TWI605029B - 不含銻的壓敏電阻組成物及積層式壓敏電阻器 - Google Patents
不含銻的壓敏電阻組成物及積層式壓敏電阻器 Download PDFInfo
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- TWI605029B TWI605029B TW105132868A TW105132868A TWI605029B TW I605029 B TWI605029 B TW I605029B TW 105132868 A TW105132868 A TW 105132868A TW 105132868 A TW105132868 A TW 105132868A TW I605029 B TWI605029 B TW I605029B
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- Prior art keywords
- additive
- zinc
- bismuth
- content
- containing compound
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims description 56
- 239000000654 additive Substances 0.000 claims description 93
- 230000000996 additive effect Effects 0.000 claims description 90
- 239000011521 glass Substances 0.000 claims description 75
- 150000001875 compounds Chemical class 0.000 claims description 52
- -1 boron bismuth zinc bismuth Chemical compound 0.000 claims description 43
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052787 antimony Inorganic materials 0.000 claims description 21
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 21
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 17
- 239000011651 chromium Substances 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 239000011701 zinc Substances 0.000 claims description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- VFDAVPHSABXRIY-UHFFFAOYSA-N lanthanum Chemical compound [La].[La].[La] VFDAVPHSABXRIY-UHFFFAOYSA-N 0.000 claims description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052797 bismuth Inorganic materials 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910001252 Pd alloy Inorganic materials 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 7
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 229910001260 Pt alloy Inorganic materials 0.000 claims description 4
- IHWJXGQYRBHUIF-UHFFFAOYSA-N [Ag].[Pt] Chemical compound [Ag].[Pt] IHWJXGQYRBHUIF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 3
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical compound N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001869 cobalt compounds Chemical class 0.000 claims description 2
