structural properties, thermal stability, and environmental resistance to thermal cycling.
- In many circuit-interrupting devices, it is typical to utilize a trailer/liner configuration, as well known in the art, so that the arc is drawn into an annular space defined between the trailer and the liner, each of which is preferably fabricated from an arc-quenching composition. The action of the gases produced by the trailer and/or liner on the confined arc tends to deionize the arc and force its extinction. Examples of trailer/liner configurations are shown in the following U.S. Pat. Nos. 2,351,826; 2,816,980; 2,816,978; 2,816,985; 4,103,129; and 3,909,570 and in Descriptive Bulletin 811-30 of S&C Electric Company, Chicago, Ill. Similarly, in high-voltage fuses, which also can be characterized as circuit interrupters, a sleeve or liner surrounds the path of the arc during fuse operation with the sleeve or liner being fabricated from an arc-extinguishing material. Reference may be made to U.S. Pat. Nos. 3,629,767 and 4,307,369 for an example of fuses of this type surrounded by arc-extinguishing sleeves or liners.
- Typical arc-extinguishing materials and their properties are disclosed in the following U.S. Pat. Nos. 3,582,586; 3,761,669; 4,251,699; and 4,444,671. One composition in U.S. Pat. No. 3,582,586 includes melamine and polyethylene. While this composition is generally suitable for various applications and exhibits desirable arc-quenching properties, for many applications, it would be desirable to achieve a composition with improved mechanical characteristics and environmental resistance to thermal cycling while maintaining the desirable arc-quenching characteristics.
- One of the most effective arc-interrupting compounds used in this art for arc-quenching is melamine (C3N6H6) which is a white crystalline powder having a melting point of about 350° F. and sublimes at its melting temperatures and below. Other, related nitrogen-containing compounds are also recognized in the prior art as arc-quenching or arc-interrupting compounds and are disclosed in Amundson et al U.S. Pat. No. 2,526,448. Melamine and its related compounds have excellent arc-interrupting characteristics but suffer from extreme structural weakness, so that they cannot be molded or pressed into satisfactory structural shapes except in combination with a suitable binder.
- For a binder to be most effective in an arc-quenching or arc-interrupting composition it should volatilize or decompose in the presence of an electric arc, as does melamine. The binder, however, does not necessarily have to provide any arc-interrupting or arc-extinguishing characteristics to the composition, since, in some cases, the arc-interrupting characteristics of the melamine included in the composition is sufficient for arc-interrupting purposes. The binder, therefore, is primarily included for purposes of providing the melamine-containing composition with sufficient moldability and to provide a molded structure of sufficient physical strength, physical and chemical stability, and electrical insulating properties to provide a structurally sound, molded product. The physical strength of the molded product is most evident in its tensile strength, its percent elongation, and the amount of energy required to break the molded structure, or impact strength.
- Structural damage, i.e., cracks have been found in prior art devices containing polyethylene as its primary binder material, and such damage is unacceptable in this art, since the break point allows another air space for the gases and arc to fill, thereby significantly lessening the arc-interrupting properties of the arc-interrupting device. Further, failed arc extinguishing compositions that contain melamine usually fail because the pressure wave associated with the arc causes the composition to physically break before it has an opportunity to extinguish the arc. The arc-extinguishing compositions described herein extinguish the arc without physically breaking. Thermoplastic polymeric binders have been found to be the most useful in arc-interrupting compositions based upon melamine or similar compounds, since the thermoplastic binders volatilize or decompose in the presence of an electric arc at lower power conditions than necessary to sublime melamine thereby producing large volumes of gas to drive the melamine into the core of the arc and to extinguish the arc under a wide range of power conditions. Further, the thermoplastic binders provide compositions with good molding characteristics, stability and electrical insulating properties.
- Typical thermoplastic polymeric resins known to be useful as binders in melamine-based arc-interrupting compositions include polyethylene, polypropylene, polytetrafluoroethylene, acrylics, polystyrene, cellulosics polyamides (nylons), polyacetals (DELRIN), polyphenylene oxides, blends such as ABS, and polyimides. Other binders, such as thermosetting resins, epoxy resins, polyester resins, phenolic resins, and the like, also are known to be useful as binders in arc-interrupting compositions. It is also known to include elastomeric, rubber-like materials as a portion of the binder in melamine-based arc-interrupting compositions such as butyl compounds, isoprene-based compounds, neoprene-based compounds and other synthetic elastomers.
- In this assignee's U.S. Pat. No. 4,975,551, there is disclosed a binder comprising a carboxylic acid group-containing polymer, particularly a copolymer of two different monomers, at least one of which contains a carboxylic acid moiety, such as an ethylene acrylic acid copolymer. As disclosed, the carboxylic acid functionalities of the binder interact with arc-extinguishing compounds having carboxylic acid-active sites, such as amine, thiol, alcohol, halogen, and the like sites, to provide added physical strength and stability to the composition. The molded composition, including the arc-interrupting compound and the binder, maintains excellent arc-interrupting capability, chemical stability and electrical insulating properties as well as increased physical strength.
- In brief, the present invention is directed to a new and improved arc extinguishing composition including, a new and improved binder for compositions containing an arc-interrupting compound, such as melamine, and to a method of extinguishing an arc by disposing the composition along the path of the arc, for contacting the arc. In one embodiment, the binder, or at least a portion of the binder, is a polymer that contains a functional group that binds to a coupling agent that is included in the arc-extinguishing composition. The coupling agent, which may be a polymer that is compatible with the binder, contains a functional group that binds to the arc-extinguishing compound to tie the polymeric binder to the arc-extinguishing compound, e.g., melamine, to provide new and unexpected physical strength and stability to the composition. In this embodiment, the molded composition, including the arc-interrupting compound coupled to the binder, maintains excellent arc-interrupting capability, while providing chemical stability and electrical insulating properties as well as unexpected physical strength.
- In other embodiments of the arc-extinguishing compositions and articles described herein, the melamine or other arc-extinguishing compound provides unexpectedly better results when incorporated into the composition in finely divided form; and improved results are provided by combining a plasticizer for the polymeric binder.
