EP4208882A1 - Corona shielding strip for a high-voltage rotating electric machine, use thereof, and electric machine - Google Patents
Corona shielding strip for a high-voltage rotating electric machine, use thereof, and electric machineInfo
- Publication number
- EP4208882A1 EP4208882A1 EP21805895.6A EP21805895A EP4208882A1 EP 4208882 A1 EP4208882 A1 EP 4208882A1 EP 21805895 A EP21805895 A EP 21805895A EP 4208882 A1 EP4208882 A1 EP 4208882A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- corona protection
- tape
- accelerator
- corona
- anhydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000009413 insulation Methods 0.000 claims abstract description 60
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 35
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 24
- 238000005470 impregnation Methods 0.000 claims abstract description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 18
- 239000003930 superacid Substances 0.000 claims abstract description 18
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- -1 sulfonium cation Chemical class 0.000 claims description 27
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 23
- 238000004804 winding Methods 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000011231 conductive filler Substances 0.000 claims description 12
- 125000002091 cationic group Chemical group 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 8
- 229910001887 tin oxide Inorganic materials 0.000 claims description 8
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000005840 aryl radicals Chemical class 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims 2
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 14
- 230000001235 sensitizing effect Effects 0.000 abstract description 3
- 210000002345 respiratory system Anatomy 0.000 abstract description 2
- 125000003118 aryl group Chemical group 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- 239000000945 filler Substances 0.000 description 16
- 150000001768 cations Chemical class 0.000 description 13
- 239000004020 conductor Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 230000036961 partial effect Effects 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 10
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 239000010445 mica Substances 0.000 description 6
- 229910052618 mica group Inorganic materials 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical class CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- 230000005684 electric field Effects 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 125000004434 sulfur atom Chemical group 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004971 Cross linker Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 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 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000037452 priming Effects 0.000 description 3
- 239000012783 reinforcing fiber Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000010981 turquoise Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- 241000270722 Crocodylidae Species 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 101100365384 Mus musculus Eefsec gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010063493 Premature ageing Diseases 0.000 description 1
- 208000032038 Premature aging Diseases 0.000 description 1
- 229910018287 SbF 5 Inorganic materials 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- VQYHBXLHGKQYOY-UHFFFAOYSA-N aluminum oxygen(2-) titanium(4+) Chemical compound [O-2].[Al+3].[Ti+4] VQYHBXLHGKQYOY-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- LNNWVNGFPYWNQE-GMIGKAJZSA-N desomorphine Chemical compound C1C2=CC=C(O)C3=C2[C@]24CCN(C)[C@H]1[C@@H]2CCC[C@@H]4O3 LNNWVNGFPYWNQE-GMIGKAJZSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FJIKWRGCXUCUIG-UHFFFAOYSA-N lormetazepam Chemical compound N=1C(O)C(=O)N(C)C2=CC=C(Cl)C=C2C=1C1=CC=CC=C1Cl FJIKWRGCXUCUIG-UHFFFAOYSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02K—DYNAMO-ELECTRIC MACHINES
- H02K3/00—Details of windings
- H02K3/32—Windings characterised by the shape, form or construction of the insulation
- H02K3/40—Windings characterised by the shape, form or construction of the insulation for high voltage, e.g. affording protection against corona discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/21—Paper; Textile fabrics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/04—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances mica
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02K—DYNAMO-ELECTRIC MACHINES
- H02K3/00—Details of windings
- H02K3/30—Windings characterised by the insulating material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/414—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of a copolymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2429/00—Presence of polyvinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2463/00—Presence of epoxy resin
Definitions
- Corona protection strip for rotating electrical high-voltage machine, use therefor and electrical machine
- the invention relates to a corona protection band, in particular a reactive corona protection band, for a rotating electrical high-voltage machine with an insulation system that can be produced by vacuum pressure impregnation process (VPI process), the impregnation agent in the VPI process being used for concerns about the airway sensitizing effect of the Anhydrides de, preferably anhydride-free.
- VPI process vacuum pressure impregnation process
- the invention also relates to the use of such a corona protection strip and an electrical machine with an insulation system that can be produced using the corona protection strip.
- an insulation system Depending on the rated voltage of the rotating electrical machine, different combinations of components of an insulation system are used when producing an insulation system .
- the external corona protection AGS.
- an AGS is usually reinforced at the ends by end corona protection EGS and from a rated voltage of approx . 12kV, the insulation system on the main insulation is reinforced by an IPS internal potential control.
- anhydride-containing crosslinkers in the impregnating agents of the insulation system, in particular the insulation systems that can be produced by VPI, the anhydride is increasingly being replaced by anhydride-free impregnating agents.
- This substitution entails a whole range of adjustment problems, since the winding tapes and/or corona protection tapes, which in turn contain organic binders such as the tape adhesive, polymer-based matrix materials and, in the case of reactive corona protective tapes also include curing catalysts, to which the newly used anhydride-free impregnating agents must be matched.
- the conductive layers of the IPS and the AGS usually consist of a composite material containing carbon black and/or graphite and based on a polymer matrix. No component of the composite material, neither the carbon black/graphite nor the polymeric matrix are resistant to partial discharges. If a partial discharge hits the conductive layer, the soot reacts with the surrounding oxygen to form CO 2 . The same applies to the polymeric matrix.
- Main insulation or AGS, EGS and IPS are usually formed by winding mica tape or corona protection tape, which is impregnated with an impregnating agent.
- the mica tape of the main insulation usually includes a barrier material, such as mica for insulation, while the corona protection tape contains electrically conductive or partially conductive fillers, such as carbon black, etc. includes .
- the corona protection tape contains electrically conductive or partially conductive fillers, such as carbon black, etc. includes .
- the tertiary amines and/or organic zinc salts that have been customary up to now and are ideally suited for anhydride-containing impregnating agents can no longer be used as so-called belt accelerators for the new, anhydride-free impregnating agents because they can no longer be used under the conditions of the Inadequate networking of the VPI process.
- a low glass transition temperature should also be avoided locally, since these areas have insufficient mechanical and electrical properties and lead to significantly premature degradation. During operation, these low-load areas are quickly thermally and electrically degraded or destroyed.
- Corona protection tapes as part of the insulation system are used in rotating electrical high-voltage machines.
- Rotating high-voltage machines are, for example, motors or generators in a power plant for generating electrical energy.
- Such rotating high-voltage machines have, in particular, a stator winding which is subject to particularly high demands in terms of strength and reliability.
- the insulation system of the stator winding at the interface between the main insulation and the laminated core, especially in rotating electrical machines from approx. 2 kV rated voltage, the stator winding is heavily loaded by high thermal, thermomechanical, dynamic and electromechanical operating stress, which means that the risk of damage to the insulation system of the stator winding due to partial discharge is high.
- the stator winding has a conductor assembly that is electrically insulated from the main insulation and that is mounted in a slot that is arranged in the laminated core.
- the stator is exposed to alternating thermal stress, as a result of which mechanical stresses are generated in the main insulation, caused by different thermal expansion rates and thermal conductivities of the conductor, the main insulation and the laminated core.
- alternating thermal stress as a result of which mechanical stresses are generated in the main insulation, caused by different thermal expansion rates and thermal conductivities of the conductor, the main insulation and the laminated core.
- localized detachment of the main insulation can occur, creating cavities between the main insulation and the sheet metal packets arise in which partial discharges can ignite.
- the partial discharges can lead to damage to the main insulation, which in the worst case can lead to an earth fault between the laminated core and the conductor, which means that the machine can no longer be operated .
- the conductor with its main insulation conventionally protrudes at the slot exits, where the interface between the conductor and the main insulation is arranged, which forms a sliding arrangement.
- FIG. 1 of EP 2362399B1 in which the section of the turbogenerator stand shown there corresponds schematically to the slot exit point dealt with here.
- the main insulation of the winding against the laminated core is an electrically highly stressed system.
- high voltages arise, which must be dissipated in the insulating volume between the conductor bar and the laminated core, which is at ground potential.
- Field increases occur at the edges of the sheets in the laminated core, which in turn cause partial discharges and ultimately lead to premature aging and, in the worst case, to destruction of the insulation.
- the exit point of the stator bars/coil legs from the laminated core, the slot exit point, is characterized by the meeting of two insulating materials, the gaseous and the solid, and the AGS and/or IPS or the laminated core.
- a boundary layer forms between the main insulation, which is solid in its aggregate state, and a gaseous medium, usually air or hydrogen .
- the resulting dielectric interface between the main insulation and the air creates a classic slip arrangement which, in addition to a purely radial field component E rad , which is perpendicular to the conductor and which occurs in the area of the laminated core, also has a tangential field component E tan arising along the conductor after AGS end has .
- a resistive-capacitive field control in the form of an end corona protection "EGS” is connected to the AGS in addition to the external corona protection "AGS" for electrical rotating machines from a rated voltage of 6kV.
- GGS external corona protection
- the highest electro-thermal load on the system does not occur at the operating voltage, but rather when the insulation system is checked with an increased test voltage .
- the insulating material is destroyed in the long term by the formation of creeping discharges on the surface.
- the end corona protection is a resistive coating directly on the surface of the main insulation.
- the external corona protection which has a surface resistance of around 1000 - 10,000 ohms
- the "EGS” the end corona protection
- the relevant resistance range of the EGS can be specified as 2x10 8 ohms to 1x10 13 ohms.
- heating, electrical erosion and chemical degradation can destroy the EGS and thus damage the insulation system and ultimately flashover as a result of the destruction of the end corona protection. It can be due to local heat development an operating point shift in addition to disrupting the functioning of the insulation system and increasing the dielectric losses.
- the AGS has a certain square resistance, which must not fall below or exceed a specific lower and upper limit. If the limit value is not reached, high circulating currents induced, which close via the ends of the laminated core and the external corona protection, can lead to high-current arcs between two laminated cores in the laminated core, resulting in high electrical losses . If the resistance is too high, high-voltage spark erosion can occur, in which case the AGS no longer acts like a field equalization, but like an insulation. Ideally, external corona protection has a pronounced anisotropy in the resistance behavior; the resistance in the tangential, i.e. axial, direction should be high and in the radial direction low.
- the object of the present invention is therefore to provide a corona protection strip for further processing in the VPI process, a carrier strip, at least one strip accelerator for the impregnating resin and at least one polymeric matrix material with an electrically conductive, optionally coated filler comprehensive, wherein the belt accelerator contained in the corona protection belt is suitable for curing-accelerating an anhydride-free impregnating agent, in particular based on epoxy resin, in the VPI process.
- the subject of the present invention is a corona protection tape for further processing into an insulation system with winding and potential control through external corona protection and/or internal potential control and/or end corona protection, the insulation system by impregnating the winding with an anhydride-free and resin-based Impregnating agent at 45 ° C to 85 ° C and under vacuum, for example by means of VPI impregnation, can be produced, the corona protection tape at least one carrier tape an electrically conductive or partially conductive filler in a polymer matrix and at least one tape accelerator suitable for Hardening and/or gelling of the impregnating agent, characterized in that the polymer matrix contains at least one polyvinyl alcohol and/or a polyvinyl alcohol copolymer and that the at least one belt accelerator is selected from the group of super acid salts , using it to speed up a katio African homopolymerization of the resin-based anhydride-free impregnating agent is suitable.
- the basis of the resin-based impregnating agent is preferably an epoxy resin, in particular also an epoxy resin mixture, for example an epoxy resin mixture comprising one or more cycloaliphatic epoxy resins.
- This mixture can also contain siloxane, for example, so that when the impregnating agent cures, a duromer with a backbone comprising —O—SiR 2 —O— units is obtained.
- the impregnating agent is in particular a phthalic anhydride or phthalic anhydride derivative-free resin or a resin mixture based on epoxy, preferably at least one cycloaliphatic epoxy resin and an epoxy resin based on bisphenol A and/or bisphenol F diglycidyl ether. and/or epoxy volak base comprehensive .
- the polymer matrix includes the tape adhesive and - at least partially - the tape accelerator dissolved and/or finely distributed in it, also called "tape catalyst".
- Tape catalyst also called "tape catalyst”.
- -Pressure impregnation (VPI) acts on the corona protection strip and the main insulation of the stator winding.This usually happens at elevated temperatures, 45 °C to 85 °C.After impregnation, the stator windings in the stator core are thermally post-hardened.
- the at least one belt accelerator is preferably present in the polymeric matrix with the fillers. During impregnation, this mixes at least partially with the impregnating agent and/or can at least partially migrate into the impregnating agent and thus serves to gel the impregnating agent before it hardens in the subsequent tempering step of the impregnating process.
- the tape accelerator which is present for example and preferably in the form of a superacid salt, is present in the polymer matrix or the tape adhesive, ie comprising at least one polyvinyl alcohol, very finely distributed and/or dissolved.
- the tape accelerator present in the corona protection tape in the form of a super acid and/or a super acid salt only reacts on contact with the impregnating agent and at elevated temperatures of 45° C. to 85° C .
- a prior reaction with the polymeric matrix is undesirable because the belt accelerator is then “loaded”. would be needed” and the impregnating agent could no longer harden, gel or harden. Therefore, a critical point of the present invention is that the belt accelerator is in the form of the extremely reactive super acid and/or a derivative thereof, with the polymer matrix of the corona protection strip does not react or reacts to an insignificant extent under conditions of up to 70 °C.
- the accelerator in the carrier tape is, for example, in an amount in the range from 0.1 g/m 2 to 15 g/m 2 , in particular from 0.25 g/m 2 to 10 g/m 2 , preferably in an amount of 0. 5 g/m 2 to 5 g/m 2 included.
- the embedded belt accelerators and belt accelerator concentrations in the components of the insulation system can be the same or different.
- the main insulation of winding bars/coils can be shielded against cavities and detachments with an inner and an outer conductive layer, precisely by means of internal potential control IPS and AGS, as explained above.
- An EGS can then be applied to the AGS.
- Corona protection tapes are known from EP 2362399 and DE 19839285 G1, in which a planar filler is bound in a polymeric matrix.
- the planar filler described consists of a mica substrate with doped metal oxide, for example titanium oxide and/or tin oxide, is coated.
- this filler is more resistant to partial discharges than the carbon-based fillers.
- the electrical resistance in the direction of the strip in the polymer matrices filled with planar fillers is significantly lower than that perpendicular through the strip, which in turn reduces the electrical conductivity in the radial direction.
- the radial resistance can be reduced by the addition of round fillers, in which quartz material or powdered quartz serves as the substrate, which in turn has also been coated with doped metal oxide.
- the electrically conductive and/or partially conductive filler has at least one component selected from the group consisting of carbon black, graphite, carbon nanotubes—CNTs—, antimony-doped tin oxide, silicon carbide and/or aluminum-doped silicon carbide, with the respective component being doped or undoped, coated or uncoated, doped coated or undoped coated.
- a capacitive-resistive field control is used to reduce the field strength increase in the area of the end of the external corona protection.
- the capacitive control is realized through the main insulation, while the resistive control takes place through the end corona protection (EGS).
- EGS end corona protection
- These are conductive surface coatings that have a square resistance of approx. 10 8 to 10 10 ohms at a field strength of 100 V/mm.
- the ohmic surface coatings can be applied either by painting from drying and/or hardenable resins, which are applied directly to the surface of the insulating material and/or together with the production of the wound main insulation, which is then applied before production or respectively Impregnation of the main insulation are wound up as tapes, either in the form of a prepreg or an already cured, porous tape.
- the main insulation of the winding is then impregnated with an impregnating resin and, for example, by means of a vacuum pressure impregnation process (VPI process) carried out therewith.
- VPI process vacuum pressure impregnation process
- epoxy resins and/or epoxy resin mixtures with anhydrides in particular are used as hardeners.
- anhydrides as hardeners, in particular phthalic anhydrides, or and/or phthalic anhydride derivatives, only anhydride-free, in particular phthalic anhydride or Phthalic anhydride derivative-free impregnating agent used.
- WO2016/124387 discloses an insulation system based on an epoxy resin with an anhydride-free impregnating agent that can be homopolymerized.
- a reactive corona protection band comprises an electrically conductive and/or semi- or partially conductive material applied to a flexible carrier such as film, fleece and/or fabric, which is referred to here as "carrier tape", which is connected to the carrier tape with one another and is optionally connected to a final cover layer and/or a further layer by means of a tape adhesive which represents the polymer matrix and/or comprises the polymer matrix.
- an electrically conductive and / or semi- or partially conductive material z.
- the mentioned electrically conductive and/or semi- or partially conductive materials such as doped titanium oxide and/or tin oxide and/or silicon carbide doped with and without aluminum can also be used without a substrate, such as mica Filler present.
- the tape that is used to produce the external corona protection winding comprises at least one binder, usually a polymer and a mixture of planar and/or globular and/or tubular electrically conductive and/or partially conductive fillers, which optionally have a u. U. have doped coating.
- the polymeric matrix comprises several polyvinyl alcohols.
- polyvinyl alcohols according to the invention can be used as the polymer matrix or part of the polymer matrix of the corona shielding strip, but some particularly suitable polyvinyl alcohols, which can be used alone or in combination, are mentioned below, for example.