- 229910000152 cobalt phosphate Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001923 silver oxide Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 3
- 238000005253 cladding Methods 0.000 claims 1
- 150000001868 cobalt Chemical class 0.000 claims 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims 1
- 229940093474 manganese carbonate Drugs 0.000 claims 1
- 235000006748 manganese carbonate Nutrition 0.000 claims 1
- 239000011656 manganese carbonate Substances 0.000 claims 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 claims 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 24
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000011787 zinc oxide Substances 0.000 description 11
- IYNWNKYVHCVUCJ-UHFFFAOYSA-N bismuth Chemical compound [Bi].[Bi] IYNWNKYVHCVUCJ-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 6
- 239000008187 granular material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012768 molten material Substances 0.000 description 6
- 229910007612 Zn—La Inorganic materials 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- VJFCXDHFYISGTE-UHFFFAOYSA-N O=[Co](=O)=O Chemical compound O=[Co](=O)=O VJFCXDHFYISGTE-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- RZRNZDQNXWVZNY-UHFFFAOYSA-N [B].[B].[B].[Cr].[Cr].[Cr].[Cr].[Cr] Chemical compound [B].[B].[B].[Cr].[Cr].[Cr].[Cr].[Cr] RZRNZDQNXWVZNY-UHFFFAOYSA-N 0.000 description 2
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 2
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- UPIXZLGONUBZLK-UHFFFAOYSA-N platinum Chemical compound [Pt].[Pt] UPIXZLGONUBZLK-UHFFFAOYSA-N 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- PCBMYXLJUKBODW-UHFFFAOYSA-N [Ru].ClOCl Chemical compound [Ru].ClOCl PCBMYXLJUKBODW-UHFFFAOYSA-N 0.000 description 1
- IVGZFMVIHQRCHJ-UHFFFAOYSA-N [Zn].[Bi].[B] Chemical compound [Zn].[Bi].[B] IVGZFMVIHQRCHJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- UHPOHYZTPBGPKO-UHFFFAOYSA-N bis(boranylidyne)chromium Chemical compound B#[Cr]#B UHPOHYZTPBGPKO-UHFFFAOYSA-N 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- VTHAZHHBZCRMKA-UHFFFAOYSA-N boranylidynelanthanum Chemical compound [La]#B VTHAZHHBZCRMKA-UHFFFAOYSA-N 0.000 description 1