- At least three embodiments of the arc-quenching materials and articles are described herein—each embodiment providing improved mechanical properties and/or arc-extinguishing results either alone or in combination with one or both of the other embodiments. Each of these three individual embodiments can be included alone in the materials and articles described herein or any two or three of these embodiments can be combined to further improve the materials and articles described herein.
- In brief, the three embodiments are as follows:
-
- (1) Incorporating a coupling agent into the arc-extinguishing composition that interacts mechanically and/or chemically with both the arc-extinguishing material and the polymeric binder to improve the mechanical properties and/or the arc-extinguishing properties of the composition and articles described herein.
- (2) Incorporating a plasticizer for a base binder polymer (e.g., caprolactam for a nylon base polymer) into the arc-extinguishing composition to enhance elongation and other mechanical properties, especially reducing brittleness of the arc-extinguishing composition; and
- (3) Incorporating a finely divided arc-quenching material into the arc-extinguishing composition. Preferably, the arc-quenching material is selected from the group consisting of melamine, guanidine, guanidine acetate, guanidine carbonate, 1,3-diphenylguanidine, cyanurates, melamine cyanurates, hydantoin, allantoin, urea, urea phosphate, benzoguanamine, dithioammelide, ammeline, and a cyanuric halide, and/or derivatives and/or mixtures thereof. In accordance with this embodiment, the arc-quenching material should have a particle size distribution such that at least 90% by weight of the particles have a particle size less than about 200 μm, preferably less than about 150 μm, more preferably less than about 100 μm, and most preferably less that about 50 μm. To achieve the full advantage of this embodiment, at least 95% by weight of the arc-quenching particles having a particle size less than about 50 μm.
- The arc-quenching compositions described herein are suitable for deionizing and extinguishing a high-voltage electrical arc. The compositions include effective amounts of an arc-extinguishing material, such as melamine, and sufficient binding polymer to achieve the desired combination of arc-extinguishing properties and structural characteristics, such as tensile strength, elongation, environmental resistance to thermal cycling, and the like. Additionally, the composition for various applications and uses may include additives, fillers or fibrous materials.
- The composition is homogenized by compounding the constituents using dry blending, roll mill, extrusion and/or other plastic compounding techniques to obtain the molding resin compositions. The molding resin then is molded into articles of the desired shape using plastic processing techniques, such as injection molding, extrusion, and the like. In a preferred composition, for example, to form a trailer for an interrupter, a nylon base polymer binder is combined with melamine and an anhydride-functional coupling agent to achieve the desired arc-extinguishing and mechanical characteristics by virtue of the bonding and/or miscibility between the melamine, nylon, and the anhydride-functional coupling agent.
- In other embodiments, as outlined above, the composition includes non-functionalized base polymeric binder(s) with or without the coupling agent and contains a finely divided arc-extinguishing material and/or a plasticizer for the base polymeric binder(s).
- Accordingly, one aspect of the compositions, articles and methods described herein is to provide a new and improved arc-quenching composition comprising effective proportions of an arc-extinguishing compound, such as melamine, and a polymeric binder containing coupling agent-interactive moieties, such as an ethylene maleic anhydride polymer, and a suitable coupling agent capable of chemically and/or mechanically attaching the arc-extinguishing compound to the coupling agent and coupling the arc-extinguishing compound to the polymeric binder to achieve improved strength and desirable environmental resistance to thermal cycling.
- Another aspect of the compositions, articles, and methods described herein is to provide a new and improved arc-extinguishing composition with improved mechanical characteristics, when molded, while exhibiting at least the same desirable electrical arc-extinguishing characteristics of previously available arc-extinguishing compositions and articles.
- Another aspect of the compositions, articles and methods described herein, is to provide a new and improved arc-extinguishing composition including an arc-interrupting compound and a polymeric binder wherein the binder is a polymer, or copolymer formed from two different monomers, including coupling agent reactive groups or moieties for coupling the binder to the arc-interrupting compound through a coupling agent.
- Another aspect of the compositions, articles and methods described herein, is to provide a new and improved arc-extinguishing composition including an arc-extinguishing compound having at least one site reactive with a coupling agent-contained functional group; or a polymeric binder material including a plurality of reactive coupling agent contained functional moieties, such that when the composition is molded under heat and pressure, the arc-extinguishing compound and the polymeric binder will chemically bond (including ionic and/or covalent bonds) to the coupling agent to provide new and unexpected physical strength in the molded composition.
- Still another aspect of the compositions, articles and methods described herein, is to provide a new and improved arc-interrupting composition including an arc-interrupting compound having at least one reactive amine site in its molecule, such as melamine, and a thermoplastic resin binder material containing an amine-reactive site and a binder-reactive site; together with a suitable coupling agent for coupling the arc-interrupting compound to the polymeric binder through the coupling agent.
- Another aspect of the compositions, articles and methods described herein, is to provide a new and improved arc-interrupting composition that provides sufficient and excellent arc-interrupting characteristics as well as new and unexpected molding and physical strength properties such as tensile strength, elongation and ability to withstand thermal cycling and resist cracking.
- The above and other aspects and advantages of the present invention will become apparent from the following detailed description of the preferred embodiments, taken in conjunction with the drawings.
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FIG. 1 is a bar graph showing mechanical toughness properties for the arc-extinguishing compositions of Table 1 in comparison toDELRIN 500; -
FIG. 2 and 3 are bar graphs showing weight changes due to water and nitric acid attack on the arc-extinguishing compositions of Table 1 in comparison toDELRIN 500; -
FIG. 4 is a bar graph showing the particle size distribution of standard grade and fine grade melamine; -
FIG. 5 is a perspective view of a fuse sleeve or liner formed from the arc-extinguishing compositions described herein; and -
FIG. 6 is a partially broken-away side view showing the sleeve or liner ofFIG. 1 surrounding a fuse. - In accordance with one embodiment of the compositions, articles, and methods described herein, it has been found that the physical and thermal properties of an arc-extinguishing composition can be unexpectedly improved when the arc-extinguishing composition includes a binder that contains a coupling agent-reactive functional group, such as an anhydride group, that bonds to coupling agent. These binders are particularly effective when used with arc-extinguishing compounds that have available reactive sites, such as amine groups; compounds containing one or more available hydroxyl groups, epoxy groups and/or aziridine groups; or compounds containing one or more available thiol groups having available carboxylic acid-reactive sulphur atoms, but are also effective with other arc-extinguishing compounds. The polymeric binders having one or more coupling agent-reactive functional groups, and the reactive coupling agents, described herein have been found to be particularly effective with melamine or other similar arc-extinguishing compounds, such as benzoguanamine, dithioammelide, ammeline, and a cyanuric halide.