- polyvinyl alcohol cannot be produced by simply polymerizing the corresponding monomer.
- the necessary monomer ethenol only exists in its tautomeric form as acetaldehyde.
- Polyvinyl alcohols are obtained by transesterification and/or alkaline saponification of polyvinyl acetate. The hydrolysis is easily controllable.
- Suitable polyvinyl alcohols have, for example, a degree of hydrolysis of more than 70 mol%.
- few or more hydroxyl groups are substituted by silicon-containing compounds.
- the polymeric matrix in the strip comprises polyvinyl alcohol with cross-linked portions. To what degree?
- the polymeric matrix in the tape comprises one or more polyvinyl alcohol(s) modified with an aldehyde and/or crosslinked with melamine.
- the polymeric matrix comprises at least one polymeric binder which is a polyvinyl alcohol which has a degree of hydrolysis of at least 70 mol%, in particular at least 85 mol% and preferably at least 87 mol% or more.
- the polymeric matrix comprises at least one polyvinyl alcohol in which the hydroxyl groups of the polyvinyl alcohol are at least partially substituted by siloxane and/or silanol groups.
- Investigation methods such as IR, UV, and/or VIS spectroscopic methods and/or scanning electronic investigation methods, including X-ray spectroscopy, for example, are used to detect the components of a corona protective strip according to one embodiment of the invention, in particular also in a finished insulation system EDX, suitable .
- the electrically conductive filler mainly comprises carbon Lenstoff-based components such as a carbon modification material - preferably carbon black, graphite and / or carbon nanotubes.
- the electrically conductive filler comprises a silicon carbide, undoped and/or doped silicon carbide.
- the electrically conductive filler comprises particles which are at least partly made of metal oxide, in particular a mixed oxide.
- a compound between a metal and oxygen is referred to as a metal oxide
- the oxygen in the compound formally, ie in simplified terms, having a 2-fold negative charge.
- the oxygen in the compound is the electronegative partner. Hence the name "oxide”.
- a mixed oxide - MOX for short - is accordingly a substance in which more than one metal cation is present in an oxidic compound, for example titanium-aluminum oxide or iron-nickel oxide or the like.
- a filler which has a coating of a doped tin oxide and/or a doped titanium oxide and/or consists of a doped tin oxide and/or titanium oxide.
- the filler particles can be in the form of hollow bodies, solid particles, coated particles and/or core-shell particles.
- At least one fraction, preferably but not necessarily exclusively, of platelet-shaped particles is applied to the carrier tape, which are held together by a polymer matrix, i.e. the binder, and thus the glow form a protective band.
- a polymer matrix i.e. the binder
- the corona protection strip has a basis weight of ⁇ 150 g/m 2 , preferably less than 100 g/m 2 .
- the carrier tape comprises reinforcing fibers, for example in the form of a fabric and/or a fiber composite, in and/or on which the polymeric matrix with the electrically conductive filler is introduced and/or with which it is connected through the binder is bonded.
- the carrier tape preferably has a basis weight of 30-60 g/m 2 .
- These reinforcing fibers are, for example, glass fibers and/or polyethylene terephthalate - PET fibers.
- the carrier tape is coated with a primer. It is particularly advantageous if the carrier tape is coated with a primer of up to 5 g/m 2 .
- the priming of the carrier tape comprises polyvinyl alcohol, epoxy and/or amine functionalities.
- priming refers to a priming coating through which the cut resistance of the reinforcing fibers and/or the carrier tape or fabric is improved and prepared for wetting and bonding with the polymeric matrix.
- the amount of coating of the carrier tape with the polymeric matrix, which contains the at least one fraction of electrically conductive filler and/or possibly also the at least one tape accelerator is in the range from 20 g/m 2 to 100 g/m 2 , in particular in the range from 20 g/m 2 to 60 g/m 2 , particularly preferably in the range from 30 g/m 2 to 45 g/m 2 .
- the corona protection strip is used to produce an external corona protection system and/or an internal potential control system and/or an end corona protection system.
- an external corona protection system produced by a corona protection strip according to the present invention and/or an internal potential control system is in the range from 0.01 kOhm to 100 kOhm, measured at a field strength of 1 V /mm lies .
- the square and/or sheet resistance values of such an internal potential control are preferably in the range from 0.01 kOhm to 10 kOhm, preferably in the range from 0.01 to 5 kOhm and particularly preferably in the range from 0.05 to 1 kOhm and/or or the square resistance values of such external corona protection in the range from 0.1 to 100 kOhm, in particular from 0.1 kOhm to 50 kOhm and particularly preferably in the range from 1 kOhm to 10 kOhm, each measured at a field strength of 1 V/mm.
- the invention relates to a corona protection strip for an electrical high-voltage machine with anhydride-free, in particular Epoxy resins free of phthalic anhydride derivatives.
- the corona protection tape presented here for the first time is adjusted with its components, in particular the connecting polymeric matrix and the embedded cationic tape accelerator, to the new epoxy resin-based VPI impregnation resins, which are also free of alkyl phthalic anhydride derivatives, for example.
- the belt accelerator is preferably an ionic compound composed of one or more sulfonium-containing cation(s) with one or more anions, in particular complex anions, such as hexafluoroantimonate anion(s), each suitable for use in a VPI Process for manufacturing an insulation system with an anhydride-free impregnating agent. .
- the belt accelerator is a cationic belt accelerator and is therefore preferably constructed ionogenically.
- the ribbon accelerator has a sulfonium-containing cation.
- a suitable cationic belt accelerator is a chemical compound that falls under one of structural formulas I, II, or III:
- Di-alkyl-aryl-sulfonium cation Di-alkyl-aryl-sulfonium cation
- the sulfonium cations I, II and III shown here form with complex anions such as BF 4 -, PF 6 -, SbF 6 -, AsF 6 -, SbF 5 (OH)-, ASF 5 (OH)Al[OC(CF 3 ) 3 ] 4 - the corresponding superacid salts useful herein as line accelerators.
- Superacids are acids that are stronger than concentrated 100% sulfuric acid with a pKa value of -3. Examples are fluorosulfonic acid, fluoroantimonic acid, per-halogenated carboranes, and others.
- a “cationic belt accelerator” is a belt accelerator which is ionic and whose cation initiates the cationic polymerization, in particular the cationic homopolymerization, of an impregnating resin in a liquid impregnating agent.
- “Ionogenic” compounds are heteropolar compounds whose chemical reactivity is characterized by the presence of a cation and an anion in the compound.
- Classic "ionogenic” compounds are salts. ze .
- complex structures with a cationic and anionic character are also referred to here as “ionogenic” compounds.
- a “sulfonium-containing cation” is a cation which, in addition to the anion or anions, includes a unit in the molecule which can be described by the simply positively charged structures II or III or by the molecular formula [SR 3 ] + .
- alkyl-aryl-sulfonium or “di-alkyl-aryl-sulfonium” in which one or two of the three radicals “R” on the sulfur atom in the sulfonium cation are alkyl groups
- alkyl groups are parts of a molecule consisting of carbon and hydrogen atoms bonded to one another.
- preferred alkyl radicals are those having 1 to 12 carbon atoms, which can be branched or linear thereby monovalently bonded to the central sulfur atom.
- a di-alkyl-aryl-sulfonium cation can have one or two alkyl radicals, which in turn can be identical or different.
- a sulfonium-containing cation in which one or two of the three radicals “R” on the sulfur atom in the sulfonium cation are aryl groups is referred to as “aryl-alkyl-sulfonium or di-aryl-alkyl-sulfonium”.
- Aryl groups are parts of a molecule that are monovalent or are attached by a single bond to the carbon skeleton, or to the sulfur atom, and have at least one aromatic nucleus, which can be partially or fully substituted or unsubstituted.
- an aryl-alkyl-sulfonium cation can have one or two aryl radicals, which in turn can be identical or different.
- the third radical can be anything, ie also an alkyl group or an aryl group, fully or partially substituted or not.
- aryl group is an organic chemical radical with an aromatic backbone. It is the designation for a monovalent atomic group derived from aromatic hydrocarbons by removing a hydrogen atom attached to the ring. Most aryl groups are derived from benzene, the simplest aryl group being the phenyl group.
- At least one aryl group is present in the sulfonium cation.
- At least one mononuclear aryl group for example an aryl group with an aryl structure derived from benzene, such as phenyl or benzyl, is present.
- the functional group can be present with or without a heteroatom such as oxygen, nitrogen, sulfur or phosphorus.
- An aryl group in which a hydrogen on the aromatic nucleus is replaced by an acetyloxy group is particularly preferred.
- a sulfonium-containing cation combined with a hexafluoroantimonate anion is present as the belt accelerator.
- the corona protection belt accelerator can be a mixture of at least two cationic belt accelerators, each of which has a different have res sulfonium cation, are present.
- the anions can be the same or different, in particular as an anion hexafluoro-antimonate.
- the corona protection strip accelerator regardless of whether it is present as an individual compound or as a mixture, preferably has a melting point in the range from 145.degree. C. to 165.degree. C., particularly preferably in the range from 150.degree. C. to 160.degree.
- the invention also relates to the use of the reactive corona protection tape for producing an anhydride-free insulation system by impregnating the solid corona protection tape with an impregnation agent, the impregnation agent comprising an aromatic and/or cycloaliphatic impregnation resin, the anhydride - is free and contains epoxy groups.
- Anions with a complex structure such as the hexafluoro-antimonate anion, are particularly suitable as the anions of the cationic belt accelerator, so that, for example, the 4-acetyloxyphenyldimethylsulphonium hexafluoroantimonate - CAS no. 135691-31-5 - Structure I .
- this novel corona protection tape is suitable for curing conventional epoxy resin-phthalic anhydride mixtures as well as novel, i.e. anhydride-free, impregnating agents with epoxy resins, particularly in combination with cycloaliphatic epoxy resins.
- sulphonium superacid derivative(s) bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycidyl ester, aliphatic and/or cycloaliphatic epoxy resins can gel and cure alone, but also in any combination.
- Successful tests have already been carried out with cycloaliphatic epoxy resins mixed with BADGE (bisphenol A diglycidyl ether) .
- a shaping crosslinker can also be applied, but the tape also has sufficient stability for winding without a shaping crosslinker.
- corona protection tape produced in this way via subsequent hot-air drying shows, with heat impregnation according to the invention at 70° C. and subsequent hot curing at 140° C. with anhydride-free epoxy resin or an advantageous mixture of approx. 80 wt. -% cycloaliphatic epoxy resin and approx. 20 wt.
- This turquoise shimmering paint suspension was then applied to a 200 mm wide glass/polyester blended fabric with a basis weight of 44.7 g/m 2 (Krempel GmbH, Vaihingen/Enz) by means of dip application in a base coater belt impregnation system (COATEMA Coating Machinery GmbH, Dormagen) and dried at a strip surface temperature of around 120°C in a hot-air fan oven vertically with a strip running at 0.8 meters/minute over a length of 1.5 m.
- a base coater belt impregnation system COATEMA Coating Machinery GmbH, Dormagen
- the result on the belt was a total dry application of 27.48 g/m 2 , with 0.77 g/m 2 of 4-acetyloxyphenyl dimethyl sulfonium hexafluoroantimonate as an accelerator substance, 22.56 g/m 2 of Iriotec 7320 as a partially conductive material for field control and 4.16 g/m 2 PovalTM 25-98 R as a binder.
- the tape had a specific total area weight of approx. 72 g/m 2 .
- the glow strip strips were then placed in the center by weights under tension, transferred to a convection oven and immersed completely for four hours in a phthalic anhydride-free epoxy resin mixture at 70° C., consisting of 80% by weight of cycloaliphatic epoxy resin of the 3,4- Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (CelloxideTM C2021P, Daicel Corporation, Tokyo; CAS No. 2386-87-0) and 20% by weight distilled bisphenol A diglycidyl ether (EpikoteTM Resin 162 , Hexion GmbH, Iserlohn; CAS No. 1675-54-3) , immersed.
- a phthalic anhydride-free epoxy resin mixture consisting of 80% by weight of cycloaliphatic epoxy resin of the 3,4- Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (CelloxideTM
- the electrically contacted corona protective tape strips were lifted out of the resin, heat-cured in the oven at 145 °C for ten hours and then cooled to room temperature. During this time the electrical resistance was continuously recorded.
- the ideal resistance characteristics of the novel corona protection tape in the range of 1-10 kOhm are retained in the full temperature range of 20-145 °C and is therefore ideally suited for deflecting electrical fields on windings in anhydride-free, VPI epoxy resin-impregnated electrical machines and generators.
- a so-called resin infection test or accelerator availability test was also carried out to check how the accelerator was washed out of the new corona protection tape.
- two corona protection tape strips measuring 2.5 cm x 4.8 cm (12 cm 2 ) were prepared and each 30 g of the abovementioned (alkyl) phthalic anhydride-free epoxy resin (80% by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate/ 20
- the stability of the novel corona protection tape could be demonstrated using fairly constant reaction enthalpies (approx. 300-400 joules per gram of epoxy resin mixture).
- the present invention discloses a corona protection strip for the first time, in which a well-suited strip accelerator that quickly initiates homopolymerization can be deposited.
- the tape accelerator is in the form of a salt of a superacid and is storage-stable for up to 6 months at a temperature of +6 °C to 23 °C in a corona protection tape that at least partially contains polyvinyl alcohol as the polymer matrix.
Abstract
The invention relates to a corona shielding strip, in particular a reactive corona shielding strip, for a high-voltage rotating electric machine, comprising an insulation system that can be produced by means of a vacuum pressure impregnation (VPI) process, wherein, owing to concerns about the sensitising effect of anhydrides on the respiratory tract, the impregnation agent for impregnating the corona shielding strip in the VPI process is preferably anhydride-free. Based on the new generation of insulation systems, which can be produced by impregnation with anhydride-free impregnation agents, the present invention discloses for the first time a corona shielding strip in which a strip accelerator that initiates homopolymerisation quickly can be placed. The strip accelerator is in the form of a salt of a superacid and is storage-stable for up to 6 months in a corona shielding strip that contains, at least in part, polyvinyl alcohol as a polymer matrix.
Description
Beschreibung description
Glimmschutzband für rotierende elektrische Hochspannungsma- schine, Verwendung dazu und elektrische Maschine Corona protection strip for rotating electrical high-voltage machine, use therefor and electrical machine
Die Erfindung betrifft ein Glimmschutzband, insbesondere ein reaktives Glimmschutzband, für eine rotierende elektrische Hochspannungsmaschine mit einem durch Vakuum-Druck- Imprägnier-Prozess (VPI-Prozess) herstellbaren Isolationssys- tem, wobei das Imprägniermittel im VPI-Prozess aus Bedenken gegenüber der atemwegssensibilisierenden Wirkung der Anhydri- de, bevorzugt Anhydrid-frei vorliegt . Außerdem betrifft die Erfindung die Verwendung eines derartigen Glimmschutzbandes sowie eine elektrische Maschine mit einem Isolationssystem, das durch die Verwendung des Glimmschutzbandes herstellbar ist . The invention relates to a corona protection band, in particular a reactive corona protection band, for a rotating electrical high-voltage machine with an insulation system that can be produced by vacuum pressure impregnation process (VPI process), the impregnation agent in the VPI process being used for concerns about the airway sensitizing effect of the Anhydrides de, preferably anhydride-free. The invention also relates to the use of such a corona protection strip and an electrical machine with an insulation system that can be produced using the corona protection strip.
Bei der Herstellung eines Isolationssystems kommen je nach Bemessungsspannung der rotierenden elektrischen Maschine ver- schiedene Kombinationen von Komponenten eines Isolationssys- tems zum Einsatz . Beispielsweise hat man bei Motoren mit un- gefähr größer 2kV Bemessungsspannung an der Nutaustrittsstel- le eine leitfähige Schicht zur Feldvergleichmäßigung, den Au- ßenglimmschutz, AGS . Ab einer ungefähren Bemessungsspannung von 6kV wird ein AGS in der Regel an den Enden durch einen Endenglimmschutz EGS verstärkt und ab einer Bemessungsspan- nung von ca . 12kV wird das Isolationssystem an der Hauptiso- lation noch durch eine Innenpotentialsteuerung IPS verstärkt . Depending on the rated voltage of the rotating electrical machine, different combinations of components of an insulation system are used when producing an insulation system . For example, in motors with a rated voltage of approximately more than 2kV, there is a conductive layer at the slot exit point to equalize the field, the external corona protection, AGS. From an approximate rated voltage of 6kV, an AGS is usually reinforced at the ends by end corona protection EGS and from a rated voltage of approx . 12kV, the insulation system on the main insulation is reinforced by an IPS internal potential control.