- DZUDZSQDKOESQQ-UHFFFAOYSA-N cobalt hydrogen peroxide Chemical compound [Co].OO DZUDZSQDKOESQQ-UHFFFAOYSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- VHMSCVSXUXWVGT-UHFFFAOYSA-N lanthanum Chemical compound [La].[La].[La].[La] VHMSCVSXUXWVGT-UHFFFAOYSA-N 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/15—Silica-free oxide glass compositions containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/6303—Inorganic additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C12/00—Powdered glass; Bead compositions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/62605—Treating the starting powders individually or as mixtures
- C04B35/62625—Wet mixtures
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Description
本創作關於一種壓敏電阻組成物，尤指一種不含銻的壓敏電阻組成物。本創作另關於一種由該組成物經低溫燒結製成的積層式壓敏電阻器。
壓敏電阻器因具有良好的抗靜電能力，目前已被廣泛應用於電子產業中的抗靜電保護元件；且為符合薄型化之市場需求，小體積的積層式壓敏電阻器更是被廣為使用。
傳統的壓敏電阻器因含有銻之毒害成分，而會對環境造成危害。近年來，隨著環保意識的提倡，以往具危害性的壓敏電阻材料也逐漸被檢討與禁止。
為避免汙染環境，美國專利公開第2012/0153237號案、美國專利公開第2005/0143262號案及台灣專利公開第200916432號案揭示使用含有鐠或鑭的壓敏電阻材料，以取代傳統含銻的壓敏電阻材料。然而，含有鐠或鑭的壓敏電阻材料需要經過燒結溫度為1200°C左右的高溫燒結製程，才能製得具有良好壓敏特性的積層式壓敏電阻器；且該等專利文獻所揭露的技術手段需要配合使用價格高昂的高純度鉑金屬、高純度鈀金屬、高鉑含量的銀鉑合金或高鈀含量的銀鈀合金作為內電極，導致不含銻的積層式壓敏電阻器之成本大幅提升。
有鑒於上述現有技術的缺點，本創作的目的在於提供一種不含銻的壓敏電阻組成物，其能與鉑含量為30 wt%以下的銀鉑合金內電極或鈀含量為30 wt%以下的銀鈀合金內電極經低溫燒結製得一具有高通流特性、抗靜電特性及低製造成本的積層式壓敏電阻器。
為達到前述的創作目的，本創作所採取的技術手段係令該不含銻的壓敏電阻組成物，其中包含： 一氧化鋅； 第一添加劑，其係選自於下列構成的群組：硼鉍鋅鐠玻璃(B-Bi-Zn-Pr glass)、硼鉍鋅鑭玻璃(B-Bi-Zn-La glass)及其混合物； 第二添加劑，其係選自於下列構成的群組：含鈷化合物、含鉻化合物、含鎳化合物、含錳化合物及其混合物； 第三添加劑，其包含二氧化錫(SnO
2)；以及 第四添加劑，其係選自於下列構成的群組：含鋁化合物、含銀化合物及其混合物； 其中，以所述不含銻的壓敏電阻組成物之整體為基準，所述第一添加劑的總含量為0.05 wt%至20 wt%，所述第二添加劑的個別含量為0.1 wt%至5.0 wt%，所述第三添加劑的含量為0.1 wt%至1.5 wt%，所述第四添加劑的個別含量為0.001 wt%至1.0 wt%。
當該第一添加劑為單獨一種時，所述「第一添加劑之總含量」係指單獨一種第一添加劑之含量；舉例而言，當第一添加劑為硼鉍鋅鐠玻璃時，該第一添加劑之總含量即為硼鉍鋅鐠玻璃之含量；同理，當第一添加劑為硼鉍鋅鑭玻璃，該第一添加劑之總含量即為硼鉍鋅鑭玻璃之含量。
當該第一添加劑為多種之混合時，所述「第一添加劑之總含量」係指多種第一添加劑之含量的總合；舉例而言，當第一添加劑為硼鉍鋅鐠玻璃與硼鉍鋅鑭玻璃之組合時，該第一添加劑之總含量即為硼鉍鋅鐠玻璃之含量與硼鉍鋅鑭玻璃之含量的總合。