- The functionalized, coupling agent-reactive polymeric binder need not form 100% of the binder material used in the arc-extinguishing compositions and excellent results have been found in improvement of known arc-extinguishing compositions when the functionalized binder is included in only a small portion, e.g., 0.5 to 20% by weight, of the binder material used. The non-reacted (non-functional) portion of the coupling agent and polymeric binder should be sufficiently compatible such that the composition, when melted, forms a homogenous composition.
- Suitable polymeric binders having one or more coupling agent-reactive functional groups include thermoplastic and thermosetting polymers having one or more functional groups selected from anhydride, carbonyl, hydroxyl, carboxyl, amine, amide, ether, lactam, lactone, epoxy, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate, and/or phosphinate; or an aromatic ring capable of covalently or ionically bonding to the coupling agent. Preferably, the binder has a functional group selected from anhydride, carbonyl, carboxyl, hydroxyl, amine, amide (particularly any nylon), ether, and/or an aromatic ring having a reactive group as part of the ring structure or as an extending coupling agent-reactive functional group. Examples of suitable polymeric binders containing these coupling agent-reactive functional groups include polypropylene, nylon 4/6, nylon 6/6, nylon 6, nylon 11, nylon 6/12, high-impact nylon, mineral-filled nylon, polycarbonate, polystyrene, acrylonitrile butadiene styrene, polysulfone, polybutylene terphthalate, polyethylene terphthalate, polyphenylene sulfide, polyester thermoplastic elastomer, polyetherimide, styrenic thermoplastic elastomer, olefinic thermoplastic elastomer, polyurethane thermoplastic, polyphenylene oxide, polyetheretherketone, phenylene ether co-polymer, polycarbonate/acrylonitrile butadiene styrene, polyarylether ketone, polyetherketoneetherketoneketone, polyphthalamide, and polyetherketoneketone and blends of any two or more of these polymers. Other suitable base resins include perfluoroalkoxy, ethylene tetrafluoroethylene, and polyvinylidene fluoride.
- The functionalized binders used in one embodiment of the arc-interrupting compositions can be used in a widely varying amount, as well known in the art, together with the arc-interrupting or arc-extinguishing compound, such as melamine, and can be a combination of a number of different thermosetting and/or thermoplastic binder materials well known in the art. The functionalized binders are usually included in amounts of at least about 10% by weight of the total arc-interrupting composition and preferably in an amount of at least about 20% by weight of the arc-interrupting composition. The best results for purposes of molding, physical and chemical stability and strength, arc-interrupting characteristics and insulation properties are achieved when the total amount of functionalized binders are in the range of about 15% to about 50% by weight of the arc-interrupting composition, preferably in the range of about 20% to about 40%, based on the total weight of the finished molded arc-interrupting composition and article.
- The coupling agents used in the coupling agent embodiment to tie the arc-extinguishing compound to the functionalized polymeric binder preferably is a monomeric or polymeric compound that contains reactive functional groups that provide covalent bonds to both the arc-extinguishing compound and the polymeric binder. However, the attractive interaction between the coupling agent and/or the arc-extinguishing compound and/or the polymeric binder also can be by any mechanism selected from the group consisting of electrostatic complexing, ionic complexing, chelation, hydrogen bonding, ion-dipole, dipole/dipole, Van Der Waals forces, and any combination thereof. The preferred coupling agent is a polymer, e.g., terpolymer, that has an anhydride functionality for reaction with the preferred melamine arc-extinguishing compound. For example, an ethylene/ethyl acrylate/maleic anhydride terpolymer coupling agent, e.g., Lotader 4720 from Atofina Chemicals Corporation, can react with a nitrogen atom of the melamine and a nitrogen atom of a nylon binder to couple the melamine to the nylon binder, e.g., nylon 6. The non-functional portion of the Lotadur coupling agent is compatible with the nylon, e.g., nylon 6 polymeric binder. Other examples of suitable coupling agents include organosilanes, organofunctional silylating agents, particularly the organosilanes having an amino, epoxy, acrylate, n-mercapto and/or vinyl functionality including (3-Acryloxypropyl)trimethoxysilane; N-(2-Aminoethyl)-3-aminopropyltrimethoxysilane; 3-Aminopropyltriethoxysilane; 3-Aminopropyltrimethoxylsilane; 3-Isocyanatoproplytriethoxysilane; (3-Glycidoxypropyl)trimethoxysilane; 3-Mercaptopropyltrimethoxysilane; 3-Methacryloxypropyltrimethoxysilane; and Vinyltrimethoxysilane.