Wegen physiologischer Bedenken gegenüber dem bislang üblichen Einsatz von Anhydrid-haltigen Vernetzern in den Imprägnier- mitteln des Isolationssystems, insbesondere der durch VPI herstellbaren Isolationssysteme, wird das Anhydrid verstärkt durch Anhydrid- freie Imprägniermittel ersetzt . Diese Substi- tution zieht eine ganze Reihe von Anpassungsproblemen nach sich, da die Wickelbänder und/oder Glimmschutzbänder, die ih- rerseits organische Bindemittel, wie den Bandkleber, polymer- basierte Matrixmaterialien und eben im Fall reaktiver Glimm-
schutzbänder auch Härtungskatalysatoren umfassen, auf die neu eingesetzten Anhydrid- freien Imprägniermittel abzustimmen sind. Because of physiological concerns about the hitherto customary use of anhydride-containing crosslinkers in the impregnating agents of the insulation system, in particular the insulation systems that can be produced by VPI, the anhydride is increasingly being replaced by anhydride-free impregnating agents. This substitution entails a whole range of adjustment problems, since the winding tapes and/or corona protection tapes, which in turn contain organic binders such as the tape adhesive, polymer-based matrix materials and, in the case of reactive corona protective tapes also include curing catalysts, to which the newly used anhydride-free impregnating agents must be matched.
Bislang gibt es keine Formulierung für ein Isolationssystem mit AGS, EGS und/oder IPS, das ein Glimmschutzband, seiner- seits etliche empfindliche Komponenten wie den Bandkleber, die Polymermatrix, die Füllstoffe, deren Beschichtungen und ein Anhydrid-freies Imprägniermittel umfasst, welche in einem gängigen VPI-Prozess zu einem brauchbaren Isolationssystem zu verarbeiten ist . So far, there has been no formulation for an insulation system with AGS, EGS and/or IPS that includes a corona protection tape, a number of sensitive components such as the tape adhesive, the polymer matrix, the fillers, their coatings and an anhydride-free impregnating agent, which in one common VPI process into a usable isolation system.
Die Leitschichten des IPS und des AGS bestehen in der Regel aus Ruß- und/oder Graphit-haltigem Verbundwerkstoff auf Basis einer polymeren Matrix . Keine Komponente des Verbundwerkstof- fes, weder der Ruß/Graphit, noch die polymere Matrix sind re- sistent gegenüber Teilentladungen. Trifft eine Teilentladung auf die Leitschicht, reagiert beispielsweise der Ruß mit dem umgebenden Sauerstoff zu CO2 ab . Gleiches gilt für die poly- mere Matrix . The conductive layers of the IPS and the AGS usually consist of a composite material containing carbon black and/or graphite and based on a polymer matrix. No component of the composite material, neither the carbon black/graphite nor the polymeric matrix are resistant to partial discharges. If a partial discharge hits the conductive layer, the soot reacts with the surrounding oxygen to form CO 2 . The same applies to the polymeric matrix.
Hauptisolation bzw. AGS, EGS und IPS werden in der Regel durch Wicklung von Glimmerband oder Glimmschutzband, das mit einem Imprägniermittel imprägniert wird, gebildet . Dabei um- fasst das Glimmerband der Hauptisolation in der Regel einen Barrierewerkstoff, wie Glimmer zur Isolation, während das Glimmschutzband elektrisch leitfähige oder teilleitfähige Füllstoffe, wie Ruß etc . umfasst . Bei Global-VPI im Gegensatz zu Single-VPI werden IPS, AGS und/oder EGS in der Regel als Bänder appliziert, bevorzugt an noch nicht imprägnierten Spu- len/Stäben und nachfolgend - besonders bevorzugt - in einem Imprägnierverfahren mit Imprägniermittel imprägniert . Main insulation or AGS, EGS and IPS are usually formed by winding mica tape or corona protection tape, which is impregnated with an impregnating agent. The mica tape of the main insulation usually includes a barrier material, such as mica for insulation, while the corona protection tape contains electrically conductive or partially conductive fillers, such as carbon black, etc. includes . In the case of Global-VPI, in contrast to Single-VPI, IPS, AGS and/or EGS are generally applied as tapes, preferably to coils/rods that have not yet been impregnated and subsequently—particularly preferably—impregnated in an impregnation process with an impregnating agent.
Insbesondere die bislang üblichen, für Anhydrid-haltige Im- prägniermittel bestens geeigneten tertiären Amine und/oder organischen Zinksalze können als sogenannte Bandbeschleuniger für die neuen, Anhydrid-freien Imprägniermittel nicht mehr eingesetzt werden, weil diese damit unter den Bedingungen des
VPI-Prozesses nur unzureichend vernetzen . Dies resultiert letztlich in unausgehärteten, weichen Bereichen in Teilen des AGS , EGS , IPS und/oder der Hauptisolierung und/oder zu Poly- merisaten mit niedriger Glasübergangstemperatur . Eine niedri- ge Glasübergangstemperatur ist auch lokal zu vermeiden, da diese Bereiche mechanisch und elektrisch ungenügende Eigen- schaften aufweisen und zu deutlich verfrühter Degradation führen . Im Betrieb werden diese gering belastbaren Bereiche thermisch und elektrisch rasch degradiert oder zerstört . In particular, the tertiary amines and/or organic zinc salts that have been customary up to now and are ideally suited for anhydride-containing impregnating agents can no longer be used as so-called belt accelerators for the new, anhydride-free impregnating agents because they can no longer be used under the conditions of the Inadequate networking of the VPI process. This ultimately results in uncured, soft areas in parts of the AGS, EGS, IPS and/or main insulation and/or to polymers with low glass transition temperature. A low glass transition temperature should also be avoided locally, since these areas have insufficient mechanical and electrical properties and lead to significantly premature degradation. During operation, these low-load areas are quickly thermally and electrically degraded or destroyed.
Glimmschutzbänder als Teil des Isolationssystems werden bei rotierenden elektrischen Hochspannungsmaschinen eingesetzt . Rotierende Hochspannungsmaschinen sind beispielsweise Motoren oder auch Generatoren in einem Kraftwerk zur Erzeugung elektrischer Energie . Derartige rotierende Hochspannungsma- schinen weisen insbesondere eine Ständerwicklung auf , an die eine besonders hohe Anforderung bezüglich Festigkeit und Zu- verlässigkeit gestellt ist . Insbesondere ist das Isolations- system der Ständerwicklung an der Grenz fläche zwischen der Hauptisolierung und dem Blechpaket , insbesondere bei rotie- renden elektrischen Maschinen ab ca . 2 kV Bemessungsspannung, der Ständerwicklung durch eine hohe thermische , thermomecha- nische , dynamische und elektromechanische Betriebsbeanspru- chung stark belastet , wodurch das Risiko einer Beschädigung des Isolationssystems der Ständerwicklung durch Teilentladung hoch ist . Corona protection tapes as part of the insulation system are used in rotating electrical high-voltage machines. Rotating high-voltage machines are, for example, motors or generators in a power plant for generating electrical energy. Such rotating high-voltage machines have, in particular, a stator winding which is subject to particularly high demands in terms of strength and reliability. In particular, the insulation system of the stator winding at the interface between the main insulation and the laminated core, especially in rotating electrical machines from approx. 2 kV rated voltage, the stator winding is heavily loaded by high thermal, thermomechanical, dynamic and electromechanical operating stress, which means that the risk of damage to the insulation system of the stator winding due to partial discharge is high.
Die Ständerwicklung weist einen mit der Hauptisolierung elektrisch isolierten Leiterverbund auf , der in einer Nut ge- lagert ist , die in dem Blechpaket angeordnet ist . Beim Be- trieb der rotierenden elektrischen Maschine ist der Ständer einer thermischen Wechselbeanspruchung ausgesetzt , wodurch, hervorgerufen durch unterschiedliche Wärmeausdehnungsge- schwindigkeiten und Wärmeleitfähigkeiten des Leiters , der Hauptisolierung und dem Blechpaket , mechanische Spannungen in der Hauptisolierung erzeugt werden . Dadurch bedingt kann ein örtlich begrenztes Ablösen der Hauptisolierung auftreten, wodurch Hohlräume zwischen der Hauptisolierung und dem Blech-
paket entstehen, in denen Teilentladungen zünden können . Die Teilentladungen können zu einer Beschädigung der Hauptisolie- rung führen, was im schlimmsten Fall zu einem Erdschluss zwi- schen Blechpaket und Leiter führen kann, wodurch die Maschine nicht mehr betreibbar ist . An den Nutaustritten steht her- kömmlich der Leiter mit seiner Hauptisolierung vor, dort ist die Grenz fläche zwischen dem Leiter und der Hauptisolierung angeordnet , die eine Gleitanordnung bildet . Dies ist bei- spielsweise aus der Figur 1 der EP 2362399B1 ersichtlich, wo- bei der Ausschnitt des dort abgebildeten Turbogeneratorstän- ders der hier behandelten Nut-Austrittsstelle schematisch entspricht . The stator winding has a conductor assembly that is electrically insulated from the main insulation and that is mounted in a slot that is arranged in the laminated core. When the rotating electrical machine is in operation, the stator is exposed to alternating thermal stress, as a result of which mechanical stresses are generated in the main insulation, caused by different thermal expansion rates and thermal conductivities of the conductor, the main insulation and the laminated core. As a result, localized detachment of the main insulation can occur, creating cavities between the main insulation and the sheet metal packets arise in which partial discharges can ignite. The partial discharges can lead to damage to the main insulation, which in the worst case can lead to an earth fault between the laminated core and the conductor, which means that the machine can no longer be operated . The conductor with its main insulation conventionally protrudes at the slot exits, where the interface between the conductor and the main insulation is arranged, which forms a sliding arrangement. This can be seen, for example, in FIG. 1 of EP 2362399B1, in which the section of the turbogenerator stand shown there corresponds schematically to the slot exit point dealt with here.
Die Hauptisolierung der Wicklung gegen das Blechpaket ist ein elektrisch hoch beanspruchtes System . Im Betrieb entstehen hohe Spannungen, welche in dem Isoliervolumen zwischen dem Leiterstab und dem auf Erdpotential liegendem Blechpaket ab- zubauen sind . An den Kanten der Bleche im Blechpaket entste- hen Feldüberhöhungen, die ihrerseits Teilentladungen hervor- rufen und schließlich zu einer vorzeitigen Alterung und im schlimmsten Fall zu einer Zerstörung der Isolierung führen . The main insulation of the winding against the laminated core is an electrically highly stressed system. During operation, high voltages arise, which must be dissipated in the insulating volume between the conductor bar and the laminated core, which is at ground potential. Field increases occur at the edges of the sheets in the laminated core, which in turn cause partial discharges and ultimately lead to premature aging and, in the worst case, to destruction of the insulation.
Die Austrittsstelle der Ständerstäbe/-spulenschenkel aus dem Blechpaket , die Nutaustrittsstelle , ist charakterisiert durch das Aufeinandertreffen zweier Isolierstoffe , dem gasförmigen und dem festen, und dem AGS und/oder IPS oder dem Blechpaket . In diesem Bereich bildet sich eine Grenzschicht zwischen der im Aggregat zustand festen Hauptisolierung und einem gasförmi- gen Medium, meist Luft oder Wasserstoff, aus . Durch die re- sultierende dielektrische Trennfläche zwischen der Hauptiso- lierung und der Luft entsteht eine klassische Gleitanordnung, die neben einer rein radialen Feldkomponente Erad, die senk- recht auf den Leiter steht und die im Bereich des Blechpakets vorkommt , zusätzlich eine tangentiale Feldkomponente Etan, die entlang des Leiters nach AGS-Ende entsteht , hat . Die dadurch tangential beanspruchten Grenz flächen, beispielsweise Haup- tisolierung zu Luft , stellen besondere Schwachstellen in ei- ner Isolieranordnung dar .
Aufgrund der geringen elektrischen Festigkeit der Luft kann es schon bei vergleichsweise geringen Spannungen in diesem Bereich des Triplepunktes „Blechpaket-Isolationssystem-Luft" , am Ende des Außenglimmschutzes „AGS" , zu Teilentladungen, be- dingt durch die lokale tangentiale Feldstärkenerhöhung von ca . 0 , 5kV/mm bei sauberer Oberfläche , kommen, die sich bei weiterer Steigerung der Spannung zu Gleitentladungen entlang der Isolierstoffoberfläche bis zu einem elektrischen Durch- schlag, der durch einen Leiter-Erde-Kurzschluss charakteri- siert ist , ausweiten können . The exit point of the stator bars/coil legs from the laminated core, the slot exit point, is characterized by the meeting of two insulating materials, the gaseous and the solid, and the AGS and/or IPS or the laminated core. In this area, a boundary layer forms between the main insulation, which is solid in its aggregate state, and a gaseous medium, usually air or hydrogen . The resulting dielectric interface between the main insulation and the air creates a classic slip arrangement which, in addition to a purely radial field component E rad , which is perpendicular to the conductor and which occurs in the area of the laminated core, also has a tangential field component E tan arising along the conductor after AGS end has . The interfaces that are tangentially stressed as a result, for example between the main insulation and the air, represent particular weak points in an insulation arrangement. Due to the low electrical strength of the air, partial discharges can occur even with comparatively low voltages in this area of the triple point "laminated core insulation system-air" at the end of the external corona protection "AGS", caused by the local tangential field strength increase of approx. 0.5kV/mm with a clean surface, which can expand as the voltage increases to form creeping discharges along the insulating material surface up to an electrical breakdown, which is characterized by a conductor-earth short circuit.
Um diese elektrischen Gleitentladungen zu unterdrücken, wird bei elektrischen rotierenden Maschinen zusätzlich zum Außen- glimmschutz „AGS" ab einer Bemessungsspannung von 6kV eine resistiv-kapazitive Feldsteuerung, in Form eines Endenglimm- schutzes „EGS" , an den AGS angebunden . Bei der Berechnung und Auslegung eines Endenglimmschutzes ist zu beachten, dass die höchste elektro-thermische Belastung des Systems nicht bei Betriebsspannung, sondern vielmehr bei der Kontrolle des I so- liersystems mit erhöhter Prüfspannung erfolgt . Durch Bildung von Gleitentladungen an der Oberfläche wird der Isolierstoff langfristig zerstört . Der Endenglimmschutz ist , genauso wie der Außenglimmschutz , eine resistive Beschichtung direkt auf der Oberfläche der Hauptisolation . Im Gegensatz zum „AGS" , dem Außenglimmschutz , der einen Oberflächenwiderstand von et- wa 1000 - 10 . 000 Ohm hat , zeigt der „EGS" , der Endenglimm- schutz einen deutlich höheren elektrischen Oberflächenwider- stand, der nichtlinear ausgestaltet ist und bei einer Feld- stärke von 100V/mm bei etwa 5 x 109 Ohm liegt . Ganz generell kann der relevante Widerstandsbereich des EGS mit 2x108 Ohm bis 1x1013 Ohm angegeben werden . In order to suppress these electrical creeping discharges, a resistive-capacitive field control in the form of an end corona protection "EGS" is connected to the AGS in addition to the external corona protection "AGS" for electrical rotating machines from a rated voltage of 6kV. When calculating and designing an end corona protection, it must be noted that the highest electro-thermal load on the system does not occur at the operating voltage, but rather when the insulation system is checked with an increased test voltage . The insulating material is destroyed in the long term by the formation of creeping discharges on the surface. Like the external corona protection, the end corona protection is a resistive coating directly on the surface of the main insulation. In contrast to the "AGS", the external corona protection, which has a surface resistance of around 1000 - 10,000 ohms, the "EGS", the end corona protection, has a significantly higher electrical surface resistance, which is non-linear and has a field strength of 100V/mm is around 5 x 10 9 ohms. In general, the relevant resistance range of the EGS can be specified as 2x10 8 ohms to 1x10 13 ohms.
Insbesondere kann es durch Erwärmung, elektrische Erosion und chemische Degradation zur Zerstörung des EGS kommen und damit zu einer Beschädigung des Isolationssystems und schließlich zum Überschlag als Folge der Zerstörung des Endenglimmschut- zes kommen . Durch lokale Wärmeentwicklung kann es aufgrund
einer Arbeitspunktverschiebung zusätzlich zur Störung der Funktionsweise des Isoliersystems und zu einem Ansteigen der dielektrischen Verluste kommen . In particular, heating, electrical erosion and chemical degradation can destroy the EGS and thus damage the insulation system and ultimately flashover as a result of the destruction of the end corona protection. It can be due to local heat development an operating point shift in addition to disrupting the functioning of the insulation system and increasing the dielectric losses.
Der AGS hat einen gewissen Quadratwiderstand, der einen be- stimmten unteren und oberen Grenzwert nicht unter- respektive überschreiten darf . Bei Unterschreitung des Grenzwertes kön- nen hohe induzierte Kreisströme , welche sich über die Enden des Blechpakets und dem Außenglimmschutz schließen, zu strom- starken Lichtbögen zwischen zwei Blechen im Blechpaket füh- ren, dadurch gibt es hohe elektrische Verluste . Bei zu hohem Widerstand kann es wiederum zu Hochspannungsfunkenerosion kommen, wobei dann der AGS nicht mehr wie eine Feldvergleich- mäßigung, sondern wie eine Isolation wirkt . Idealerweise hat ein Außenglimmschutz eine ausgeprägte Anisotropie im Wider- standsverhalten, der Widerstand in tangentialer, also axialer Richtung sollte hoch und in radialer Richtung gering sein . The AGS has a certain square resistance, which must not fall below or exceed a specific lower and upper limit. If the limit value is not reached, high circulating currents induced, which close via the ends of the laminated core and the external corona protection, can lead to high-current arcs between two laminated cores in the laminated core, resulting in high electrical losses . If the resistance is too high, high-voltage spark erosion can occur, in which case the AGS no longer acts like a field equalization, but like an insulation. Ideally, external corona protection has a pronounced anisotropy in the resistance behavior; the resistance in the tangential, i.e. axial, direction should be high and in the radial direction low.