所述「第二添加劑之個別含量」係指單獨一種第二添加劑之含量。舉例而言，當第二添加劑由含鈷化合物所組成時，第二添加劑之個別含量為0.1 wt%至5.0 wt%。同理，當第二添加劑由含鉻化合物所組成時，其第二添加劑之個別含量為0.1 wt%至5.0 wt%；當第二添加劑由含鎳化合物所組成時，其第二添加劑之個別含量為0.1 wt%至5.0 wt%；當第二添加劑由含錳化合物所組成時，其第二添加劑之個別含量為0.1 wt%至5.0 wt%。
較佳的是，所述第二添加劑為含鈷化合物、含鉻化合物、含鎳化合物及含錳化合物之組合，且該第二添加劑之總含量為0.4 wt%至20.0 wt%。
所述「第二添加劑之總含量」係指多種第二添加劑之個別含量的總和。舉例而言，當第二添加劑同時具有含鈷化合物、含鉻化合物、含鎳化合物和含錳化合物時，第二添加劑之總含量為0.4 wt%至20.0 wt%。
較佳的是，所述第二添加劑的含鈷化合物可為鈷氧化物、鈷的氫氧化物[Co(OH)
2]、高鈷酸鹽、碳酸鈷(CoCO
3)及磷酸鈷[Co
3(PO
4)
2]中之至少一者，但不以此為限。舉例而言，所述鈷氧化物可為四氧化三鈷(Co
3O
4)，所述高鈷酸鹽為高鈷酸鉀(K
3CoO
4)但不以此為限。
較佳的是，所述第二添加劑的含鉻化合物可為鉻氧化物、重鉻酸鹽、鉻硼化物及鉻氮化物中之至少一者，但不以此為限。舉例而言，所述鉻氧化物可為三氧化二鉻(Cr
2O
3)，所述重鉻酸鹽可為重鉻酸銨[(NH
4)
2Cr
2O
7]，所述鉻硼化物可為一硼化鉻(CrB)或二硼化鉻(CrB
2)，所述鉻氮化物可為一氮化二鉻(Cr
2N)，但不以此為限。
較佳的是，所述第二添加劑的含鎳化合物可為鎳氧化物、碳酸鎳(NiCO
3)及硝酸鎳[Ni(NO
3)
2]中之至少一者，但不以此為限。舉例而言，所述鎳氧化物可為一氧化鎳(NiO)，但不以此為限。
較佳的是，所述第二添加劑的含錳化合物可為錳氧化物、碳酸錳(MnCO
3)、硝酸錳[Mn(NO
3)
2]及硼氫化錳[Mn(BH
4)
2]中之至少一者，但不以此為限。舉例而言，所述錳氧化物可為四氧化三錳(Mn
3O
4)或一氧化二錳(Mn
2O)，但不以此為限。
較佳的是，所述第三添加劑包含二氧化矽或二氧化鍺。
所述「第四添加劑之個別含量」係指單獨一種第四添加劑之含量。舉例而言，當第四添加劑由含鋁化合物所組成時，第四添加劑之個別含量為0.001 wt%至1.0 wt%。同理，當第四添加劑由含銀化合物所組成時，其第二添加劑之個別含量為0.001 wt%至1.0 wt%。
較佳的是，所述第四添加劑為含鋁化合物及含銀化合物之組合，且該第四添加劑之總含量為0.002 wt%至2.0 wt%。
所述「第四添加劑之總含量」係指多種第四添加劑之個別含量的總和。舉例而言，當第四添加劑由含鋁化合物及含銀化合物所組成時，第四添加劑之總含量為0.002 wt%至2.0 wt%。
較佳的是，所述第四添加劑的含鋁化合物可為鋁氧化物[如：三氧化二鋁(Al
2O
3)]及硝酸鋁[Al(NO
3)
3]，所述第四添加劑的含銀化合物可為銀氧化物[如：一氧化二銀(Ag
2O)]及硝酸銀(AgNO
3)；舉例而言，所述硝酸鋁可為九水合硝酸鋁[Al(NO
3)
3‧9H
2O]，但不以此為限。
較佳的是，以所述硼鉍鋅鐠玻璃中所含有的硼、鉍、鋅及鐠之總量為基準，所述硼鉍鋅鐠玻璃的硼含量為20 at%至70 at%，所述硼鉍鋅鐠玻璃的鉍含量為2 at%至30 at%，所述硼鉍鋅鐠玻璃的鋅含量為10 at%至60 at%，所述硼鉍鋅鐠玻璃的鐠含量為 5 at%至30 at%。
更佳的是，以所述硼鉍鋅鐠玻璃中所含有的硼、鉍、鋅及鐠之總量為基準，所述硼鉍鋅鐠玻璃的硼含量為30 at%至60 at%，所述硼鉍鋅鐠玻璃的鉍含量為5 at%至20 at%，所述硼鉍鋅鐠玻璃的鋅含量為20 at%至50 at%，所述硼鉍鋅鐠玻璃的鐠含量為10 at%至20 at%。
較佳的是，以所述硼鉍鋅鑭玻璃中所含有的硼、鉍、鋅及鑭之總量為基準，所述硼鉍鋅鑭玻璃的硼含量為20 at%至70at%，所述硼鉍鋅鑭玻璃的鉍含量為2 at%至30 at%，所述硼鉍鋅鑭玻璃的鋅含量為10 at%至60 at%，所述硼鉍鋅鑭玻璃的鑭含量為5 at%至30 at%。
更佳的是，以所述硼鉍鋅鑭玻璃中所含有的硼、鉍、鋅及鑭之總量為基準，所述硼鉍鋅鑭玻璃的硼含量為30 at%至60 at%，所述硼鉍鋅鑭玻璃的鉍含量為5 at%至20 at%，所述硼鉍鋅鑭玻璃的鋅含量為20 at%至50 at%，所述硼鉍鋅鑭玻璃的鑭含量為10 at%至20 at%。
本創作的不含銻的壓敏電阻組成物可作為積層式壓敏電阻器之燒結體之原料，令積層式壓敏電阻器具有優異的抗靜電放電性質及高峰值電流等壓敏電阻特性。且由於所述壓敏電阻組成物係不含有銻金屬，故能符合環保需求。
較佳的是，以所述不含銻的壓敏電阻組成物之整體為基準，所述第一添加劑的含量為1.5 wt%至5.5 wt%，從而令由本創作的不含銻的壓敏電阻組成物所製得的積層式壓敏電阻器的抗靜電放電性質及高峰值電流進一步提升。