- The preferred coupling agents are functionalized polyolefins, e.g., polyethylene or polypropylene that is functionalized with one or more reactive functionalities that provide reactivity or electrostatic association with the arc-extinguishing material and with the polymeric binder. The coupling agent preferably includes glycidylmethacrylate (GMA) and/or maleic anhydride (MAH) functional groups for better compatibility with polyester, polyamide and/or polyolefin polymeric binders. The most preferred coupling agents are functionalized polyolefins, particularly terpolymers of ethylene or propylene (PE or PP) with ethylacrylate (EA) and maleic anhydride (MAH) or glycidylmethacrylate having 6.5-30 wt. % EA; 0.3-3.1 wt. % MAH or GMA with the remaining 66.9 wt. % to 93.2 wt. % being PE or PP, preferably polyethylene. The terpolymer containing MAH is sold under the trade name Lotader, from Atofina Chemicals. Other suitable coupling agents include terpolymers of PE or PP with MAH and n-butyl acrylate (Lotader grades 2210, 3210, 4210 and 3410); MAH grafted ethylene/butane copolymers (elastomers), having about 0.25 wt. % to 1 wt. % MAH, sold by Dow Plastics, as AMPLIFY GR 208 functional polymers; titanate quarternary ammonium compounds, such as those sold by KENRICH petrochemicals as KEN-REACT® Water Soluble Chelate Titanate Quats and KEN-REACT® LICA®; KEN-REACT® NZ® Neoalkoxy Zinconates and Quats; KEN-REACT® KZ® Cycloheteroatom Zinconates; KEN-REACT® KA Reluminates; CAPOW® KR® and L® Series Titanate Coupling Agent Powders; styrene/maleic anhydride copolymers; epoxy modified polyolefins, particularly terpolymers of ethylene/methyl acrylate/glycidylmethacrylate (E-MA-GMA) or copolymers of ethylene and glycidylmethacrylate (E-GMA) having a GMA content of 3-8 wt. % and a methyl acrylate (MA) content of 0 or about 24-25% sold by Atofina Chemicals as Lotader AX8840; Lotader AX 8900 and Lotader AX8930; copolymers of ethylene and/or propylene with methacrylic acid (E/MAA) or (P/MAA), wherein the MAA acid groups have been partially neutralized, e.g., with metal, e.g., lithium, sodium or zinc, ions (DuPont SURLYN® 9320W); any Maleic Anhydride grafted polyolefin; any styrene/acrylonitrile grafted polyolefin; polypropylene/polymethylmethacrylate graft copolymers sold by Crompton Corporation as INTERLOY™ W1095H1; or the like.
- The arc-interrupting compound included in the compositions described herein, such as melamine, is included in the compositions in their normal amounts, well-known in the art, and generally in amounts of about 5% to about 90% by total weight of the arc-interrupting composition, preferably about 10% to about 70%, more preferably about 20% to about 50%, based on the total weight of the composition. Excellent results are achieved with arc-interrupting compounds and binder materials present in proportions ranging from about four parts by weight of arc-interrupting compound to one part by weight of polymeric binder material by weight to about one part by weight of arc-interrupting compound to one part by weight of polymeric binder material. Best results are achieved when the arc-interrupting compound is included in the composition in an amount of two to three parts by weight of arc-interrupting compound per part by weight of polymeric binder material.
- In the coupling agent embodiment described herein, of the total polymeric binder(s) included in the arc-interrupting composition, the functional group-containing polymers or copolymers should be included in an amount sufficient to improve the tensile strength of the molded composition, preferably more than a 10% increase in tensile strength, as a result of the addition of the functional group-containing binder.
- For example, a typical prior art arc-interrupting composition includes melamine in a polyethylene binder in proportions of three parts by weight of melamine to one part by weight of polyethylene binder and has a tensile strength of 1133 psi. By replacing only 5% of the polyethylene with a coupling agent-interacting functionalized polymeric binder, such as ethylene/maleic anhydride, together with a suitable coupling agent for both the functionalized polymer and the melamine, the tensile strength is increased more than 10%. By totally eliminating the polyethylene and substituting 100% ethylene/maleic anhydride as the binder material for melamine, the tensile strength is increased to 1677 psi, or almost 50%. Physical strength improvements are achieved with the inclusion of the functional group-containing binder materials, and a coupling agent-reactive therewith, in binder amounts as low as about 0.5% based on the total weight of binders present in the composition up to 100% replacement of the binder material with the functional group-containing binder(s).
- In the coupling agent embodiment described herein, to achieve the full advantage, the binder material used with the arc-interrupting compound should include the functional group-containing polymers or copolymers described herein in amounts of about 2% by weight to about 100% by weight preferably about 50% to about 100% by weight, based on the total weight of polymeric binders contained in the composition. The remaining percentage of binder material can be any binder effective for moldability and arc-extinguishing characteristics, such as the polyolefins, e.g. polyethylene and/or polypropylene; polyfluorinated resins, such as polytetrafluoroethylene, acrylic resins, polyamides, such as any nylon, and any other suitable binders, including thermosetting resins, such as epoxy resins, polyester resins, phenolic resins, and the like. Various elastomeric materials also may be included to improve the elongation properties of the molded compositions, such as butyl-based and/or isoprene-based and/or neoprene-based synthetic elastomers.
- In the coupling agent embodiment described herein, the binders are useful with any arc-interrupting compound(s) to provide an arc-quenching composition that is readily moldable into a desired shape while exhibiting structural properties, thermal stability, and environmental resistance to thermal cycling heretofore impossible with known arc-quenching compositions. Very unexpected structural (mechanical) property improvements are achieved for the coupling agent embodiment when the arc-interrupting compound is a material that includes one or more reactive sites that are chemically reactive with one or more reactive moieties of a coupling agent, which is also chemically reactive with the functional binders described herein. For example, melamine (C6N6H6) includes three equally spaced reactive primary amine moieties that can chemically bond (including ionic and/or covalent bonds) with the extending functional moieties of a vinyl/maleic anhydride binder, wherein the anhydride group acts as a coupling agent for the melamine, thereby achieving new and unexpected tensile strength, elongation and resistance to thermal cycling, while maintaining excellent arc-extinguishing properties.
- In the preferred embodiment, the percentage of functional group-containing monomer used in forming a functionalized binder polymer or copolymer, such as in the copolymerization of ethylene with maleic anhydride, and the like, can be varied widely to provide sufficient reactive, e.g., anhydride moieties, in the copolymer for chemical bonding (including ionic and/or covalent bonds) at one, two or all three of the reactive amine sites extending from the melamine vinyl structure. In this manner, different degrees of compound-binder chemical bonding can be provided for different properties when the functional group-containing polymers are used as at least a portion of the binder in the manufacture of arc-quenching compositions.
- In the coupling agent embodiment described herein, generally, the amount of functional group-containing monomer that should be polymerized, or copolymerized with a second monomer in forming copolymers, is from about 0.5 percent to about 80%, based on the total weight of the polymerizable monomers, with the second monomer present in an amount of about 20% by weight to about 95% by weight based on the total weight of both monomers. Such copolymers are readily available, such as the ethylene/maleic anhydride copolymers manufactured by Atofinacontaining various amounts of maleic anhydride monomer. The copolymer coupling agent sold by Atofina under the TrademarkLODATER 4720, provides an arc-quenching composition having exceptionally good structural characteristics, thermal stability and environmental resistance to thermal cycling. Other functionalized polymers and copolymers can be used having more or less coupling agent-reactive moieties, e.g., an anhydride percentage, and should provide similar structural improvements when used as a coupled binder in arc-quenching compositions.