In der Praxis ist diese gewünschte Eigenschaft des AGS aber nicht realisierbar, so dass bislang der AGS in tangentialer Richtung stets niederohmiger ist als in radialer Richtung . Diese Phänomene sind auch in einschlägiger Fachliteratur nachzulesen, beispielsweise in „Hochspannungstechnik" von A. Küchler, Springer Verlag, Vol 15 , 2009 ISBN 3-540-78412- 8 und „Design Dependent Slot Discharge and Vibration Sparking on High Voltage Windings" von M . Liese und M . Brown, IEEE Trans DIE , August 2008 , pp 927- 932 . In practice, however, this desired property of the AGS cannot be realized, so that hitherto the AGS has always had lower resistance in the tangential direction than in the radial direction. These phenomena can also be read in relevant specialist literature, for example in "High Voltage Technology" by A. Küchler, Springer Verlag, Vol 15, 2009 ISBN 3-540-78412-8 and "Design Dependent Slot Discharge and Vibration Sparking on High Voltage Windings" by M . Liese and M. Brown, IEEE Trans DIE, August 2008, pp 927-932.
Aufgabe der vorliegenden Erfindung ist es daher, ein Glimm- schutzband zur Weiterverarbeitung im VPI-Verfahren bereitzu- stellen, ein Trägerband, zumindest einen Band-beschleuniger für das Imprägnierharz und zumindest ein polymeres Matrixma- terial mit einem elektrisch leitfähigen, gegebenenfalls be- schichteten Füllstoff umfassend, wobei der in dem Glimm- schutzband enthaltene Bandbeschleuniger geeignet ist , auf ein Anhydrid- freies Imprägniermittel , insbesondere auf Epoxid- harzbasis , im VPI-Prozess härtungsbeschleunigend zu wirken .
Die Lösung dieser Aufgabe wird durch den Gegenstand der vor- liegenden Erfindung, wie er in der Beschreibung, den Ansprü- chen und den Figuren offenbart ist , bereitgestellt . The object of the present invention is therefore to provide a corona protection strip for further processing in the VPI process, a carrier strip, at least one strip accelerator for the impregnating resin and at least one polymeric matrix material with an electrically conductive, optionally coated filler comprehensive, wherein the belt accelerator contained in the corona protection belt is suitable for curing-accelerating an anhydride-free impregnating agent, in particular based on epoxy resin, in the VPI process. The solution to this problem is provided by the subject matter of the present invention, as disclosed in the description, the claims and the figures.
Dementsprechend ist Gegenstand der vorliegenden Erfindung ein Glimmschutzband für die Weiterverarbeitung zu einem Isolati- onssystem mit Wicklung und Potentialsteuerung durch Außen- glimmschutz und/oder Innenpotentialsteuerung und/oder En- denglimmschutz , das Isolationssystem durch Imprägnieren der Wicklung mit einem Anhydrid- freien und Harz-basierten Impräg- niermittel bei 45 ° C bis 85 ° C und unter Vakuum, beispielsweise mittels VPI- Imprägnierung, herstellbar, wobei das Glimm- schutzband zumindest ein Trägerband einen elektrisch leitfä- higem oder teilleitfähigem Füllstoff in einer Polymermatrix und zumindest einen Band-Beschleuniger geeignet zur Härtung und/oder Gelierung des Imprägniermittels umfasst , dadurch ge- kennzeichnet , dass die Polymermatrix zumindest einen Polyvi- nylalkohol und/oder ein Polyvinylalkohol-Copolymerisat ent- hält und dass der zumindest eine Band-Beschleuniger ausge- wählt ist aus der Gruppe der Supersäuresal ze , wobei er zur Beschleunigung einer kationischen Homopolymerisation des Harz-basierten Anhydrid-f reien Imprägniermittels geeignet ist . Accordingly, the subject of the present invention is a corona protection tape for further processing into an insulation system with winding and potential control through external corona protection and/or internal potential control and/or end corona protection, the insulation system by impregnating the winding with an anhydride-free and resin-based Impregnating agent at 45 ° C to 85 ° C and under vacuum, for example by means of VPI impregnation, can be produced, the corona protection tape at least one carrier tape an electrically conductive or partially conductive filler in a polymer matrix and at least one tape accelerator suitable for Hardening and/or gelling of the impregnating agent, characterized in that the polymer matrix contains at least one polyvinyl alcohol and/or a polyvinyl alcohol copolymer and that the at least one belt accelerator is selected from the group of super acid salts , using it to speed up a katio African homopolymerization of the resin-based anhydride-free impregnating agent is suitable.
Die Basis des Harz-basierten Imprägniermittels ist bevorzugt ein Epoxidharz , insbesondere auch eine Epoxidharzmischung, beispielsweise eine ein oder mehrere cycloaliphatische Epo- xidharze umfassende Epoxidharzmischung . In dieser Mischung kann beispielsweise auch Siloxan enthalten sein, so dass bei Aushärtung des Imprägniermittels ein Duromer mit -O-SiR2-O- Einheiten umfassendem Rückgrat erhalten wird . The basis of the resin-based impregnating agent is preferably an epoxy resin, in particular also an epoxy resin mixture, for example an epoxy resin mixture comprising one or more cycloaliphatic epoxy resins. This mixture can also contain siloxane, for example, so that when the impregnating agent cures, a duromer with a backbone comprising —O—SiR 2 —O— units is obtained.
Nach einer vorteilhaften Ausführungsform der Erfindung ist das Imprägniermittel ein insbesondere Phthalsäureanhydrid- respektive Phthalsäureanhydrid-Derivat- freies Harz oder eine Harzmischung auf Epoxidbasis , bevorzugt zumindest ein cyc- loaliphatisches Epoxidharz und ein Epoxidharz auf Bisphenol- A- und/oder Bisphenol-F-Diglycidylether- und/oder Epoxyno-
volak-Basis umfassend . Beispielsweise liegt eine Imprägnier- harzmischung auf der Basis von cycloaliphatischem Epoxidharz und Bisphenol-A-Diglycidylether im Mischungsverhältnis im Be- reich von 50 : 50 bis 90 : 10 , insbesondere im Mischungsverhält- nis von 80 : 20 (m/m) vor . According to an advantageous embodiment of the invention, the impregnating agent is in particular a phthalic anhydride or phthalic anhydride derivative-free resin or a resin mixture based on epoxy, preferably at least one cycloaliphatic epoxy resin and an epoxy resin based on bisphenol A and/or bisphenol F diglycidyl ether. and/or epoxy volak base comprehensive . For example, there is an impregnating resin mixture based on cycloaliphatic epoxy resin and bisphenol A diglycidyl ether in a mixing ratio in the range from 50:50 to 90:10, in particular in a mixing ratio of 80:20 (m/m).
Beispielsweise umfasst die Polymermatrix den Bandkleber und - zumindest teilweise - den darin gelösten und/oder feinst- verteilten Bandbeschleuniger, auch „Band-Katalysator" ge- nannt . Der Bandbeschleuniger dient zur Gelierung eines dünn- flüssigen Imprägnierharzes , das beispielsweise in einer Vaku- um-Druck- Imprägnierung (VPI ) auf das Glimmschutzband und die Hauptisolation der Ständerwicklung einwirkt . Dies passiert üblicherweise bei erhöhten Temperaturen, 45 ° C bis 85 ° C . Nach dem Imprägnieren werden die Ständerwicklungen im Statorblech- paket noch thermisch nach-gehärtet . For example, the polymer matrix includes the tape adhesive and - at least partially - the tape accelerator dissolved and/or finely distributed in it, also called "tape catalyst". -Pressure impregnation (VPI) acts on the corona protection strip and the main insulation of the stator winding.This usually happens at elevated temperatures, 45 °C to 85 °C.After impregnation, the stator windings in the stator core are thermally post-hardened.
Der zumindest eine Band-Beschleuniger liegt vorzugsweise in der polymeren Matrix mit den Füllstoffen vor . Während des Im- prägnierens vermischt sich dieser zumindest teilweise mit dem Imprägniermittel und/oder kann in das Imprägniermittel zumin- dest teilweise migrieren und dient so zur Gelierung des Im- prägniermittels vor dessen Aushärtung im nachfolgenden Tem- perschritt des Imprägnierverfahrens . The at least one belt accelerator is preferably present in the polymeric matrix with the fillers. During impregnation, this mixes at least partially with the impregnating agent and/or can at least partially migrate into the impregnating agent and thus serves to gel the impregnating agent before it hardens in the subsequent tempering step of the impregnating process.
Nach einer Ausführungsform der Erfindung liegt der Bandbe- schleuniger, der beispielsweise und vorzugsweise in Form ei- nes Supersäuren-Sal zes vorliegt , in der Polymermatrix, res- pektive dem Bandkleber, also zumindest einen Polyvinylalkohol umfassend, feinstverteilt und/oder gelöst vor . According to one embodiment of the invention, the tape accelerator, which is present for example and preferably in the form of a superacid salt, is present in the polymer matrix or the tape adhesive, ie comprising at least one polyvinyl alcohol, very finely distributed and/or dissolved.
Wegen der geforderten und erwünschten Lagerstabilität des Glimmschutzbandes ist es vorteilhaft , wenn die im Glimm- schutzband vorhandene Bandbeschleuniger in Form einer Super- säure und/oder eines Supersäuresal zes erst bei Kontakt mit dem Imprägniermittel und erhöhten Temperaturen von 45 ° C bis 85 ° C reagiert . Eine vorherige Reaktion mit der polymeren Mat- rix ist unerwünscht , weil der Bandbeschleuniger dann „aufge-
braucht" wäre und das Imprägniermittel nicht mehr anhärten, gelieren respektive aushärten könnte . Deshalb ist ein kriti- scher Punkt der vorliegenden Erfindung der, dass der Bandbe- schleuniger zwar in Form der extrem reaktiven Supersäure und/oder eines Derivats davon vorliegt , mit der Polymermatrix des Glimmschutzbandes aber unter Bedingungen bis zu 70 ° C nicht oder in nicht nennenswerter Menge reagiert . Because of the required and desired storage stability of the corona protection tape, it is advantageous if the tape accelerator present in the corona protection tape in the form of a super acid and/or a super acid salt only reacts on contact with the impregnating agent and at elevated temperatures of 45° C. to 85° C . A prior reaction with the polymeric matrix is undesirable because the belt accelerator is then “loaded”. would be needed" and the impregnating agent could no longer harden, gel or harden. Therefore, a critical point of the present invention is that the belt accelerator is in the form of the extremely reactive super acid and/or a derivative thereof, with the polymer matrix of the corona protection strip does not react or reacts to an insignificant extent under conditions of up to 70 °C.
Der Beschleuniger im Trägerband ist beispielsweise in einer Menge im Bereich von 0 , 1 g/m2 bis 15 g/m2 , insbesondere von 0 , 25 g/m2 bis 10 g/m2 , bevorzugt in einer Menge von 0 . 5 g/m2 bis 5 g/m2 enthalten . The accelerator in the carrier tape is, for example, in an amount in the range from 0.1 g/m 2 to 15 g/m 2 , in particular from 0.25 g/m 2 to 10 g/m 2 , preferably in an amount of 0. 5 g/m 2 to 5 g/m 2 included.
Dabei können die eingelagerten Band-Beschleuniger und Bandbe- schleunigerkonzentrationen in den Komponenten des Isolations- systems gleich oder ungleich sein . The embedded belt accelerators and belt accelerator concentrations in the components of the insulation system can be the same or different.
Die „Komponenten des Isolationssystems" die hier vor allem betroffen sind, sind beispielsweise The "components of the insulation system" that are primarily affected here are, for example
- die Wicklung der Hauptisolation - ohne leitfähige oder teilleitfähige Füllstoffe , da die Hauptisolation elektrisch isolierend ist , - the winding of the main insulation - without conductive or partially conductive fillers, since the main insulation is electrically insulating,
- die Wicklung der IPS , des AGS und/oder des EGS , die ab- gestufte elektrische Leitfähigkeit oder Teilleitfähig- keit haben, siehe oben . - the winding of the IPS , AGS and/or EGS , which have graded electrical conductivity or partial conductivity, see above .
Um Teilentladungen zu vermeiden, kann die Hauptisolierung von Wicklungsstäben /-Spulen mit einer inneren und einer äußeren Leitschicht gegen Hohlräume und Ablösungen abgeschirmt wer- den, eben durch Innenpotentialsteuerung IPS und AGS , wie oben erläutert . An den AGS anschließend kann ein EGS aufgebracht werden . In order to avoid partial discharges, the main insulation of winding bars/coils can be shielded against cavities and detachments with an inner and an outer conductive layer, precisely by means of internal potential control IPS and AGS, as explained above. An EGS can then be applied to the AGS.
Aus der EP 2362399 und aus der DE 19839285 Gl sind Glimm- schutzbänder bekannt , in denen ein planarer Füllstoff gebun- den in einer polymeren Matrix vorliegt . Der beschriebene planare Füllstoff besteht aus einem Glimmersubstrat , das mit
dotiertem Metalloxid, beispielsweise Titanoxid und/oder Zin- noxid, beschichtet ist . Dieser Füllstoff ist insbesondere re- sistenter gegenüber Teilentladungen als die Kohlenstoff- basierten Füllstoffe . Corona protection tapes are known from EP 2362399 and DE 19839285 G1, in which a planar filler is bound in a polymeric matrix. The planar filler described consists of a mica substrate with doped metal oxide, for example titanium oxide and/or tin oxide, is coated. In particular, this filler is more resistant to partial discharges than the carbon-based fillers.
Ganz grundsätzlich ist bei den mit planaren Füllstoffen ge- füllten polymeren Matrizen der elektrische Widerstand in Bandrichtung deutlich geringer als der senkrecht durchs Band, was wiederum die elektrische Leitfähigkeit in radialer Rich- tung vermindert . Durch Zugabe von runden Füllstoffen, bei de- nen als Substrat Quarzgut oder Quarzmehl dient , das wiederum ebenfalls mit dotiertem Metalloxid beschichtet wurde , kann der radiale Widerstand reduziert werden . In principle, the electrical resistance in the direction of the strip in the polymer matrices filled with planar fillers is significantly lower than that perpendicular through the strip, which in turn reduces the electrical conductivity in the radial direction. The radial resistance can be reduced by the addition of round fillers, in which quartz material or powdered quartz serves as the substrate, which in turn has also been coated with doped metal oxide.
Der elektrisch leitfähige und/oder teilleitfähige Füllstoff hat nach einer bevorzugten Ausführungsform zumindest eine Komponente , ausgewählt aus der Gruppe enthaltend Ruß , Gra- phit , Carbonnanotubes - CNTs- , Antimon dotiertes Zinnoxid, Siliziumkarbid und/oder Aluminium dotiertes Siliziumkarbid, wobei die jeweilige Komponente dotiert oder undotiert , be- schichtet oder unbeschichtet , dotiert beschichtet oder undo- tiert beschichtet vorliegen kann . According to a preferred embodiment, the electrically conductive and/or partially conductive filler has at least one component selected from the group consisting of carbon black, graphite, carbon nanotubes—CNTs—, antimony-doped tin oxide, silicon carbide and/or aluminum-doped silicon carbide, with the respective component being doped or undoped, coated or uncoated, doped coated or undoped coated.
Zur Reduzierung der Feldstärkenüberhöhung im Bereich des En- des des Außenglimmschutzes wird eine kapazitiv-resistive Feldsteuerung eingesetzt . Die kapazitive Steuerung wird durch die Hauptisolierung realisiert , während die resistive Steue- rung durch den Endenglimmschutz (EGS ) stattfindet . Hierbei handelt es sich um leitfähige Oberflächenbeläge , die einen quadratischen Widerstand von ca . 108 bis 1010 Ohm bei einer Feldstärke von 100 V/mm haben . Mit Hil fe der starken Nichtli- nearität des Widerstandes der eingesetzten Materialien im EGS wird versucht , das elektrische Feld aus den Bereichen hoher Feldstärken zu verdrängen . Dieses hat in der Verringerung des spezi fischen Widerstands mit steigender elektrischer Feld- stärke ihre Ursache .