較佳的是，所述第一添加劑的粒徑介於50 nm至500 nm之間。藉此，令所述壓敏電阻組成物可經由低溫燒結製程製得具有高緻密度的壓敏電阻。
本創作另提供一種積層式壓敏電阻器，其中包含： 一燒結體，其具有一第一端及一位置相對於該第一端的第二端； 數個內電極，該等內電極間隔設置於該燒結體內，且相鄰的兩內電極分別與該第一端及該第二端相接； 一第一外電極，其包覆設置於該第一端上且與相對應的內電極接觸；以及 一第二外電極，其包覆設置於該第二端上且與相對應的內電極接觸； 其中，該燒結體係由如前述的不含銻的壓敏電阻組成物所製成。
本創作的積層式壓敏電阻器因具有由如前述的不含銻的壓敏電阻組成物所製成之燒結體，故該積層式壓敏電阻器能兼具有良好的抗靜電放電性質及高峰值電流等壓敏電阻特性等優點，且亦可避免危害環境，從而具有廣泛的應用性。
較佳的是，該燒結體係由前述的不含銻的壓敏電阻組成物可經燒結溫度低於1200°C之燒結製程所製得。該燒結溫度較佳為900°C至1150°C，該燒結溫度更佳為950°C至1100°C。
較佳的是，該等內電極包含鈀含量為30 wt%以下的銀鈀合金或鉑含量為30 wt%以下的銀鉑合金。
據此，本創作的積層式壓敏電阻器係可由本創作的不含銻的壓敏電阻組成物與低鈀含量的銀鈀合金或低鉑含量的銀鉑合金之內電極經由900°C至1150°C之燒結製程而製得，從而降低本創作的積層式壓敏電阻器之製造成本及燒結溫度。
本創作的不含銻的壓敏電阻組成物包含有一氧化鋅、第一添加劑、第二添加劑、第三添加劑及第四添加劑。所述第一添加劑係選自於下列構成的群組：硼鉍鋅鐠玻璃(B-Bi-Zn-Pr glass)、硼鉍鋅鑭玻璃(B-Bi-Zn-La glass)及其混合物。所述第二添加劑係選自於下列構成的群組：含鈷化合物、含鉻化合物、含鎳化合物、含錳化合物及其混合物。所述第三添加劑包含二氧化錫(SnO
2)。所述第四添加劑係選自於下列構成的群組：含鋁化合物、含銀化合物及其混合物。其中，以所述不含銻的壓敏電阻組成物之整體為基準，所述第一添加劑的總含量為0.05 wt%至20 wt%，所述第二添加劑個別含量為0.1 wt%至5.0 wt%所述第三添加劑的含量為0.1 wt%至1.5 wt%，所述第四添加劑的個別含量為0.001 wt%至1.0 wt%。
所述硼鉍鋅鐠玻璃之製法：令三氧化二硼(B
2O
3)、三氧化二鉍(Bi
2O
3)、一氧化鋅(ZnO)及十一氧化六鐠(Pr
6O
11)的粉末經由混合、研磨及烘乾後獲得一預處理粉末，其中，以三氧化二硼、三氧化二鉍、一氧化鋅及十一氧化六鐠之總重量為基準，三氧化二硼之用量為10 wt%至30 wt%，三氧化二鉍之用量為10 wt%至30 wt%，一氧化鋅之用量為10 wt%至30 wt%，十一氧化六鐠之用量為10 wt%至30 wt%。再令該預處理粉末於500°C至900°C之溫度下轉變為一熔融物質。接著，令該熔融物質經高壓噴塗形成數個液滴。最後，快速凝固該等液滴獲得所述硼鉍鋅鐠玻璃，且所述硼鉍鋅鐠玻璃之粒徑為50 奈米(nm)至500 nm。
所述硼鉍鋅鑭玻璃之製法與前述硼鉍鋅鐠玻璃之製法大致相同，所述硼鉍鋅鑭玻璃之製法與前述硼鉍鋅鐠玻璃之製法不同之處在於：所述硼鉍鋅鑭玻璃係由三氧化二硼(B
2O
3)、三氧化二鉍(Bi
2O
3)、一氧化鋅(ZnO)及三氧化二鑭(La
2O
3)所製得，且以三氧化二硼、三氧化二鉍、一氧化鋅及三氧化二鑭之總重量為基準，三氧化二鑭之用量為10 wt%至30 wt%。
如圖1所示，本創作的積層式壓敏電阻器10包含有一燒結體11、數個內電極12、13、一第一外電極14及一第二外電極15，該燒結體11具有一第一端及一位置相對於該第一端的第二端，該等內電極12、13間隔設置於該燒結體11內，且相鄰的兩內電極12、13分別與該第一端及該第二端相接，該第一外電極14包覆設置於該第一端上且與相對應的內電極12接觸，該第二外電極15包覆設置於該第二端上且與相對應的內電極13接觸。
所述的積層式壓敏電阻器係經低溫燒結製成。且所述的積層式壓敏電阻器之燒結體可由前述不含銻的壓敏電阻組成物所製成。所述的積層式壓敏電阻器之製法如下：
首先，混合所述第一添加劑、第二添加劑、第三添加劑及第四添加劑後獲得一混合物；再令該混合物於750°C至950°C之溫度下煅燒2小時，獲得一煅燒粉末；接著，研磨該煅燒粉末以獲得一複合粉料；之後，均勻混合該複合粉料與氧化鋅粉後，加入分散劑、黏結劑、塑化劑及有機溶劑，獲得一陶瓷漿料；然後，以刮刀將該陶瓷漿料刮成厚度約5微米(μm)至150 μm的生胚薄片。
之後，將數個生胚薄片重疊製成厚度約200 μm的上蓋及下蓋；然後，於所述下蓋上印刷上內電極，並將印刷有內電極的下蓋烘乾；之後，將數個厚度為30 μm的生胚薄片依序層疊於該下蓋上，其中，於各生胚薄片於被相鄰的生胚薄片重疊之前，各生胚薄片係先被印刷設置有內電極，且所述內電極可為鉑(Pt)、鈀(Pd)、金(Au)、銀(Ag)、鎳(Ni)或其中至少兩種金屬之合金。接著，於將該上蓋疊置於最上層的生胚薄片上後，壓合該上蓋、該等生胚薄片及該下蓋以獲得一堆疊體。