- In the coupling agent embodiment described herein, it is theorized that a reactive site on the arc-quenching compound chemically bonds (ionically and/or covalently) with the functional moiety of the polymeric binder to achieve new and unexpected tensile strength, elongation and resistance to cracking heretofore unachieved in the prior art. In addition to the reactive amine groups extending from melamine arc-quenching compounds, other arc-quenching compounds also include reactive sites, such as benzoguanamine having a pair of extending reactive amine groups; thio substituted organic arc-quenching compounds, such as dithioammelide; ammeline; and halogenated compounds such as cyanuric chloride. Each of these compounds has the ability to generate large volumes of arc-extinguishing gases under the influence of an electric arc. Each of these compounds is useful in accordance with compositions, materials, and articles described herein, in combination with the coupling agent-reactive binders; and/or finely divided form of the arc-extinguishing compounds; and/or the plasticizers for the polymeric binders, to achieve new and unexpected structural, mechanical and physical properties in an arc-extinguishing or arc-interrupting composition.
- In accordance with the coupling agent embodiment described herein, it is theorized that a reactive, arc-extinguishing compound, such as melamine, undergoes chemical bonds (ionic and/or covalent bonding) with the functionalized polymeric binders described herein by reacting with the reactive functional group at one or more of the reactive compound sites.
- Similarly, any arc-extinguishing compounds that have reactive epoxy groups, aziridine groups, thiol groups, hydroxyl groups, halogen groups, and like -reactive sites, also can chemically bond (including ionic and/or covalent bonds) with the reactive functional groups from the polymeric binders used in the compositions described herein to provide new and unexpected structural properties, thermal stability, and thermal cycling resistance.
- The molecular weights of the reactive, functionalized polymeric binders vary widely and can range from a low of about 250 weight average molecular weight to a high of about 500,000 or more while achieving exceptionally good physical properties, thermal stability and resistance to thermal cycling in accordance with the compositions, articles, and methods described herein. It is preferred that the weight average molecular weight of the polymeric binders be in the range of about 1,000 to about 100,000 weight average molecular weight, and more preferably in the range of about 1,000 to about 50,000 weight average molecular weight.
- Other materials may be added to the compositions and articles described herein for additional insulating, strength, and/or arc-extinguishing properties, generally in amounts of about 0.1% to about 10% each, based on the total weight of the composition. Fibrous additives include glass, inorganic fibers and organic fibers, such as polyacrylonitrile, polyamide and polyester fibers. Fillers that may be included are, for example, cellulosic materials, calcium carbonate, metal oxides, comminuted polymers, carbon black, and natural and synthetic silica materials.
-
FIG. 1 shows one example of a specific use of the arc-extinguishing materials in the form of molded or extruded annular fuse sheath orliner 10, manufactured (molded or extruded) from the arc-extinguishing compositions described herein, that is dimensioned to surround afuse 12 disposed within afuse tube 14.Such fuses 12 may be provided to interrupt both low and high level fault currents. At low fault currents, if thesheath 10 does not burst or rupture and remains integral, the arc between terminals is elongated entirely within thefuse tube 14. The elongating arc interacts with the arc-extinguishing material of thesheath 10, evolving arc-extinguishing gases. If sufficient arc-extinguishing gas is evolved from the sheath and if the pressure of this gas within the sheath remains sufficiently high at a current zero, there will be sufficient dielectric strength due to the presence of the arc-extinguishing gas to prevent reignition of the arc. Thefuse 12 may also be called upon to interrupt high fault currents. At high fault currents the sheath usually ruptures and the extinguishment of the arc formed and elongated between terminals of the fuse is primarily due to the evolution of the arc-extinguishing gas from the bore of thefuse tube 14. - Data
- In order to show the unexpected structural properties that are achieved with the embodiments described and claimed herein, as compared to other arc-extinguishing compositions, various compositions were prepared and tested, as shown in Tables 1-7.
TABLE 1 ARC-extinguishing-EXTINGUISHING COMPOSITIONS Toughness Numbers Material/Toughness Unnotched Izod Impact Measurement Elongation, % Strength, ft-lbs/in Delrin 15-30 24-40 X-Material* 0.55 0.25 TX-Material** 3.9 3.2 70% Nylon/30% Melamine 2.9 2.8
*70% melamine/30% nylon
**72% melamine/28% EAA
-
TABLE 2 Material %, Type Nylon 6 %/Type Melamine % Coupling Agent 6.1 50 (note 1) 30, Fine 20 (3) 6.2 50 (note 1) 30, regular 20 (3) 6.6 50 (note 2) 30, regular 20 (3)
Notes:
1. This nylon 6 was impact modified, and plasticized with 4-8% Caprolactam (the monomer used to make Nylon 6)
2. This nylon 6 was impact modified, no plasticizer.
3. The coupling agent was Lotader 4720 (Atofina), 30% Ethyl Acrylate, 0.3% maleic Anhydride (Functional group), balance Ethylene.
4. Both materials 6.1 and 6.2 had a rubber-like feel to them. Material 6.6 was less rubbery, and had more stiffness (increased modulus). From this data it is clear that the caprolactam is an effective material in imparting toughness (6.2 vs. 6.6) and the fine melamine also improved toughness (6.1 vs. 6.2).
# However, the biggest effect is from the coupling agent/impact modifier. The increase in toughness is dramatically better than that seen going from X-Material to TX-Material. It is also clear a family of materials with a balance of toughness and stiffness can be made.
5. 6.1 material also proved to be a better AEM than Delrin, and to be more resistant to ozone and nitric acid. In addition, it can handle higher temperatures than X or TX.
- For the electrical tests, samples were molded into arc compressor parts and slat-shaped parts. Results of the molding runs appear in the following data. These parts were then assembled in Arc Compressor Assemblies, using production parts to complete the assemblies.