Die ohmschen Oberflächenbeläge können entweder durch Anstri- che aus trocknenden und/oder härtbaren Harzen, welche unmit- telbar auf die Isolierstoffoberfläche aufgebracht werden und/oder zusammen mit der Herstellung der gewickelten Haup- tisolation, die aber dann schon vor der Herstellung respekti- ve der Imprägnierung der Hauptisolation als Bänder aufgewi- ckelt werden, entweder in Form eines Prepregs oder eines be- reits ausgehärteten, porösen Bandes , hergestellt werden . A capacitive-resistive field control is used to reduce the field strength increase in the area of the end of the external corona protection. The capacitive control is realized through the main insulation, while the resistive control takes place through the end corona protection (EGS). These are conductive surface coatings that have a square resistance of approx. 10 8 to 10 10 ohms at a field strength of 100 V/mm. With the help of the strong non-linearity of the resistance of the materials used in the EGS, an attempt is made to displace the electric field from the areas of high field strength. This is due to the reduction in specific resistance as the electrical field strength increases. The ohmic surface coatings can be applied either by painting from drying and/or hardenable resins, which are applied directly to the surface of the insulating material and/or together with the production of the wound main insulation, which is then applied before production or respectively Impregnation of the main insulation are wound up as tapes, either in the form of a prepreg or an already cured, porous tape.
Die Hauptisolierung der Wicklung wird dann mit einem Impräg- nierharz und beispielsweise durch einen damit ausgeführten Vakuum-Druck- Imprägnier-Prozess (VPI-Prozess ) imprägniert . Dabei kommen herkömmlich, also nach dem Stand der Technik, vor allem Epoxidharze und/oder Epoxidharz-Gemische mit Anhyd- riden als Härtern zum Einsatz . Wegen der atemwegssensibili- sierenden Wirkung und entsprechenden Bedenken gegen die un- eingeschränkte Verwendung Anhydriden als Härter, insbesondere von Phthalsäureanhydriden, respektive und/oder auch Phthal- säureanhydrid-Derivaten werden vorliegend nur Anhydrid- freie , insbesondere Phthalsäureanhydrid- bzw . Phthalsäureanhydrid- Derivat- freie Imprägniermittel eingesetzt . Aus der The main insulation of the winding is then impregnated with an impregnating resin and, for example, by means of a vacuum pressure impregnation process (VPI process) carried out therewith. Conventionally, that is to say according to the state of the art, epoxy resins and/or epoxy resin mixtures with anhydrides in particular are used as hardeners. Because of the sensitizing effect on the respiratory tract and corresponding concerns about the unrestricted use of anhydrides as hardeners, in particular phthalic anhydrides, or and/or phthalic anhydride derivatives, only anhydride-free, in particular phthalic anhydride or Phthalic anhydride derivative-free impregnating agent used. From the
WO2016/ 124387 ist beispielsweise ein Isoliersystem auf Basis eines Epoxidharzes mit einem Anhydrid- freien Imprägniermit- tel , das homopolymerisierbar ist , bekannt . For example, WO2016/124387 discloses an insulation system based on an epoxy resin with an anhydride-free impregnating agent that can be homopolymerized.
Ein reaktives Glimmschutzband umfasst dementsprechend auf ei- nem flexiblen Träger wie Folie , Vlies und/oder Gewebe , das hier als „Trägerband" bezeichnet wird, ein aufgebrachtes elektrisch leitfähiges und/oder halb- beziehungsweise teil- leitfähiges Material , das mit dem Trägerband, miteinander und gegebenenfalls mit einer abschließenden Decklage und/oder ei- nes weiteren Lage mittels eines Bandklebers , der die Polymer- matrix darstellt und/oder die Polymermatrix umfasst , verbun- den ist . Accordingly, a reactive corona protection band comprises an electrically conductive and/or semi- or partially conductive material applied to a flexible carrier such as film, fleece and/or fabric, which is referred to here as "carrier tape", which is connected to the carrier tape with one another and is optionally connected to a final cover layer and/or a further layer by means of a tape adhesive which represents the polymer matrix and/or comprises the polymer matrix.
Als elektrisch leitfähiges und/oder halb- beziehungsweise teilleitfähiges Material werden z . B . Füllstoffe auf Kohlen- stoffbasis und/oder keramisches , insbesondere Glimmer-
basiertes , Material mit teilleitfähiger, insbesondere durch Dotierung erzielter leitfähiger Beschichtung, beispielsweise aus Titanoxid und/oder Zinnoxid, und/oder mit und ohne Alumi- nium dotiertem Silizumkarbid bezeichnet . Andererseits können alternativ dazu oder ergänzend die genannten elektrisch leit- fähigen und/oder halb- beziehungsweise teilleitfähigen Mate- rialien wie dotiertes Titanoxid und/oder Zinnoxid, und/oder mit und ohne Aluminium dotiertes Silizumkarbid auch ohne Sub- strat - wie beispielsweise Glimmer - als Füllstoff vorliegen . As an electrically conductive and / or semi- or partially conductive material z. B. Carbon-based fillers and/or ceramic, in particular mica based material with a partially conductive coating, in particular a conductive coating obtained by doping, for example made of titanium oxide and/or tin oxide, and/or silicon carbide doped with and without aluminum. On the other hand, as an alternative or in addition, the mentioned electrically conductive and/or semi- or partially conductive materials such as doped titanium oxide and/or tin oxide and/or silicon carbide doped with and without aluminum can also be used without a substrate, such as mica Filler present.
Das Band, das zur Herstellung der Außenglimmschutzwicklung eingesetzt wird, umfasst zumindest ein Bindemittel , in der Regel ein Polymer und eine Mischung aus planaren und/oder globularen und/oder tubulären elektrisch leitfähigen und/oder teilleitfähigen Füllstoffen, die gegebenenfalls eine u . U . do- tierte Beschichtung aufweisen . The tape that is used to produce the external corona protection winding comprises at least one binder, usually a polymer and a mixture of planar and/or globular and/or tubular electrically conductive and/or partially conductive fillers, which optionally have a u. U. have doped coating.
Nach einer vorteilhaften Ausführungsform der Erfindung um- fasst die polymere Matrix mehrere Polyvinylalkohole . Grund- sätzlich sind Polyvinylalkohole gemäß der Erfindung als Poly- mermatrix oder Teil der Polymermatrix des Glimmschutzbandes einsetzbar, jedoch beispielsweise seien im Folgenden einige besonders geeignete Polyvinylalkohole , die allein oder in Kombination einsetzbar sind, genannt . According to an advantageous embodiment of the invention, the polymeric matrix comprises several polyvinyl alcohols. In principle, polyvinyl alcohols according to the invention can be used as the polymer matrix or part of the polymer matrix of the corona shielding strip, but some particularly suitable polyvinyl alcohols, which can be used alone or in combination, are mentioned below, for example.
Polyvinylalkohol mit der GAS Nummer 9002- 89-5 und der Summen- formel ( - C2H4O- ) n der Wiederholeinheit , ist ein Thermoplast und liegt handelsüblich als ein kristalliner, weiß bis gelb- licher, wasserlöslicher Kunststoff vor . Polyvinyl alcohol with the GAS number 9002-89-5 and the molecular formula (-C 2 H 4 O-) n the repeating unit is a thermoplastic and is commercially available as a crystalline, white to yellowish, water-soluble plastic.
Im Gegensatz zu den meisten Vinylpolymeren kann Polyvinylal- kohol nicht durch einfache Polymerisation des entsprechenden Monomers hergestellt werden . Das dafür notwendige Monomer Ethenol existiert lediglich in seiner tautomeren Form als Acetaldehyd . Polyvinylalkohole werden durch Umesterung und/oder durch alkalische Versei fung von Polyvinylacetat ge- wonnen . Die Hydrolyse ist gut steuerbar . Es gibt Polyvinylal- kohol-Copolymerisate und verschiedene Derivate , bei denen ein
Teil der Hydroxylgruppen durch chemisch ähnliche reagierende Gruppen wie Siloxane ersetzt sind . Unlike most vinyl polymers, polyvinyl alcohol cannot be produced by simply polymerizing the corresponding monomer. The necessary monomer ethenol only exists in its tautomeric form as acetaldehyde. Polyvinyl alcohols are obtained by transesterification and/or alkaline saponification of polyvinyl acetate. The hydrolysis is easily controllable. There are polyvinyl alcohol copolymers and various derivatives in which a Some of the hydroxyl groups are replaced by chemically similar reactive groups such as siloxanes.
Geeignete Polyvinylalkohole besitzen beispielsweise einen Hydrolysegrad von größer 70 mol% . Vorteilhafter Weise sind dabei wenige oder mehrere Hydroxylgruppen durch Silizium hal- tige Verbindungen substituiert . Suitable polyvinyl alcohols have, for example, a degree of hydrolysis of more than 70 mol%. Advantageously, few or more hydroxyl groups are substituted by silicon-containing compounds.
Nach einer vorteilhaften Ausführungsform der Erfindung um- fasst die polymere Matrix im Band Polyvinylalkohol mit quer- vernetzten Anteilen . In welchem Grad? According to an advantageous embodiment of the invention, the polymeric matrix in the strip comprises polyvinyl alcohol with cross-linked portions. To what degree?
Nach einer vorteilhaften Ausführungsform umfasst die polymere Matrix im Band einen oder mehrere mit einem Aldehyd- modi fizierte und/oder mit Melamin quervernetzte Polyvinylal- kohol ( e ) . According to an advantageous embodiment, the polymeric matrix in the tape comprises one or more polyvinyl alcohol(s) modified with an aldehyde and/or crosslinked with melamine.
Nach einer vorteilhaften Ausführungsform der Erfindung um- fasst die polymere Matrix zumindest ein polymeres Bindemit- tel , das ein Polyvinylalkohol ist , der einen Hydrolysegrad von mindestens 70 mol% , insbesondere mindestens 85 mol% und bevorzugt von mindestens 87 mol% oder mehr aufweist . According to an advantageous embodiment of the invention, the polymeric matrix comprises at least one polymeric binder which is a polyvinyl alcohol which has a degree of hydrolysis of at least 70 mol%, in particular at least 85 mol% and preferably at least 87 mol% or more.
Nach einer weiteren vorteilhaften Ausführungsform der Erfin- dung umfasst die polymere Matrix zumindest einen Polyvinylal- kohol , bei dem die Hydroxylgruppen des Polyvinylalkohols zu- mindest teilweise durch Siloxan- und/oder Silanolgruppen sub- stituiert sind . According to a further advantageous embodiment of the invention, the polymeric matrix comprises at least one polyvinyl alcohol in which the hydroxyl groups of the polyvinyl alcohol are at least partially substituted by siloxane and/or silanol groups.
Zum Nachweis der Bestandteile eines Glimmschutzbandes nach einer Ausführungsform der Erfindung, insbesondere auch in ei- nem fertigen Isolationssystem, sind Untersuchungsmethoden wie IR- , UV- , und/oder VIS-spektroskopische Methoden und/oder rasterelektronische Untersuchungsmethoden, unter anderem auch mit Röntgenspektroskopie , beispielsweise EDX, geeignet . Investigation methods such as IR, UV, and/or VIS spectroscopic methods and/or scanning electronic investigation methods, including X-ray spectroscopy, for example, are used to detect the components of a corona protective strip according to one embodiment of the invention, in particular also in a finished insulation system EDX, suitable .
Nach einer vorteilhaften Ausführungsform der Erfindung um- fasst der elektrisch leitfähige Füllstoff hauptsächlich Koh-
lenstoff-basierte Komponenten wie beispielsweise eine Kohlen- stoffmodifikation - bevorzugt Ruß , Graphit und/oder Carbon Nanotubes . According to an advantageous embodiment of the invention, the electrically conductive filler mainly comprises carbon Lenstoff-based components such as a carbon modification material - preferably carbon black, graphite and / or carbon nanotubes.
Nach einer weiteren vorteilhaften Ausführungsform der Erfin- dung umfasst der elektrisch leitfähige Füllstoff ein Silizi- umcarbid, undotiert und/oder dotiertes Siliziumcarbid . According to a further advantageous embodiment of the invention, the electrically conductive filler comprises a silicon carbide, undoped and/or doped silicon carbide.
Nach einer weiteren vorteilhaften Ausführungsform der Erfin- dung umfasst der elektrisch leitfähige Füllstoff Partikel , die zumindest zum Teil aus Metalloxid, insbesondere einem Mischoxid, sind . According to a further advantageous embodiment of the invention, the electrically conductive filler comprises particles which are at least partly made of metal oxide, in particular a mixed oxide.
Als Metalloxid wird vorliegend eine Verbindung zwischen einem Metall und Sauerstoff bezeichnet , wobei der Sauerstoff in der Verbindung formell , also vereinfacht , 2- fach negativ geladen ist . Grundsätzlich ist der Sauerstoff in der Verbindung der elektronegative Partner . Daher die Bezeichnung ,,-oxid" . In the present case, a compound between a metal and oxygen is referred to as a metal oxide, the oxygen in the compound formally, ie in simplified terms, having a 2-fold negative charge. Basically, the oxygen in the compound is the electronegative partner. Hence the name "oxide".
Als Mischoxid - kurz MOX - wird entsprechend eine Substanz bezeichnet , in der mehr als ein Metall-Kation in einer oxidi- schen Verbindung vorliegt , also beispielsweise Titan- Aluminium-Oxid oder Eisen-Nickel-Oxid oder ähnliches . A mixed oxide - MOX for short - is accordingly a substance in which more than one metal cation is present in an oxidic compound, for example titanium-aluminum oxide or iron-nickel oxide or the like.
Nach einer vorteilhaften Ausführungsform der Erfindung wird ein Füllstoff eingesetzt , der eine Beschichtung aus einem do- tierten Zinnoxid und/oder einem dotierten Titanoxid hat und/oder der aus einem dotierten Zinnoxid und/oder Titanoxid besteht . According to an advantageous embodiment of the invention, a filler is used which has a coating of a doped tin oxide and/or a doped titanium oxide and/or consists of a doped tin oxide and/or titanium oxide.
Die Füllstoffpartikel können als Hohlkörper, als massive Teilchen, als beschichtete Teilchen und/oder als Core-Shell- Partikel vorliegen . The filler particles can be in the form of hollow bodies, solid particles, coated particles and/or core-shell particles.
Auf dem Trägerband ist zumindest eine Fraktion vorzugsweise aber nicht notwendigerweise ausschließlich plättchenförmiger Partikel appliziert , die durch eine Polymermatrix, also das Bindemittel zusammengehalten werden und somit das Glimm-
schutzband bilden. Zur Einstellung des elektrischen Wider- stands kann es dabei vorteilhaft sein, die Fraktion an plätt- chenförmigen Füllstoffpartikeln mit kugelförmigen, also glo- bularen Füllstoffpartikeln zu ergänzen. At least one fraction, preferably but not necessarily exclusively, of platelet-shaped particles is applied to the carrier tape, which are held together by a polymer matrix, i.e. the binder, and thus the glow form a protective band. In order to adjust the electrical resistance, it can be advantageous to supplement the fraction of platelet-shaped filler particles with spherical, ie globular, filler particles.
Nach einer vorteilhaften Ausführungsform der Erfindung hat das Glimmschutzband ein Flächengewicht von < 150 g/m2, bevor- zugt kleiner 100 g/m2. According to an advantageous embodiment of the invention, the corona protection strip has a basis weight of <150 g/m 2 , preferably less than 100 g/m 2 .
Nach einer vorteilhaften Ausführungsform umfasst das Träger- band Verstärkungsfasern, beispielsweise in Form eines Gewebes und/oder eines Faserverbunds, in und/oder auf den die polyme- re Matrix mit dem elektrisch leitfähigen Füllstoff einge- bracht ist und/oder mit dem sie durch das Bindemittel ver- klebt ist . According to an advantageous embodiment, the carrier tape comprises reinforcing fibers, for example in the form of a fabric and/or a fiber composite, in and/or on which the polymeric matrix with the electrically conductive filler is introduced and/or with which it is connected through the binder is bonded.
Das Trägerband besitzt bevorzugt ein Flächengewicht von 30 - 60 g/m2 . The carrier tape preferably has a basis weight of 30-60 g/m 2 .
Diese Verstärkungsfasern sind beispielsweise Glasfasern und/oder Polyethylenterephthalat - PET-Fasern. These reinforcing fibers are, for example, glass fibers and/or polyethylene terephthalate - PET fibers.
Nach einer vorteilhaften Ausführungsform ist das Trägerband mit einer Primerung beschichtet . Dabei ist es insbesondere vorteilhaft, wenn das Trägerband mit einer Primerung von bis zu 5 g/m2 beschichtet ist . According to an advantageous embodiment, the carrier tape is coated with a primer. It is particularly advantageous if the carrier tape is coated with a primer of up to 5 g/m 2 .
Insbesondere hat sich als vorteilhaft erwiesen, wenn die Pri- merung des Trägerbandes Polyvinylalkohol, Epoxid- und/oder Aminfunktionalitäten umfasst . In particular, it has proven to be advantageous if the priming of the carrier tape comprises polyvinyl alcohol, epoxy and/or amine functionalities.
Als Primerung wird vorliegend eine grundierende Beschichtung bezeichnet, durch die die Verstärkungsfasern und/oder das Trägerband, -gewebe in ihrer Schnittfestigkeit verbessert werden und für eine Benetzung und Anbindung mit der polymeren Matrix vorbereitet werden.