接下來，將該堆疊體切割為數個生胚粒；然後，將所述生胚粒放入排膠爐中，以300°C至600°C之溫度進行排膠；再以900°C至1200°C之溫度燒結排膠後的生胚粒，獲得所述燒結體；再以600°C至900°C於所述燒結體之兩端燒附上所述外電極，以獲得所述積層式壓敏電阻器；其中，所述外電極包含銀(Ag)或銅(Cu)等金屬。其中，排膠溫度較佳為400°C，燒結溫度較佳為950°C至1050°C。
以下，將藉由實施例說明本發明之實施方式，熟習此技藝者可經由本說明書之內容輕易地了解本發明所能達成之優點與功效，並且於不悖離本發明之精神下進行各種修飾與變更，以施行或應用本發明之內容。
實施例
1
：
硼鉍鋅鐠玻璃之製備
令三氧化二硼、三氧化二鉍、一氧化鋅及十一氧化六鐠的粉末經由混合、研磨及烘乾後獲得一預處理粉末，其中，三氧化二硼、三氧化二鉍、一氧化鋅及十一氧化六鐠之重量比為20：20：30：30。再加熱該預處理粉末至850°C以獲得一熔融物質。 接著，令該熔融物質經高壓噴塗形成數個液滴。最後，快速凝固該等液滴獲得本實施例之硼鉍鋅鐠玻璃，且本實施例之硼鉍鋅鐠玻璃之粒徑為200奈米，本實施例之硼鉍鋅鐠玻璃之組份示於表1中。
實施例
2
：
硼鉍鋅鑭玻璃之製備
令三氧化二硼、三氧化二鉍、一氧化鋅及三氧化二鑭經由混合、研磨及烘乾後獲得一預處理粉末，其中，三氧化二硼、三氧化二鉍、一氧化鋅及三氧化二鑭之重量比為20：20：30：30。再加熱該預處理粉末至850°C以獲得一熔融物質。接著，令該熔融物質經高壓噴塗形成數個液滴。最後，快速凝固該等液滴獲得本實施例之硼鉍鋅鑭玻璃，且本實施例之硼鉍鋅鑭玻璃之粒徑為200奈米，本實施例之硼鉍鋅鑭玻璃之組份示於表1中。
表1：實施例1之硼鉍鋅鐠玻璃與實施例2之硼鉍鋅鑭玻璃之組份
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 元素種類 </td><td> 硼(B) </td><td> 鉍(Bi) </td><td> 鋅(Zn) </td><td> 鐠(Pr) </td><td> 鑭(La) </td><td> 總合 </td></tr><tr><td> 實施例1 </td><td> 47.68 at% </td><td> 7.12 at% </td><td> 30.58 at% </td><td> 14.62 at% </td><td> 0.00 at% </td><td> 100 at% </td></tr><tr><td> 實施例2 </td><td> 47.36 at% </td><td> 7.08 at% </td><td> 30.38 at% </td><td> 0.00 at% </td><td> 15.18 at% </td><td> 100 at% </td></tr></TBODY></TABLE>
實施例
3
至
8
：積層式壓敏電阻器之製備
實施例3至8係以實施例1之硼鉍鋅鐠玻璃、四氧化三鈷、三氧化二鈷、一氧化二錳、一氧化鎳、二氧化錫、硝酸鋁、硝酸銀及一氧化鋅為原料，依據表2所示的比例進行積層式壓敏電阻器之製備如下：
混合實施例1之硼鉍鋅鐠玻璃、四氧化三鈷、三氧化二鈷、一氧化二錳、一氧化鎳、二氧化錫、硝酸鋁及硝酸銀獲得一混合物；於研磨該混合物後，令該混合物於850°C之溫度下煅燒2小時，獲得一煅燒粉末；然後，研磨該煅燒粉末以獲得一複合粉料；於混合該複合粉料、氧化鋅粉、黏結劑、塑化劑及甲苯後，進行24小時的球磨處理，獲得一陶瓷漿料；然後，以刮刀將該陶瓷漿料刮成厚度約30 μm的生胚薄片。其中，以所述陶瓷漿料為基準，該分散劑為1 wt%，該黏結劑為10 wt%、塑化劑為2 wt%，且黏結劑為聚乙烯醇縮丁醛[poly(vinyl butyral)]，塑化劑為醇類塑化劑或酯類塑化劑；於實施例3至8中，塑化劑係使用三乙二醇雙(2-乙酸己酯)[triethylene glycol bis(2-ethylhexanoate)]。
之後，將數個生胚薄片重疊製成厚度約200 μm的下蓋；然後，於所述下蓋上印刷上內電極，並將印刷有內電極的下蓋烘乾；之後，將數個厚度為30 μm的生胚薄片依序層疊於該下蓋上，其中，於各生胚薄片於被相鄰的生胚薄片重疊之前，各生胚薄片係先被印刷設置有內電極，且所述內電極為銀鈀合金，且所述內電極中所含有的銀與鈀的重量比為70：30。接著，將數個生胚薄片重疊製成厚度約200 μm的上蓋，且於將該上蓋疊置於最上層的生胚薄片上後，壓合該上蓋、該等生胚薄片及該下蓋以獲得一堆疊體。
接下來，將該堆疊體切割為數個長、寬、高依序為1.0毫米(mm)、0.55 mm、0.55 mm的生胚粒；然後，將所述生胚粒放入排膠爐中，以400°C之溫度進行排膠24小時；接著，令排膠後的生胚粒進行燒結溫度為1000°C、燒結時間為2小時之燒結處理，以獲得一燒結體；接下來，以750°C於所述燒結體之兩端燒附上外電極，製得各實施例之積層式壓敏電阻器；其中，所述外電極包含銀。