- Test Procedures
- Three types of tests were performed: Mechanical, Environmental, and Electrical.
- Mechanical Tests:
- Tensile testing was performed per ASTM D 638. Elongation was estimated from crosshead movement. Unnotched Izod impact testing was performed per ASTM D 4812. Since the Nylon 6 is hygroscopic, samples were tested in both the conditioned, and dry as molded (DAM) state. The results for
Delrin 500 from a previous experiment were used for comparison. - Environmental Test:
- The environmental test consisted of immersing flex bars of material (½″ by ⅛″ by 5″ long) most of the way into a solution of 10% Nitric Acid in DI water (by volume) for 7 days. Due to a miscalculation, the first 3 days were in a 7% solution. By not immersing the samples completely, an air/solution interface is created that tends to accelerate the chemical attack. Since Nylon 6 is hygroscopic, a control in 100% DI water was also run. The effect on weight and width was documented.
- Electrical Test:
- Electrical tests were run. In the first, the interruption test, the High Power Lab set up provided a nominal 25 kV, 400 A circuit. A travel record and timing shot were first done, then the switch was opened and closed, with arcing times on opening and pre-strike times on closing recorded.
- For this testing, the samples were placed into a Mini-Rupter switch. A steel (unpainted) ground plane was placed in front of the Mini-Rupter, 8 inches from the tip of the Mini-Rupter blade when in the open condition. The Mini-Rupter strut was energized, and the ground plane, frame, and adjacent phases were grounded. No barrier boards were used anywhere in the switch. The results are shown in the graph of
FIG. 1 . Composition 6.1 was the first AEM material tested that matched or exceeded the toughness numbers for Delrin. Composition 6.1 also displayed rubber-like properties. - Environmental Tests:
- The results of the environmental test appear in
FIG. 2 (Weight Change) andFIG. 3 (Size Change). A positive change indicates a weight or size gain, a negative indicates a weight or size loss. - Both the 6.1 and the F.1 compositions provided much better resistance to nitric acid than the Delrin. They suffer surface attack in the form of yellowing, but no significant material loss. The Delrin sample showed severe erosion at the waterline, looking much like Delrin samples from the Swamp.
- Note that the Nylon 6 material both gained 1.6% in weight and 1.6% in size due to water absorption.
- Electrical Tests:
- The results of the testing at 25 kV, 400 A (nominal) testing for composition 6.1 appears in Table3. The arcing times for the 6.1 material was surprisingly better than the acetrolu material (DELRIN). In the tests that involved restrikes for material 6.1, these restrikes were due to the compressors being too flexible, and allowing some hot gases to escape.
TABLE 3 Compressors, Electrical Results, 25 kV, 400 A. Closing Opening Voltage, Current, Pre- Arc Time, Trace # kV A Strike, ms ms Video, ID Notes 29 24.6 382 3.6 6.1 30 24.2 381 14 31 24.5 389 3.4 32 24.4 375 19 33 24.7 387 1.5 34 24.9 383 13.2 9 35 25.6 400 4.9 10 36 24.8 378 13.9 11 37 25.4 392 2.1 12 38 24.6 385 13.5 13 39 24.5 399 1 14 40 24.9 383 16.8 15 Restrike, clear n/a n/a n/a n/a No data 44 n/a 382 12.8 17 Restrike, no clear -
TABLE 4 Unnotched Izod Impact Strength, Modulus Material Elongation, % ft-lbs/in (ksi) 70% Nylon/30% 2.9 2.8 na Melamine (control) TX-Material 3.9 3.2 na (Control) 6.1 36.7 No Break(1) 50 6.2 20.5 No Break(1) 60 6.6 9.46 No Break(1) 137
Note 1:
material folds under blade without breaking.
- Both materials 6.1 and 6.2 had a rubber like feel to them. Material 6.6 was less rubbery, and had more stiffness (increased modulus). From this data it is clear that the caprolactam is an effective material in imparting toughness (6.2 vs. 6.6) and the fine melamine also improved toughness (6.1 vs. 6.2). However, the biggest effect is from the coupling agent/impact modifier. The increase in toughness is dramaticly better than that seen going from X-Material to TX-Material. It is also clear a family of materials with a balance of toughness and stiffness can be made.
- 6.1 material also proved to be a better AEM than Delrin, and to be more resistant to ozone and nitric acid. In addition, it can handle higher temperatures than X or TX.
TABLE 5 AEM Weight Change Change Due Change Due Material to Water, % To Nitric, % F.1 0.87 −0.42 (melamine with acrylic binder) 6.1 1.70 2.12 Delrin 5000.41 −20.07 -
TABLE 6 AEM Size Change Change Due Change Due Material to Water, % To Nitric, % F.1 1.43 0.00 (melamine with acrylic binder) 6.1 1.63 0.61 Delrin 5000.10 −12.34 - In accordance with a second embodiment of the arc-extinguishing compositions, articles and methods described herein, it has been found that when the arc-extinguishing compound is provided in finely divided form (see Table 2 and
FIG. 4 ), the molded arc-extinguishing composition has unexpectedly increased toughness, and especially elongation, thereby preventing breakage of the molded articles. - In accordance with the second embodiment, wherein the arc-extinguishing compound is provided in finely divided form, it has been found that the compound should have a particle size distribution such that at least 90% by weight, up to 100%, of the particles have a size less than about 200 microns (μm). Preferably, at least 90% by weight of the particles have a particle size less than about 100 μm and, more preferably, at least 99% by weight of the arc-extinguishing compound particles have a particle size less than 100 μm. To achieve the full advantage of this second embodiment of the compositions, articles and methods described herein, at least 90% by weight, up to 100% by weight, of the arc-extinguishing compound particles should have a particle size less than 50 μm. Excellent increases in elongation of molded arc-extinguishing devices have been achieved with a finely divided melamine obtained from DSM, sold for other purposes, as Melamine Grade 003 having a particle size distribution as follows: 99 wt. % below 40 μm; 90 wt. % below 30 μm; 50 wt. % below 15 μm; and 10 wt. % below 5 μm.
- In accordance with a third embodiment of the compositions, articles and methods described herein, it has been found that by including a plasticizer for the binder polymer into the compositions, the structural properties of the molded articles are increased without sacrificing arc-extinguishing properties.