Nach einer vorteilhaften Ausführungsform der Erfindung liegt die Menge der Beschichtung des Trägerbandes mit der polymeren Matrix, die die zumindest eine Fraktion an elektrisch leitfä- higem Füllstoff und/oder gegebenenfalls auch den zumindest einen Band-Beschleuniger enthält im Bereich von 20 g/m2 bis 100 g/m2 , insbesondere im Bereich von 20 g/m2 bis 60 g/m2 , be- sonders bevorzugt im Bereich von 30 g/m2 bis 45 g/m2 , vor . In the present case, priming refers to a priming coating through which the cut resistance of the reinforcing fibers and/or the carrier tape or fabric is improved and prepared for wetting and bonding with the polymeric matrix. According to an advantageous embodiment of the invention, the amount of coating of the carrier tape with the polymeric matrix, which contains the at least one fraction of electrically conductive filler and/or possibly also the at least one tape accelerator, is in the range from 20 g/m 2 to 100 g/m 2 , in particular in the range from 20 g/m 2 to 60 g/m 2 , particularly preferably in the range from 30 g/m 2 to 45 g/m 2 .
Nach der Erfindung wird das Glimmschutzband zur Herstellung eines Außenglimmschutzsystems und/oder eines Innenpotential- steuerungssystems und/oder eines Endenglimmschutzsystems ein- gesetzt . According to the invention, the corona protection strip is used to produce an external corona protection system and/or an internal potential control system and/or an end corona protection system.
Dabei ist es vorteilhaft , wenn der Quadrat- und/oder Flächen- widerstand eines durch ein Glimmschutzband gemäß der vorlie- genden Erfindung hergestellten Außenglimmschutzsystems und/oder eines Innenpotentialsteuerungssystems im Bereich von 0 , 01 kOhm bis 100 kOhm, gemessen bei einer Feldstärke von 1 V/mm liegt . It is advantageous if the square and/or surface resistance of an external corona protection system produced by a corona protection strip according to the present invention and/or an internal potential control system is in the range from 0.01 kOhm to 100 kOhm, measured at a field strength of 1 V /mm lies .
Insbesondere liegen die Quadrat- und/oder Flächenwiderstands- werte einer derartigen Innenpotentialsteuerung bevorzugt im Bereich von 0 , 01 kOhm bis 10 kOhm, bevorzugt im Bereich von 0 , 01 bis 5 kOhm und besonders bevorzugt im Bereich von 0 , 05 bis 1 kOhm und/oder die Quadratwiderstandswerte eines derar- tigen Außenglimmschutzes im Bereich von 0 , 1 bis 100 kOhm, insbesondere von 0 , 1 kOhm bis 50 kOhm und besonders bevorzugt im Bereich von 1 kOhm bis 10 kOhm, jeweils gemessen bei einer Feldstärke von 1 V/mm . In particular, the square and/or sheet resistance values of such an internal potential control are preferably in the range from 0.01 kOhm to 10 kOhm, preferably in the range from 0.01 to 5 kOhm and particularly preferably in the range from 0.05 to 1 kOhm and/or or the square resistance values of such external corona protection in the range from 0.1 to 100 kOhm, in particular from 0.1 kOhm to 50 kOhm and particularly preferably in the range from 1 kOhm to 10 kOhm, each measured at a field strength of 1 V/mm.
Bei der Herstellung eines Endenglimmschutzes mittels eines Glimmschutzbandes gemäß der vorliegenden Erfindung ist es vorteilhaft , wenn ein Flächenwiderstand im Bereich von Ixl O8 bis 1 x 1012 Ohm, insbesondere im Bereich von Ixl O8 bis Ixl O12 Ohm bei einer Feldstärke von 100 V/mm vorliegt . When producing an end corona protection using a corona protection band according to the present invention, it is advantageous if a surface resistance in the range from Ixl O 8 to 1 x 10 12 ohms, in particular in the range from Ixl O 8 to Ixl O 12 ohms, at a field strength of 100 V /mm is present.
Die Erfindung betrifft ein Glimmschutzband für eine elektri- sche Hochspannungsmaschine mit Anhydrid- freien, insbesondere
Phthalsäureanhydridderivatfreien Epoxidharzen . Das hier erst- mals vorgestellte Glimmschutzband ist mit seinen Komponenten, insbesondere der verbindenden polymeren Matrix und dem einge- lagerten kationischen Band-Beschleuniger auf die neuen, bei- spielsweise auch Alkyl-Phthalsäureanhydridderivat- freien VPI- Imprägnierharze auf Epoxidharzbasis eingestellt . The invention relates to a corona protection strip for an electrical high-voltage machine with anhydride-free, in particular Epoxy resins free of phthalic anhydride derivatives. The corona protection tape presented here for the first time is adjusted with its components, in particular the connecting polymeric matrix and the embedded cationic tape accelerator, to the new epoxy resin-based VPI impregnation resins, which are also free of alkyl phthalic anhydride derivatives, for example.
Bevorzugt ist der Bandbeschleuniger eine ionogen aufgebaute Verbindung aus einem oder mehreren Sulfonium -haltigen Kati- on ( en) mit einem oder mehreren Anionen, insbesondere komplex aufgebauten Anionen, wie beispielsweise Hexafluoroantimonat- Anion ( en) , jeweils geeignet für den Einsatz in einem VPI- Prozess zur Herstellung eines Isolationssystems mit einem An- hydrid- freien Imprägniermittel . . The belt accelerator is preferably an ionic compound composed of one or more sulfonium-containing cation(s) with one or more anions, in particular complex anions, such as hexafluoroantimonate anion(s), each suitable for use in a VPI Process for manufacturing an insulation system with an anhydride-free impregnating agent. .
Der Bandbeschleuniger ist ein kationischer Bandbeschleuniger und ist daher bevorzugt ionogen auf gebaut . Insbesondere hat der Bandbeschleuniger ein Sulfonium -haltiges Kation . The belt accelerator is a cationic belt accelerator and is therefore preferably constructed ionogenically. In particular, the ribbon accelerator has a sulfonium-containing cation.
Beispielsweise ist ein geeigneter kationischer Bandbeschleu- niger eine chemische Verbindung, die unter eine der Struktur- formeln I , II oder III fällt :
For example, a suitable cationic belt accelerator is a chemical compound that falls under one of structural formulas I, II, or III:
Supersäuren-Salz mit Sulfonium -Kation Struktur I
Superacid salt with sulfonium cation Structure I
Struktur I
Structure I
Kation Struktur II
cation structure II
Di -Aryl-Alkyl-Sulfonium -Kation 15
Di-aryl-alkyl-sulfonium cation 15
Kation Struktur III
cation structure III
Di-Alkyl-Aryl-Sulfonium-Kation Die hier gezeigten Sulfonium-Kationen I, II und III bilden mit komplexen Anionen wie BF4-, PF6-, SbF6-, AsF6-, SbF5(OH)-, ASF5(OH) Al[OC (CF3) 3] 4- die entsprechenden Supersäure-Salze, die vorliegend als Band-Beschleuniger einsetzbar sind. Di-alkyl-aryl-sulfonium cation The sulfonium cations I, II and III shown here form with complex anions such as BF 4 -, PF 6 -, SbF 6 -, AsF 6 -, SbF 5 (OH)-, ASF 5 (OH)Al[OC(CF 3 ) 3 ] 4 - the corresponding superacid salts useful herein as line accelerators.
Als „Supersäuren" werden Säuren bezeichnet, die stärker als konzentrierte 100-prozentige Schwefelsäure mit dem pKs-Wert = -3, sind. Beispiele sind Fluorsulfonsäure, Fluor- Antimonsäure, per-halogenierte Carborane und andere. "Superacids" are acids that are stronger than concentrated 100% sulfuric acid with a pKa value of -3. Examples are fluorosulfonic acid, fluoroantimonic acid, per-halogenated carboranes, and others.
Dabei zeigt die Strukturformel „Struktur I" den kationischen Teil eines Bandbeschleunigers gemäß einem bevorzugten Ausfüh- rungsbeispiel der vorliegenden Erfindung. The structural formula "Structure I" shows the cationic part of a belt accelerator according to a preferred embodiment of the present invention.
Als „kationischer Bandbeschleuniger" wird ein Bandbeschleuni- ger bezeichnet, der ionogen aufgebaut ist und dessen Kation in einem flüssigen Imprägniermittel die kationische Polymeri- sation, insbesondere die kationische Homopolymerisation eines vorgelegten Imprägnierharzes initiiert. A "cationic belt accelerator" is a belt accelerator which is ionic and whose cation initiates the cationic polymerization, in particular the cationic homopolymerization, of an impregnating resin in a liquid impregnating agent.
Als „ionogen" aufgebaute Verbindung werden heteropolare Ver- bindungen bezeichnet, deren chemische Reaktivität vom Vorlie- gen eines Kations und eines Anions in der Verbindung geprägt sind. Klassische „ionogen" vorliegende Verbindungen sind Sal-
ze . Aber auch komplexe Strukturen mit kationischem und anio- nischem Charakter werden vorliegend als „ionogen" aufgebaute Verbindungen bezeichnet . "Ionogenic" compounds are heteropolar compounds whose chemical reactivity is characterized by the presence of a cation and an anion in the compound. Classic "ionogenic" compounds are salts. ze . However, complex structures with a cationic and anionic character are also referred to here as “ionogenic” compounds.
Ein „Sulfonium -haltiges Kation" ist ein Kation, das im Mole- kül neben dem Anion oder den Anionen eine Einheit umfasst , die durch die einfach positiv geladenen Strukturen II oder III oder durch die Summenformel [ SR3 ] + zu beschreiben ist . A “sulfonium-containing cation” is a cation which, in addition to the anion or anions, includes a unit in the molecule which can be described by the simply positively charged structures II or III or by the molecular formula [SR 3 ] + .
Als „Alkyl-Aryl-Sulfonium " oder „Di-Alkyl-Aryl-Sulfonium " wird dabei ein Sulfonium -haltiges Kation bezeichnet , bei dem ein oder zwei der drei Reste „R" am Schwefel-Atom im Sul foni- um-Kation Alkylgruppen sind . Alkylgruppen sind Teile eines Moleküls , die aus miteinander verbundenen Kohlenstoff- und Wasserstoff-Atomen bestehen . Im Sinne der Erfindung sind be- vorzugte Alkylreste solche mit 1 bis 12 C-Atomen, die ver- zweigt oder linear vorliegen können . Die Alkylgruppen sind dabei einwertig mit dem zentralen Schwefelatom verbunden . A sulfonium-containing cation is referred to as “alkyl-aryl-sulfonium” or “di-alkyl-aryl-sulfonium” in which one or two of the three radicals “R” on the sulfur atom in the sulfonium cation are alkyl groups Alkyl groups are parts of a molecule consisting of carbon and hydrogen atoms bonded to one another.In the context of the invention, preferred alkyl radicals are those having 1 to 12 carbon atoms, which can be branched or linear thereby monovalently bonded to the central sulfur atom.
Gemäß der Erfindung können bei einem Di-Alkyl-Aryl-Sulfonium - Kation ein oder zwei Alkylreste vorliegen, die ihrerseits gleich oder verschieden sein können . According to the invention, a di-alkyl-aryl-sulfonium cation can have one or two alkyl radicals, which in turn can be identical or different.
Als „Aryl-Alkyl-Sulfonium oder Di-Aryl-Alkyl-Sulfonium " wird dabei ein Sulfonium -haltiges Kation bezeichnet , bei dem ein oder zwei der drei Reste „R" am Schwefel-Atom im Sulfonium - Kation Arylgruppen sind . Arylgruppen sind Teile eines Mole- küls , die einwertig bzw . per Einfachbindung an dem Kohlen- stoff-Gerüst , respektive am Schwefelatom, hängen und zumin- dest einen aromatischen Kern, der teilweise oder ganz - sub- stituiert oder - unsubstituiert , sein kann, haben . A sulfonium-containing cation in which one or two of the three radicals “R” on the sulfur atom in the sulfonium cation are aryl groups is referred to as “aryl-alkyl-sulfonium or di-aryl-alkyl-sulfonium”. Aryl groups are parts of a molecule that are monovalent or are attached by a single bond to the carbon skeleton, or to the sulfur atom, and have at least one aromatic nucleus, which can be partially or fully substituted or unsubstituted.
Gemäß der Erfindung können bei einem Aryl-Alkyl-Sulfonium - Kation ein oder zwei Arylreste vorliegen, die ihrerseits gleich oder verschieden sein können .
Der dritte Rest kann dabei beliebig, also auch eine Alkyl- gruppe oder eine Arylgruppe , ganz oder teilweise substituiert oder nicht , sein . According to the invention, an aryl-alkyl-sulfonium cation can have one or two aryl radicals, which in turn can be identical or different. The third radical can be anything, ie also an alkyl group or an aryl group, fully or partially substituted or not.
Eine Arylgruppe ist ein organisch-chemischer Rest mit einem aromatischen Grundgerüst . Es ist die Bezeichnung für eine einwertige Atomgruppe , die sich von aromatischen Kohlenwas- serstoffen durch Entzug eines an den Ring gebundenen Wasser- stoffatoms ableiten . Die meisten Arylgruppen leiten sich vom Benzol ab, die einfachste Arylgruppe ist die Phenylgruppe . An aryl group is an organic chemical radical with an aromatic backbone. It is the designation for a monovalent atomic group derived from aromatic hydrocarbons by removing a hydrogen atom attached to the ring. Most aryl groups are derived from benzene, the simplest aryl group being the phenyl group.
Nach einer bevorzugten Ausführungsform liegt im Sulfonium - Kation zumindest eine Arylgruppe vor . According to a preferred embodiment, at least one aryl group is present in the sulfonium cation.
Dabei ist bevorzugt , wenn zumindest eine einkernige Arylgrup- pe , also beispielsweise eine Arylgruppe mit einer von Benzol abgeleiteten Aryl-Struktur, wie beispielsweise Phenyl- oder Benzyl- vorliegt . It is preferred if at least one mononuclear aryl group, for example an aryl group with an aryl structure derived from benzene, such as phenyl or benzyl, is present.
Insbesondere ist auch bevorzugt , wenn an einem einkernigen aromatischen Rest der Arylgruppe des Sulfonium -haltigen Kati- ons zumindest eine Substitution vorliegt , also ein Wasser- stoff am aromatischen Kern ersetzt ist , beispielsweise durch eine funktionelle Gruppe oder eine Alkylgruppe . In particular, it is also preferred if there is at least one substitution on a mononuclear aromatic radical of the aryl group of the sulfonium-containing cation, ie a hydrogen on the aromatic nucleus is replaced, for example by a functional group or an alkyl group.
Die funktionelle Gruppe kann dabei mit oder ohne Heteroatom wie Sauerstoff, Stickstoff, Schwefel , Phosphor vorliegen . The functional group can be present with or without a heteroatom such as oxygen, nitrogen, sulfur or phosphorus.
Besonders bevorzugt ist eine Arylgruppe , bei dem ein Wasser- stoff am aromatischen Kern durch eine Acetyloxy-gruppe , er- setzt ist . An aryl group in which a hydrogen on the aromatic nucleus is replaced by an acetyloxy group is particularly preferred.
Des Weiteren ist besonders bevorzugt , dass als Bandbeschleu- niger ein Sulfonium -haltiges Kation kombiniert mit einem He- xafluoroantimonat-Anion vorliegt . Furthermore, it is particularly preferred that a sulfonium-containing cation combined with a hexafluoroantimonate anion is present as the belt accelerator.
Der Glimmschutz-Bandbeschleuniger kann als Mischung zumindest zweier kationischer Bandbeschleuniger, die jeweils ein ande-
res Sulfonium -Kation haben, vorliegen . Die Anionen können gleich oder verschieden sein, insbesondere als Anion Hexaflu- oro-Antimonat . The corona protection belt accelerator can be a mixture of at least two cationic belt accelerators, each of which has a different have res sulfonium cation, are present. The anions can be the same or different, in particular as an anion hexafluoro-antimonate.
Der Glimmschutz-Bandbeschleuniger, egal ob als Einzel- Verbindung oder als Mischung vorliegend, hat bevorzugt einen Schmel zpunkt im Bereich von 145 ° C bis 165 ° C, insbesondere be- vorzugt im Bereich von 150 ° C bis 160 ° C . The corona protection strip accelerator, regardless of whether it is present as an individual compound or as a mixture, preferably has a melting point in the range from 145.degree. C. to 165.degree. C., particularly preferably in the range from 150.degree. C. to 160.degree.
Außerdem ist Gegenstand der Erfindung die Verwendung des re- aktiven Glimmschutzbandes zur Herstellung eines Anhydrid- freien Isolationssystems durch Imprägnieren des festen Glimm- schutzbandes mit einem Imprägniermittel , wobei das Impräg- niermittel ein aromatisches und/oder cyclo-aliphatisches Im- prägnierharz umfasst , das Anhydrid- frei und Epoxidgruppen- haltig ist . The invention also relates to the use of the reactive corona protection tape for producing an anhydride-free insulation system by impregnating the solid corona protection tape with an impregnation agent, the impregnation agent comprising an aromatic and/or cycloaliphatic impregnation resin, the anhydride - is free and contains epoxy groups.