實施例
9
至
14
：積層式壓敏電阻器之製備
實施例9至14係以與實施例3至8大致相同的方法製作積層式壓敏電阻器，惟實施例9至14係改以實施例2之硼鉍鋅鑭玻璃、四氧化三鈷、三氧化二鈷、一氧化二錳、一氧化鎳、二氧化錫、硝酸鋁、硝酸銀及一氧化鋅為原料，實施例9至14的原料之組成比例示於表2中。
實施例
15
至
19
：積層式壓敏電阻器之製備
實施例15至19係以與實施例3至8大致相同的方法製作積層式壓敏電阻器，惟實施例15至19係以實施例1之硼鉍鋅鐠玻璃、實施例2之硼鉍鋅鑭玻璃、四氧化三鈷、三氧化二鈷、一氧化二錳、一氧化鎳、二氧化錫、硝酸鋁、硝酸銀及一氧化鋅為原料，實施例15至19的原料之組成比例示於表2中。
實施例
20
至
26
：積層式壓敏電阻器之製備
實施例20至26係以與實施例3至8大致相同的方法製作積層式壓敏電阻器，惟實施例20至26的原料之組成比例如表3所示。
實施例
27
至
33
：積層式壓敏電阻器之製備
實施例27至33係以與實施例9至14大致相同的方法製作積層式壓敏電阻器，惟實施例27至33之的原料之組成比例如表3所示。
比較例：積層式壓敏電阻器之製備
比較例係以與實施例3至26大致相同的方法製作積層式壓敏電阻器，惟比較例之原料未含有實施例1之硼鉍鋅鐠玻璃及實施例2之硼鉍鋅鑭玻璃，比較例的原料之組成比例如表4所示。
表2：實施例3至19之原料的組成比例(單位：wt%)及測試例之測試結果
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 實施例 </td><td> 原料的組成比例(總合：100 wt%) </td><td> 壓敏電阻特性 </td></tr><tr><td> ZnO </td><td> B-Bi-Zn-Pr glass </td><td> B-Bi-Zn-La glass </td><td> Co<sub>3</sub>O<sub>4</sub></td><td> Cr<sub>2</sub>O<sub>3</sub></td><td> Mn<sub>2</sub>O </td><td> NiO </td><td> SnO<sub>2</sub></td><td> AgNO<sub>3</sub></td><td> Al(NO<sub>3</sub>)<sub>3</sub></td><td> 崩潰電壓(V<sub>1mA</sub>) </td><td> 非線性 係數(α) </td><td> 最大峰值電流 </td><td> 抗ESD性 </td></tr><tr><td> 3 </td><td> 95.35 </td><td> 0.05 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 84.2 V </td><td> 25.1 </td><td> 10 A </td><td> 10kV </td></tr><tr><td> 4 </td><td> 93.4 </td><td> 2.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 30.4 V </td><td> 45.4 </td><td> 20 A </td><td> 30kV </td></tr><tr><td> 5 </td><td> 90.4 </td><td> 5.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 20.7 V </td><td> 35.6 </td><td> 20 A </td><td> 30kV </td></tr><tr><td> 6 </td><td> 85.4 </td><td> 10.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 18.5 V </td><td> 28.5 </td><td> 20 A </td><td> 25kV </td></tr><tr><td> 7 </td><td> 80.4 </td><td> 15.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 10.3 V </td><td> 18.0 </td><td> 20 A </td><td> 15kV </td></tr><tr><td> 8 </td><td> 75.4 </td><td> 20.