- To determine which plasticizer(s) is suitable for a particular polymer binder, compatible plasticizers should have a solubility parameter (δ) suitable for the particular polymeric binder, as well known in the art. One method of determining solubility parameters (δ) is in accordance with ASTM Designation D-3132-84 (Re-approved 1990). The plasticizer for the polymeric binders should have a solubility parameter (δ) as close as possible to the solubility parameter of the polymeric binder. For example, some of the preferred polyamide (nylon) polymeric binders have solubility parameters (δ) as follows:
Preferred δ for δ for ε- δ for binder plasticizer caprolactam Nylon 6: δ = 12.83 11.5-14.0 12.7 Nylon 8: δ = 12.7 11.5-14.0 Nylon 11: δ = 11.065 10-13 Nylon 12: δ = 10.72 9-13 Nylon 6/6: δ = 12.95-13.6 11.5-14.0 Nylon 6/10: δ = 11.86 11-14 - Polyester polymeric binders have solubility parameters δ in the range of about 9.5 to 12. Maleic Anhydride has a δ of about 13.6. The adipate plasticizers have relatively low solubility parameters, but are suitable for plasticizing amines. Epoxys have δs of about 9-11 and ethers have δs of about 7.5-11. Ketones have δs of about 8.4-10; lactones of about 10-14; maleates about 8.5-10; phenols about 9.5-13; phosphates about 7.5-10; phosphonates about 8-10. The above are general guidelines, and the solubility parameters for polymers (polymeric binders) and compatible solvents (plasticizers) for the polymeric binders are available, for example, in Specific Interactions and the Miscibility of Polymer Blends: Practical Guides for Predicting & Designing Miscible Polymer Mixtures, Michael M. Coleman, et al., Lancaster, Pa., U.S.A.; Technomic Pub. Co., c1991; and in C. M. Hansen, J Paint Technol., 1967. 39. 104.
- In general, any of the monomers used to form a polymeric binder can be used as a plasticizer for that polymer binder (e.g., ε-caprolactam used to plasticize nylon 6) in accordance with the third (plasticizer) embodiment described herein. The plasticizer need only be compatible with the polymeric binder such that a homogeneous mixture is achieved when the arc-extinguishing composition is melted during the article molding process. If the plasticizer is not sufficiently compatible with the polymeric binder, the plasticizer will separate from the binder when melted, or will not form a homogeneous composition when melted together with the arc-extinguishing compound and other components of the composition.
- The data of Table 7 compares the percent elongation achieved in molded articles containing DSM Melamine Grade 003 in comparison to the standard grade melamine. Compositions with and without a plasticizer also are shown in Table 7. A comparison of the finely divided melamine versus standard grade melamine is shown in
FIG. 4 . - As shown in Table 7, in comparison to control AEM-containing compositions containing (1) 70% nylon/30% melamine and (2) one of the materials of this assignee's U.S. Pat. No. 4,975,551 containing 72% melamine/28% ethylene acrylic acid (EAA), the compositions containing a reactive-functionality containing polymer binder (an ethylene/maleic anhydride copolymer) and a coupling agent for the reactive binder (LOTADER 4720-30% ethyle acrylate/0.3% maleic anhydride/69.7% ethylene copolymer).
Claims (28)
1. An arc-extinguishing composition comprising an effective amount of an arc-extinguishing compound;
a polymeric binder for the arc-extinguishing compound; and
a coupling agent that binds the arc-extinguishing compound to the polymeric binder.
2. The composition of claim 1 , wherein the polymeric binder includes a functionality selected from the group consisting of anhydride, hydroxyl, carbonyl, carboxyl, amine, amide, ether, lactam, lactone, epoxy, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate, and combinations thereof.
3. The composition of claim 2 , wherein the polymeric binder includes a functionality selected from the group consisting of anhydride, carbonyl, carboxyl, hydroxyl, amine, amide, ether, ester, and combinations thereof.
4. The composition of claim 3 , wherein the binder comprises a polyamide.
5. The composition of claim 4 , wherein the polyamide is a nylon.
6. The composition of claim 5 , wherein the nylon is selected from the group consisting of nylon 4/6, nylon 6, nylon 6/6, nylon 11 and nylon 6/12.
7. The composition of claim 1 , wherein the arc-extinguishing compound is selected from the group consisting of melamine, guanidine, guanidine acetate, guanidine carbonate, 1,3-diphenylguanidine, a cyanurate, a melamine cyanurate, hydantoin, allantoin, urea, urea phosphate, benzoguanidine, dithioammelide, ammeline, a cyanuric halide, and combinations thereof.
8. The composition of claim 7 , wherein the arc-extinguishing compound is selected from the group consisting of melamine, benzoguanidine, dithioammelide, ammeline, a cyanuric halide, and combinations thereof.
9. The composition of claim 8 , wherein the arc-extinguishing compound is melamine.
10. The composition of claim 9 , wherein the melamine has a particle size such that at least 90% by weight of the melamine particles have a size less than 200 μm.
11. The composition of claim 10 , wherein the melamine has a particle size such that at least 90% by weight of the melamine particles have a size less than 100 μm.
12. The composition of claim 11 , wherein the melamine has a particle size such that at least 90% by weight of the melamine particles have a size less than 50 μm.
13. An arc-extinguishing composition comprising an effective amount of an arc-extinguishing compound;
a polymeric binder for the arc-extinguishing compound; and
a coupling agent that binds the arc-extinguishing compound to the polymeric binder; and
a compatible plasticizer for said polymeric binder.
14. The composition of claim 13 , wherein the polymeric binder includes a functionality selected from the group consisting of anhydride, hydroxyl, carbonyl, carboxyl, amine, amide, ether, lactam, lactone, epoxy, ester, sulfate, sulfonate, sulfinate, sulfamate, phosphate, phosphonate, phosphinate, and combinations thereof.
15. The composition of claim 14 , wherein the polymeric binder includes a functionality selected from the group consisting of anhydride, carbonyl, carboxyl, hydroxyl, amine, amide, ether, ester, and combinations thereof.