Als Anionen des kationischen Bandbeschleunigers eignen sich insbesondere komplex aufgebaute Anionen, wie das Hexafluoro- antimonat-Anion, so dass als Bandbeschleuniger beispielsweise das 4 -Acetyloxyphenyl-dimethylsul fonium-hexafluoroantimonat - CAS-Nr . 135691-31-5 - Struktur I , vorliegt . Anions with a complex structure, such as the hexafluoro-antimonate anion, are particularly suitable as the anions of the cationic belt accelerator, so that, for example, the 4-acetyloxyphenyldimethylsulphonium hexafluoroantimonate - CAS no. 135691-31-5 - Structure I .
Im Folgenden wird die Erfindung anhand eines Anwendungsbei- spiels , das eine Ausführungsform der Erfindung beschreibt , näher erläutert : The invention is explained in more detail below using an application example that describes an embodiment of the invention:
Durch Verwendung des in Struktur I genannten Sulphoniumsuper- säurederivats 4 -Acetyloxyphenyl -dimethylsulfonium - hexafluoroantimonat in wässriger Abmischung mit bevorzugter- weise silanolgruppenmodifiziertem Polyvinylalkohol und plätt- chenförmigen, mit Zinnoxid teilleitfähig eingestelltem, bei- spielsweise dotiertem Füllstoff, sowie organischem Lösemit- tel , wie z . B . 2-Butanon, und Wasser lässt sich ein Lack be- reiten, der zum Imprägnieren/Applizieren auf Polymer- und/oder Glasgewebeträger befähigt ist und mit dem sich nach Trocknung eine Schicht gewünschter, erfindungsgemäßer Leitfä- higkeit , d . h . mit Quadratwiderständen im Bereich von R =1- 10
kOhm über einen Temperaturbereich von 20- 150 ° C, auf dem Poly- mer- und/oder Glasgewebeträger einstellen lässt . By using the sulphonium superacid derivative 4-acetyloxyphenyl-dimethylsulfonium-hexafluoroantimonate mentioned in structure I in an aqueous mixture with preferably silanol-group-modified polyvinyl alcohol and flake-form filler which has been made partially conductive with tin oxide, for example doped, and organic solvents, such as e.g . B. 2-butanone, and water can be prepared a paint that is capable of impregnating/applying to polymer and/or glass fabric carriers and with which, after drying, a layer of the desired conductivity according to the invention, d. H . with square resistances in the range of R =1- 10 kOhm over a temperature range of 20-150 °C, can be set on the polymer and/or glass fabric carrier.
Durch Verwenden eines Sulphoniumsupersäurederivats als Ver- netzungsbeschleuniger ist dieses neuartige Glimmschutzband zum Härten von herkömmlichen Epoxidharz-Phthalsäureanhydrid- Mischungen als auch von neuartigen, also Anhydrid- freien Im- prägniermitteln mit Epoxidharzen, insbesondere in Kombination mit cycloaliphatischen Epoxidharzen, tauglich . Derartige Sulphoniumsupersäurederivat ( e ) , können Bisphenol-A- Diglycidylether , Bisphenol-F-Diglycidylether , Glycidylester , aliphatische und/oder cycloaliphatische Epoxidharze jeweils alleine , aber auch in beliebiger Kombination gelieren und aushärten . Erfolgreiche Tests wurden bereits mit Cycloalipha- tischen Epoxidharzen in Mischung mit BADGE (Bisphenol-A- diglycidylether ) durchgeführt . By using a sulphonium superacid derivative as a crosslinking accelerator, this novel corona protection tape is suitable for curing conventional epoxy resin-phthalic anhydride mixtures as well as novel, i.e. anhydride-free, impregnating agents with epoxy resins, particularly in combination with cycloaliphatic epoxy resins. Such sulphonium superacid derivative(s), bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycidyl ester, aliphatic and/or cycloaliphatic epoxy resins can gel and cure alone, but also in any combination. Successful tests have already been carried out with cycloaliphatic epoxy resins mixed with BADGE (bisphenol A diglycidyl ether) .
Es hat sich auch überraschend gezeigt , dass im Sinne der Bandstabilität bzgl . der elektrischen Leitfähigkeit der Schicht ein formgebender Quervernetzer zusätzlich appliziert werden kann, das Band aber auch ohne formgebenden Quervernet- zer ausreichende Stabilität zur Wicklung aufweist . It has also surprisingly turned out that in terms of tape stability with regard to the electrical conductivity of the layer, a shaping crosslinker can also be applied, but the tape also has sufficient stability for winding without a shaping crosslinker.
Das so über anschließende Heißlufttrocknung hergestellte Glimmschutzband zeigt bei erfindungsgemäßer Wärmeimprägnie- rung bei 70 ° C und anschließender Heißhärtung bei 140 ° C mit Anhydrid- freiem Epoxidharz bzw . einer vorteilhaften Mischung aus ca . 80 Gew . -% cycloaliphatischem Epoxidharz und ca . 20 Gew . -% destilliertem Bisphenol-A-Diglycidylether , nur gering- fügiges , nachteiliges Quellverhalten, sodass der auf dem Glimmschutzband originär eingestellte Quadratwiderstand auch während und nach der Aushärtung mit flüssigem Epoxidharz , an- hydridfreier Natur, am bevorzugtesten hauptsächlich, aber nicht ausschließlich cycloaliphatischer Struktur, erhalten bleibt und so die teilleitfähige Charakteristik bei Applika- tion des Glimmschutzbandes in einer elektrischen Maschine zum Abbau hoher elektrischer Feldstärken in Statorwicklungen kon- serviert wird .
Erfindungsgemäß wurden demnach zur Lackherstellung 20.0g 4- Acetyloxyphenyl -dimethyl sulf onium-hexafluoroantimonat in 200.0g Ethylmethylketon gelöst. Diese klare, organische Lö- sung wurde bei Raumtemperatur unter Rühren langsam zu einer Suspension von 590.0g Iriotec 7320 (Fa. Merck KGaA, Darm- stadt) und 108.7g Poval™ 25-98 R (Fa. Kuraray Europe GmbH, Hattersheim am Main) in 2400.0g destilliertem Wasser zuge- tropft und weitere 30min bei Raumtemperatur gerührt, z.B. per Dissolver mit Zahndispergierscheibe um durch Scherung im Nah- bereich der Scheibe etwaige Agglomerate zu zerkleinern. The corona protection tape produced in this way via subsequent hot-air drying shows, with heat impregnation according to the invention at 70° C. and subsequent hot curing at 140° C. with anhydride-free epoxy resin or an advantageous mixture of approx. 80 wt. -% cycloaliphatic epoxy resin and approx. 20 wt. -% distilled bisphenol A diglycidyl ether, only slight, disadvantageous swelling behavior, so that the square resistance originally set on the corona protection tape also during and after curing with liquid epoxy resin, anhydride-free nature, most preferably mainly, but not exclusively cycloaliphatic structure, is retained and so the partially conductive characteristic is preserved when the corona protection tape is applied in an electrical machine to reduce high electrical field strengths in the stator windings. According to the invention, 20.0 g of 4-acetyloxyphenyldimethylsulfonium hexafluoroantimonate were dissolved in 200.0 g of ethyl methyl ketone to produce the lacquer. This clear, organic solution was slowly stirred at room temperature to form a suspension of 590.0 g of Iriotec 7320 (Merck KGaA, Darmstadt) and 108.7 g of Poval™ 25-98 R (Kuraray Europe GmbH, Hattersheim am Main ) was added dropwise to 2400.0 g distilled water and stirred for a further 30 minutes at room temperature, eg using a dissolver with a toothed dispersing disc in order to break up any agglomerates by shearing in the vicinity of the disc.
Diese türkis-schimmernde Lacksuspension wurde sodann auf 200mm breites Glas-/Polyester-Mischgewebe mit 44.7 g/m2 Flä- chengewicht (Fa. Krempel GmbH, Vaihingen/Enz ) mittels Tauch- auftrag in einer Basecoater-Bandimprägnieranlage (Fa. COATEMA Coating Machinery GmbH, Dormagen) aufgebracht und bei etwa 120°C Band-Oberflächentemperatur im Heißluftgebläseofen ver- tikal unter einem Bandlauf von 0.8 Meter/Minute über eine Länge von 1,5m getrocknet. Es ergab sich als Resultat auf dem Band ein Trockengesamtauftrag von 27.48 g/m2, mit 0.77 g/m2 4 -Acetyloxyphenyl -dimethyl sulf onium-hexafluoroantimonat als Beschleunigersubstanz, 22.56 g/m2 Iriotec 7320 als teilleit- fähigem Material für die Feldabsteuerung sowie 4.16 g/m2 Poval™ 25-98 R als Bindemittel. In Summe hatte das Band also ein spezifisches Flächengesamtgewicht von ca. 72 g/m2. This turquoise shimmering paint suspension was then applied to a 200 mm wide glass/polyester blended fabric with a basis weight of 44.7 g/m 2 (Krempel GmbH, Vaihingen/Enz) by means of dip application in a base coater belt impregnation system (COATEMA Coating Machinery GmbH, Dormagen) and dried at a strip surface temperature of around 120°C in a hot-air fan oven vertically with a strip running at 0.8 meters/minute over a length of 1.5 m. The result on the belt was a total dry application of 27.48 g/m 2 , with 0.77 g/m 2 of 4-acetyloxyphenyl dimethyl sulfonium hexafluoroantimonate as an accelerator substance, 22.56 g/m 2 of Iriotec 7320 as a partially conductive material for field control and 4.16 g/m 2 Poval™ 25-98 R as a binder. In total, the tape had a specific total area weight of approx. 72 g/m 2 .
Das haptisch hervorragende, sehr gut wickelbare, klebfreie, geruchsarme, türkisfarbene, robuste und neuartige Glimm- schutzband wies bei 20-23°C einen Quadratwiderstand Rrj=6.5 kOhm auf, gemessen mittels 10cm2 -Hochohm- Federzungenelektrode 3501FE nach DIN 53482 bzw. DIN EN 62631-3-2 ( Fa. H.-P. Fi- scher Elektronik GmbH & Co., Mittenwalde) . The tactile, excellent, very easy to wind, non-tacky, low-odour, turquoise, robust and innovative corona protection tape had a square resistance Rrj=6.5 kOhm at 20-23°C, measured using a 10cm 2 high-ohm spring tongue electrode 3501FE according to DIN 53482 or DIN EN 62631-3-2 (H.-P. Fischer Elektronik GmbH & Co., Mittenwalde).
Zur Untersuchung des kritischen Quellverhaltens des neuarti- gen Glimmschutzbandes während der VPI-Imprägnierung und wäh- rend des Heißhärtens in erfindungsgemäßem, phthalsäureanhyd- ridfreien Epoxidharz auf Basis von Mischungen aus cyc-
loaliphatischen Epoxidharz und Glycidyletherepoxidharz , wur- den zwei Glimmschutzbandstreifen der Abmessung 12 cm x 2.5 cm präpariert und die Enden je zu einem Centimeter Breite beid- seitig mit handelsüblichem Silberleitlack versehen, sodass zwei elektrisch kontaktierbare Glimmschutzbandstreifen der Abmessung 10 cm * 2.5 cm erhalten wurden. Diese Steifen wur- den am Silberleitlackkontakt mit hitzebeständigen Krokodil- klemmen kontaktiert und an ein Multikanal- Präzessionsmessgerät Almemo® 2890-9 (Fa. Ahlborn Mess- und Regelungstechnik GmbH, Holzkirchen) zur kontinuierlichen Wi- derstandsaufzeichnung angeschlossen . To investigate the critical swelling behavior of the novel corona protection strip during VPI impregnation and during hot curing in the phthalic anhydride-free epoxy resin according to the invention based on mixtures of cyclic loaliphatic epoxy resin and glycidyl ether epoxy resin, two corona protection tape strips measuring 12 cm x 2.5 cm were prepared and the ends, each one centimeter wide, were provided with commercially available conductive silver paint on both sides, so that two electrically contactable corona protection tape strips measuring 10 cm x 2.5 cm were obtained. These strips were contacted with heat-resistant crocodile clips at the conductive silver paint contact and connected to a multi-channel precession measuring device Almemo® 2890-9 (from Ahlborn Mess- und Regeltechnik GmbH, Holzkirchen) for continuous resistance recording.
Die Glimmbandstreifen wurden sodann mittig jeweils durch Ge- wichte unter Zug stehend, in einen Umluftofen überführt und vollständig für vier Stunden in ein 70°C heißes, phthalsäure- anhydridfreies Epoxidharzgemisch, bestehend aus 80 Gew.-% cycloaliphatischem Epoxidharz des Typs 3,4- Epoxycyclohexylmethyl-3 ' , 4 ' -epoxycyclohexancarboxylat (Cel- loxide™ C2021P, Fa . Daicel Corporation, Tokyo; CAS-Nr. 2386- 87-0) sowie 20 Gew.-% destilliertem Bisphenol-A- Diglycidylether (Epikote™ Resin 162, Fa . Hexion GmbH, Iser- lohn; CAS-Nr. 1675-54-3) , getaucht. The glow strip strips were then placed in the center by weights under tension, transferred to a convection oven and immersed completely for four hours in a phthalic anhydride-free epoxy resin mixture at 70° C., consisting of 80% by weight of cycloaliphatic epoxy resin of the 3,4- Epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate (Celloxide™ C2021P, Daicel Corporation, Tokyo; CAS No. 2386-87-0) and 20% by weight distilled bisphenol A diglycidyl ether (Epikote™ Resin 162 , Hexion GmbH, Iserlohn; CAS No. 1675-54-3) , immersed.
Nach dieser vierstündigen, die 70 °C-VPI-Imprägnierphase nach- stellenden Zeitspanne, wurden die elektrisch kontaktierten Glimmschutzbandstreifen aus dem Harz gehoben, thermisch zehn Stunden bei 145°C im Ofen heißgehärtet und im Anschluss auf Raumtemperatur abgekühlt. Während dieser Zeit wurde der elektrische Widerstand kontinuierlich auf gezeichnet . Durch Umrechnung des über die Zeit auf gezeichneten Widerstandes in den Quadratwiderstand (10 cm * 2.5 cm) wurde überraschend festgestellt, dass die ideale Widerstandscharakteristik des neuartigen Glimmschutzbandes im Bereich von 1-10 kOhm im vol- len Temperaturbereich von 20-145 °C beibehalten wird und somit zum Absteuern elektrischer Felder an Wicklungen in an- hydridfreien, VPI-Epoxidharz-imprägnierten, elektrischen Ma- schinen und Generatoren bestens geeignet ist.
Zur Überprüfung der Beschleunigerauswaschung aus dem neuen Glimmschutzband wurde zudem ein sog. Harzinfizierungsversuch bzw. Beschleunigerverfügbarkeitstest vollzogen. Dazu wurden zwei Glimmschutzbandstreifen der Abmessungen 2.5 cm x 4.8 cm (12 cm2) präpariert und in jeweils 30g des o.g. (Al- kyl ) phthalsäureanhydridfreien Epoxidharzes (80 Gew.-% 3,4- Epoxycyclohexylmethyl-3 ' , 4 ' -epoxycyclohexancarboxylat / 20After this four-hour period of time, following the 70 °C VPI impregnation phase, the electrically contacted corona protective tape strips were lifted out of the resin, heat-cured in the oven at 145 °C for ten hours and then cooled to room temperature. During this time the electrical resistance was continuously recorded. By converting the resistance recorded over time into the square resistance (10 cm * 2.5 cm), it was surprisingly found that the ideal resistance characteristics of the novel corona protection tape in the range of 1-10 kOhm are retained in the full temperature range of 20-145 °C and is therefore ideally suited for deflecting electrical fields on windings in anhydride-free, VPI epoxy resin-impregnated electrical machines and generators. A so-called resin infection test or accelerator availability test was also carried out to check how the accelerator was washed out of the new corona protection tape. For this purpose, two corona protection tape strips measuring 2.5 cm x 4.8 cm (12 cm 2 ) were prepared and each 30 g of the abovementioned (alkyl) phthalic anhydride-free epoxy resin (80% by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate/ 20
Gew.-% destillierter Bisphenol-A-Diglycidylether ) vier Stun- den bei 70°C ausgelagert. Danach wurden die imprägnierten Glimmschutzbandstreifen aus dem Liquid entnommen und dieses verbliebene Epoxidharzgemisch weitere 20 Stunden bei 100°C gelagert. Nach Abkühlung auf 70 °C wurde jeweils die dynami- sche Viskosität (ηProbe1 , 20h/100°C, ηProbe2, 20h/100°C) bestimmt. Unter Abzug eines glimmschutzbandfreien Harzblindwertes ( ηBW, 20h/100°C) ergaben sich folgende Werte bzw. Eigenschaften: ηBW, 20h/100°C = 24.87 mPa·s ηProbe1, 20h/100°C = 43.78 mPa·s ηProbe2, 20h/100°C = 56.93 mPa·s% by weight of distilled bisphenol A diglycidyl ether) aged at 70° C. for four hours. The impregnated corona protection tape strips were then removed from the liquid and this remaining epoxy resin mixture was stored at 100° C. for a further 20 hours. After cooling to 70° C., the dynamic viscosity (η sample 1, 20 h/100° C. , η sample 2, 20 h/100° C. ) was determined in each case. Subtracting a glow shield band-free resin blank value (η BW , 20h/100°C ) resulted in the following values or properties: η BW , 20h/100°C = 24.87 mPa s η Sample1 , 20h/100°C = 43.78 mPa s η Sample2 , 20h/100°C = 56.93 mPa s
ErscheinungsbildProbe1&2, 20h/100°C = Glimmband- streifen sind steif, kein Tack BeschleunigerverfügbarkeitProbe1, 20h/100°C = 43.78 mPa·s - 24.87 mPa·s = 18.91 mPa·s Appearance Sample1&2 , 20h/100°C = glow strips are stiff, no tack Accelerator availability Sample1 , 20h/100°C = 43.78 mPa s - 24.87 mPa s = 18.91 mPa s
BeschleunigerverfügbarkeitProbe2, 20h/100°C = 56.93 mPa·s - 24.87 mPa·s = 32.06 mPa·s Accelerator availability Sample2 , 20h/100°C = 56.93 mPa s - 24.87 mPa s = 32.06 mPa s
Weiter wurde die Reaktivität des neuartigen Glimmschutzbandes nach bis zu vier Wochen Raumtemperaturlagerung untersucht. Dazu wurden Stanzproben aus dem Glimmschutzband entnommen, mit anhydridfreiem Epoxidharz (80 Gew.-% 3,4- Epoxycyclohexylmethyl-3 ', 4 ' -epoxycyclohexancarboxylat / 20 Gew.-% destillierter Bisphenol-A-Diglycidylether) in einem DSG-Tiegel benetzt und per dynamischer Differenzkalorimetrie (Fa. Net zsch-Gerätebau GmbH, Selb; DSC Phoenix Fl) bei 10 K/min die Reaktionsenthalpie bestimmt (vgl. Abb. 5) . Die Sta- bilität des neuartigen Glimmschutzbandes konnte anhand recht konstanter Reaktionsenthalpien (ca. 300-400 Joule pro Gramm Epoxidharzmischung) gezeigt werden.
Ausgehend von der neuen Generation an Isolationssystemen, die durch Imprägnieren mit Anhydrid- freien Imprägniermitteln her- stellbar sind, wird durch die vorliegende Erfindung erstmals ein Glimmschutzband offenbart , in das ein gut geeigneter, rasch die Homopolymerisation initiierender Band-Beschleuniger deponierbar ist . Der Band-Beschleuniger liegt in Form eines Sal zes einer Supersäure vor und ist in einem Glimmschutzband, das als Polymermatrix zumindest teilweise Polyvinylalkohol enthält , bis zu 6 Monate bei einer Temperatur von + 6 ° C bis 23 ° C lagerstabil .
Furthermore, the reactivity of the novel corona protection tape was examined after storage at room temperature for up to four weeks. For this purpose, punched samples were taken from the corona protection tape, wetted with anhydride-free epoxy resin (80% by weight of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate/20% by weight of distilled bisphenol A diglycidyl ether) in a DSG crucible and the reaction enthalpy was determined at 10 K/min by differential scanning calorimetry (Netzsch-Devicebau GmbH, Selb; DSC Phoenix Fl) (cf. Fig. 5). The stability of the novel corona protection tape could be demonstrated using fairly constant reaction enthalpies (approx. 300-400 joules per gram of epoxy resin mixture). Based on the new generation of insulation systems that can be produced by impregnation with anhydride-free impregnating agents, the present invention discloses a corona protection strip for the first time, in which a well-suited strip accelerator that quickly initiates homopolymerization can be deposited. The tape accelerator is in the form of a salt of a superacid and is storage-stable for up to 6 months at a temperature of +6 °C to 23 °C in a corona protection tape that at least partially contains polyvinyl alcohol as the polymer matrix.
Claims
1 . Glimmschutzband für die Weiterverarbeitung zu einem Isola- tionssystem, eine imprägnierte Wicklung mit Potentialsteue- rung durch Außenglimmschutz „AGS" und/oder Innenpotential- steuerung „IPS" und/oder Endenglimmschutz „EGS" umfassend, das Isolationssystem durch Imprägnieren der Wicklung mit ei- nem Anhydrid- freien und Harz-basierten Imprägniermittel bei 45 - 85 ° C und unter Vakuum herstellbar, wobei das Glimm- schutzband zumindest ein Trägerband, einen elektrisch leitfä- higen und/oder teilleitfähigen Füllstoff in einer Polymer- matrix und zumindest einen Band-Beschleuniger, geeignet zur Härtung und/oder Gelierung des Imprägniermittels umfasst , dadurch gekennzeichnet , dass die Polymermatrix zumindest ei- nen Polyvinylalkohol und/oder ein Polyvinylalkohol- Copolymerisat enthält und dass der zumindest eine Band- Beschleuniger ausgewählt ist aus der Gruppe der Supersäuren und/oder der Supersäurensalze , die zur Beschleunigung einer kationischen Homopolymerisation des Harz-basierten Anhydrid- freien Imprägniermittels geeignet ist . 1 . Corona protection tape for further processing into an insulation system, comprising an impregnated winding with potential control through external corona protection "AGS" and/or internal potential control "IPS" and/or end corona protection "EGS", the insulation system by impregnating the winding with a Anhydride-free and resin-based impregnation agent can be produced at 45 - 85 °C and in a vacuum, with the corona protection tape having at least one carrier tape, an electrically conductive and/or partially conductive filler in a polymer matrix and at least one tape accelerator, suitable for hardening and/or gelling the impregnating agent, characterized in that the polymer matrix contains at least one polyvinyl alcohol and/or a polyvinyl alcohol copolymer and that the at least one belt accelerator is selected from the group of super acids and/or super acid salts , which is based on accelerating a cationic homopolymerization of the resin Anhydride-free impregnating agent is suitable.
2 . Glimmschutzband nach Anspruch 1 , bei dem die Basis des Harz-basierten Imprägniermittels ein anhydridfreies Epoxid- harz ist . 2 . Corona protection tape according to claim 1, wherein the base of the resin-based impregnating agent is an anhydride epoxy resin.
3 . Glimmschutzband nach einem der Ansprüche 1 oder 2 , bei dem zumindest ein Ion eines Supersäurensal zes , das zumindest Teil des Band-Beschleunigers ist , ein Sulfonium -Kation ist . 3 . Corona protection tape according to one of Claims 1 or 2, in which at least one ion of a super acid salt which is at least part of the tape accelerator is a sulfonium cation.
4 . Glimmschutzband nach einem der Ansprüche 1 oder 2 , bei dem zumindest ein Ion eines Supersäurensal zes , das zumindest Teil des Band-Beschleunigers ist , ein Sulfonium -Kation mit einem Arylrest ist . 4 . Corona protection tape according to one of Claims 1 or 2, in which at least one ion of a superacid salt which is at least part of the tape accelerator is a sulfonium cation with an aryl radical.
5. Glimmschutzband nach einem der vorhergehenden Ansprüche , bei dem mehrere Bandbeschleuniger in Kombination vorliegen .
5. Corona protection belt according to one of the preceding claims, in which several belt accelerators are present in combination.
6. Glimmschutzband nach einem der Ansprüche 3 oder 4, bei dem ein Sulfonium-Kation in Form eines Aryl-Alkyl-Sulfonium- Kations vorliegt. 6. Corona protection band according to one of claims 3 or 4, in which a sulfonium cation is present in the form of an aryl-alkyl-sulfonium cation.
7. Glimmschutzband nach einem der vorhergehenden Ansprüche, bei dem zumindest ein Di-Alkyl-Aryl-Sulfonium-Kation vor- liegt . 7. Corona protection band according to one of the preceding claims, in which at least one di-alkyl-aryl-sulfonium cation is present.
8. Glimmschutzband nach einem der vorhergehenden Ansprüche, bei dem zumindest ein Di-Aryl-Alkyl-Sulfonium-Kation vor- liegt . 8. Corona protection band according to one of the preceding claims, in which at least one di-aryl-alkyl-sulfonium cation is present.
9. Glimmschutzband nach einem der vorhergehenden Ansprüche 3 bis 8, bei dem ein Aryl-Rest eines Sulfonium-Kations substi- tuiert vorliegt. 9. Corona protection band according to one of the preceding claims 3 to 8, in which an aryl radical of a sulfonium cation is substituted.
10. Glimmschutzband nach einem der vorhergehenden Ansprüche, bei dem ein Bandbeschleuniger mit einem Sulfonium-Kation mit einem Aryl-Rest, der einen Phenylrest umfasst, der Acetyloxy- ist, vorliegt. 10. Corona protective tape according to one of the preceding claims, in which a tape accelerator with a sulfonium cation with an aryl radical comprising a phenyl radical which is acetyloxy- is present.
11. Glimmschutzband nach einem der vorhergehenden Ansprüche, das als Bandbeschleuniger ein Supersäuren-Salz mit folgender chemischer Struktur umfasst:
11. Corona protection band according to one of the preceding claims, which comprises a superacid salt with the following chemical structure as the band accelerator:
Glimmschutzband nach einem der vorhergehenden Ansprüche, wobei die Polymermatrix mehrere Polyvinylalkohole umfasst.
Corona protection band according to one of the preceding claims, wherein the polymer matrix comprises a plurality of polyvinyl alcohols.
13. Glimmschutzband nach einem der vorhergehenden Ansprüche, wobei die Polymermatrix zumindest einen Polyvinylalkohol mit quervernetzten Anteilen umfasst. 13. Corona protection band according to one of the preceding claims, wherein the polymer matrix comprises at least one polyvinyl alcohol with crosslinked portions.
14. Glimmschutzband nach einem der vorhergehenden Ansprüche, wobei der elektrisch leitfähige und/oder teilleitfähige Füll- stoff zumindest eine Komponente, ausgewählt aus der Gruppe enthaltend Ruß, Graphit, Carbonnanotubes - CNTs-, Antimon do- tiertes Zinnoxid, Siliziumkarbid und/oder Aluminium dotiertes Siliziumkarbid, die jeweilige Komponente dotiert oder undo- tiert, beschichtet oder unbeschichtet, dotiert beschichtet oder undotiert beschichtet vorliegend, umfassen kann. 14. Corona protection band according to claim 1, wherein the electrically conductive and/or partially conductive filler material contains at least one component selected from the group consisting of carbon black, graphite, carbon nanotubes—CNTs—, antimony-doped tin oxide, silicon carbide, and/or aluminum Silicon carbide, the respective component can include doped or undoped, coated or uncoated, doped coated or undoped coated.
15. Verwendung eines Glimmschutzbandes nach einem der vorher- gehenden Ansprüche 1 bis 14 zur Herstellung eines Isolations- systems mit AGS, IPS und/oder EGS . 15. Use of a corona protection band according to one of the preceding claims 1 to 14 for producing an insulation system with AGS, IPS and/or EGS.
16. Elektrische rotierende Maschine mit einem Isolationssys- tem, das durch eine Verwendung nach Anspruch 15 erhältlich ist .
16. Electrical rotating machine with an insulation system, which is obtainable through a use according to claim 15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP20205914.3A EP3996113A1 (en) | 2020-11-05 | 2020-11-05 | Shielding stripe for rotary electric high voltage machine, use of same and electric machine |
| PCT/EP2021/080326 WO2022096429A1 (en) | 2020-11-05 | 2021-11-02 | Corona shielding strip for a high-voltage rotating electric machine, use thereof, and electric machine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4208882A1 true EP4208882A1 (en) | 2023-07-12 |
Family
ID=73448777
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20205914.3A Withdrawn EP3996113A1 (en) | 2020-11-05 | 2020-11-05 | Shielding stripe for rotary electric high voltage machine, use of same and electric machine |
| EP21805895.6A Pending EP4208882A1 (en) | 2020-11-05 | 2021-11-02 | Corona shielding strip for a high-voltage rotating electric machine, use thereof, and electric machine |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP20205914.3A Withdrawn EP3996113A1 (en) | 2020-11-05 | 2020-11-05 | Shielding stripe for rotary electric high voltage machine, use of same and electric machine |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20240006948A1 (en) |
| EP (2) | EP3996113A1 (en) |
| CN (1) | CN116368183A (en) |
| WO (1) | WO2022096429A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0995644A (en) * | 1994-12-12 | 1997-04-08 | Kansai Paint Co Ltd | Thermosetting type coating material composition |
| DE19839285C1 (en) | 1998-08-28 | 2000-04-27 | Siemens Ag | Glow protection tape |
| DE102010009462A1 (en) | 2010-02-26 | 2011-09-01 | Siemens Aktiengesellschaft | A method of making an end corona shielding material and an end corona shield with the final corona shielding material |
| DE102015214872A1 (en) | 2015-02-05 | 2016-08-11 | Siemens Aktiengesellschaft | Insulating tape for a coil and winding tape insulation system for electrical machines |
| EP3389058A1 (en) * | 2017-04-10 | 2018-10-17 | Siemens Aktiengesellschaft | Corona shielding band for electric high voltage machine |
| EP3716290A1 (en) * | 2019-03-28 | 2020-09-30 | Siemens Aktiengesellschaft | Formulation for an insulation system, insulation system thereof, and electric machine with insulation system |
-
2020
- 2020-11-05 EP EP20205914.3A patent/EP3996113A1/en not_active Withdrawn
-
2021
- 2021-11-02 CN CN202180074618.0A patent/CN116368183A/en active Pending
- 2021-11-02 EP EP21805895.6A patent/EP4208882A1/en active Pending
- 2021-11-02 US US18/251,492 patent/US20240006948A1/en active Pending
- 2021-11-02 WO PCT/EP2021/080326 patent/WO2022096429A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| CN116368183A (en) | 2023-06-30 |
| US20240006948A1 (en) | 2024-01-04 |
| WO2022096429A1 (en) | 2022-05-12 |
| EP3996113A1 (en) | 2022-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE19839285C1 (en) | Glow protection tape | |
| DE202016008773U1 (en) | Solid, in particular band-shaped insulation material, use thereof and electrical machine | |
| EP3278423B1 (en) | Resistance covering for a corona shield of an electric machine | |
| WO2011138413A2 (en) | Electrical insulation material and insulating tape for electrically insulating a medium and high voltage | |
| CH650010A5 (en) | HARDENABLE RESIN COMPOSITION, THIS CONTAINING Mica tape, ELECTRICALLY INSULATED COIL AND METHOD FOR THE PRODUCTION THEREOF. | |
| DE602004001781T2 (en) | ELECTRICAL PIPE COATED WITH A LIQUID LAYER AND MANUFACTURING PROCESS THEREOF | |
| EP4183028A1 (en) | Powder coating formulation for an insulation system of an electric machine, electric machine having an insulation system of this kind, and a method for producing an insulation system of this kind | |
| DE102010032949A1 (en) | Insulating systems with improved partial discharge resistance | |
| WO2020094328A1 (en) | Electrical operating means having an insulation system, and method for producing the insulation system | |
| EP3593361B1 (en) | Corona shielding band for electric high voltage machine | |
| EP4208882A1 (en) | Corona shielding strip for a high-voltage rotating electric machine, use thereof, and electric machine | |
| DE102014211122A1 (en) | Electrically defined conductive multifunctional tape, method of manufacture and use therefor | |
| DE102010041594A1 (en) | Filler for controlling electrical potentials in transformers, generators or the like | |
| EP3963605A1 (en) | Impregnating formulation, insulation material, method for producing an insulation material, and electrical machine with an insulation material | |
| DE602005001078T2 (en) | Organic thermistor with positive temperature coefficient | |
| WO2015090935A1 (en) | Breakdown-resistant and anti-arcing cast resin composition | |
| WO2023170112A1 (en) | Sub-conductor insulation and sub-conductor composite of an electric rotating machine | |
| DE3218287A1 (en) | INSULATING TAPE FOR PRODUCING AN INSULATING SLEEVE FOR ELECTRIC CONDUCTORS IMPREGNATED WITH A HEAT-CURING EPOXY RESIN-ACIDANHYDRIDE MIXTURE | |
| WO2005076290A1 (en) | Semiconducting winding strip and use thereof | |
| WO2024088848A1 (en) | Formulation for an insulation system, use of same and moulded body | |
| DE102014204416A1 (en) | Insulation tape, its use as electrical insulation for electrical machines, electrical insulation and method of making the insulation tape | |
| WO2021043541A1 (en) | Tape accelerator and use thereof, solid insulating material, and anhydride-free insulation system | |
| DE102021209276A1 (en) | Corona protection system, electrical machine and use of the corona protection system in an electrical machine | |
| EP4362048A1 (en) | Formulation for an insulation system, use thereof, and shaped body | |
| CH696992A5 (en) | Mica tape, useful for insulating windings of rotating electric machines, comprises carrier, mica layer and adhesive comprising copolymer, produced from ethylene and/or alpha-olefin, and olefin comonomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
| PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
| STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
| 17P | Request for examination filed |
Effective date: 20230405 |
|
| AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
| RAP1 | Party data changed (applicant data changed or rights of an application transferred) |
Owner name: INNOMOTICS GMBH |
|
| DAV | Request for validation of the european patent (deleted) | ||
| DAX | Request for extension of the european patent (deleted) |