16. The composition of claim 15 , wherein the binder comprises a polyamide.
17. The composition of claim 16 , wherein the polyamide is a nylon.
18. The composition of claim 17 , wherein the nylon is selected from the group consisting of nylon 4/6, nylon 6, nylon 6/6, nylon 11 and nylon 6/12.
19. The composition of claim 13 , wherein the arc-extinguishing material is selected from the group consisting of melamine, guanidine, guanidine acetate, guanidine carbonate, 1,3-diphenylguanidine, a cyanurate, a melamine cyanurate, hydantoin, allantoin, urea, urea phosphate, benzoguanidine, dithioammelide, ammeline, a cyanuric halide, and combinations thereof.
20. The composition of claim 19 , wherein the arc-extinguishing compound is selected from the group consisting of melamine, benzoguanidine, dithioammelide, ammeline, a cyanuric halide, and combinations thereof.
21. The composition of claim 20 , wherein the arc-extinguishing compound is melamine.
22. The composition of claim 21 , wherein the melamine has a particle size such that at least 90% by weight of the melamine particles have a size less than 200 μm.
23. The composition of claim 22 , wherein the melamine has a particle size such that at least 90% by weight of the melamine particles have a size less than 100 μm.
24. The composition of claim 23 , wherein the melamine has a particle size such that at least 90% by weight of the melamine particles have a size less than 50 μm.
25. An arc-extinguishing composition comprising an effective amount of melamine having a particle size distribution such that at least 90% by weight of melamine particles have a size less than 200 μm; and a binder for the melamine.
26. An arc-extinguishing sheath disposed to surround an electrical fuse, said sheath formed from the composition of claim 1 .
27. An arc-extinguishing sheath disposed to surround an electrical fuse, said sheath formed from the composition of claim 13 .
28. An arc-extinguishing sheath disposed to surround an electrical fuse, said sheath formed from the composition of claim 25.
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PCT/US2005/017100 WO2006016932A1 (en) | 2004-07-09 | 2005-05-16 | Arc-extinguishing composition and articles manufactured therefrom |
AU2005272193A AU2005272193B2 (en) | 2004-07-09 | 2005-05-16 | Arc-extinguishing composition and articles manufactured therefrom |
BRPI0513059-0A BRPI0513059A (en) | 2004-07-09 | 2005-05-16 | arc extinguishing composition and arc extinguishing shell |
EP05749425.4A EP1787307B1 (en) | 2004-07-09 | 2005-05-16 | Arc-extinguishing composition and articles manufactured therefrom |
CA2572987A CA2572987C (en) | 2004-07-09 | 2005-05-16 | Arc-extinguishing composition and articles manufactured therefrom |
CN200580022981.9A CN1981355B (en) | 2004-07-09 | 2005-05-16 | Arc-extinguishing composition and articles manufactured therefrom |
US11/969,651 US7893380B2 (en) | 2004-07-09 | 2008-01-04 | Arc-extinguishing composition and articles manufactured therefrom |
US12/137,765 US20080237194A1 (en) | 2004-07-09 | 2008-06-12 | Metal-hydrate containing arc-extinguishing compositions and methods |
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US20080237194A1 (en) * | 2004-07-09 | 2008-10-02 | S & C Electric Co. | Metal-hydrate containing arc-extinguishing compositions and methods |
US20080250892A1 (en) * | 2007-04-11 | 2008-10-16 | Dura Global Technologies, Inc. | Transmission Cable Assembly for High Temperature Environments |
US8857289B2 (en) * | 2007-04-11 | 2014-10-14 | Dura Operating, Llc | Transmission cable assembly for high temperature environments |
EP2133388A2 (en) | 2008-06-12 | 2009-12-16 | S & C Electric Company | Metal-hydrate containing arc-extinguishing compositions and methods |
EP2133388A3 (en) * | 2008-06-12 | 2010-02-17 | S & C Electric Company | Metal-hydrate containing arc-extinguishing compositions and methods |
AU2009202223B2 (en) * | 2008-06-12 | 2015-09-10 | S & C Electric Company | Metal-hydrate containing arc-extinguishing compostions and methods |
US20110290624A1 (en) * | 2010-05-28 | 2011-12-01 | ABB Techology AG | Switching chamber insulation arrangement for a circuit breaker |
US8420971B2 (en) * | 2010-05-28 | 2013-04-16 | Abb Technology Ag | Switching chamber insulation arrangement for a circuit breaker |
CN104559169A (en) * | 2014-12-29 | 2015-04-29 | 浙江俊尔新材料股份有限公司 | Inflaming retarding aerosis polyamide arc extinguishing composite material |
WO2016145556A1 (en) * | 2015-03-13 | 2016-09-22 | Abb Technology Ltd | Thermoplastic arc-quenching tube and its application |
EP3985709A1 (en) * | 2020-10-15 | 2022-04-20 | Littelfuse, Inc. | Fuse with arc quenching silicone composition |
Also Published As
Publication number | Publication date |
---|---|
CN1981355A (en) | 2007-06-13 |
WO2006016932B1 (en) | 2006-04-06 |
AU2005272193A1 (en) | 2006-02-16 |
WO2006016932A1 (en) | 2006-02-16 |
US7893380B2 (en) | 2011-02-22 |
EP1787307B1 (en) | 2015-01-28 |
BRPI0513059A (en) | 2008-04-22 |
CN1981355B (en) | 2012-06-06 |
US20080169271A1 (en) | 2008-07-17 |
CA2572987A1 (en) | 2006-02-16 |
CA2572987C (en) | 2012-12-11 |
AU2005272193B2 (en) | 2010-11-25 |
EP1787307A1 (en) | 2007-05-23 |
MX2007000272A (en) | 2007-04-10 |
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Legal Events
Date | Code | Title | Description |
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AS | Assignment |
Owner name: S&C ELECTRIC CO., ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MOORE, JEFFREY A.;REEL/FRAME:015105/0217 Effective date: 20040709 |
|
AS | Assignment |
Owner name: S & C ELECTRIC CO., ILLINOIS Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:MOORE, MR. JEFFREY A.;REEL/FRAME:015109/0393 Effective date: 20040709 |
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STCB | Information on status: application discontinuation |
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