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 7.6 V </td><td> 12.7 </td><td> 15 A </td><td> 10kV </td></tr><tr><td> 9 </td><td> 95.35 </td><td> 0 </td><td> 0.05 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 72.4 V </td><td> 21.2 </td><td> 10 A </td><td> 10kV </td></tr><tr><td> 10 </td><td> 93.4 </td><td> 0 </td><td> 2.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 26.1 V </td><td> 41.2 </td><td> 20 A </td><td> 30kV </td></tr><tr><td> 11 </td><td> 90.4 </td><td> 0 </td><td> 5.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 18.2 V </td><td> 32.3 </td><td> 20 A </td><td> 30kV </td></tr><tr><td> 12 </td><td> 85.4 </td><td> 0 </td><td> 10.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 15.4 V </td><td> 24.4 </td><td> 20 A </td><td> 25kV </td></tr><tr><td> 13 </td><td> 80.4 </td><td> 0 </td><td> 15.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 10.6 V </td><td> 14.6 </td><td> 15 A </td><td> 15kV </td></tr><tr><td> 14 </td><td> 75.4 </td><td> 0 </td><td> 20.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 8.4 V </td><td> 10.4 </td><td> 15 A </td><td> 10kV </td></tr><tr><td> 15 </td><td> 93.4 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 28.4 V </td><td> 43.2 </td><td> 20 A </td><td> 30kV </td></tr><tr><td> 16 </td><td> 90.4 </td><td> 2.5 </td><td> 2.5 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 17.7 V </td><td> 32.4 </td><td> 20 A </td><td> 30kV </td></tr><tr><td> 17 </td><td> 85.4 </td><td> 5.0 </td><td> 5.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 15.5 V </td><td> 24.5 </td><td> 20 A </td><td> 25kV </td></tr><tr><td> 18 </td><td> 80.4 </td><td> 7.5 </td><td> 7.5 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 9.3 V </td><td> 14.6 </td><td> 20 A </td><td> 15kV </td></tr><tr><td> 19 </td><td> 75.4 </td><td> 10 </td><td> 10 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 8.6 V </td><td> 10.8 </td><td> 15 A </td><td> 10kV </td></tr></TBODY></TABLE>
表3：實施例27至33之原料的組成比例(單位：wt%)及測試例之測試結果
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> 實施例 </td><td> 原料的組成比例(總合：100 wt%) </td><td> 壓敏電阻特性 </td></tr><tr><td> ZnO </td><td> B-Bi-Zn-Pr glass </td><td> B-Bi-Zn-La glass </td><td> Co<sub>3</sub>O<sub>4</sub></td><td> Cr<sub>2</sub>O<sub>3</sub></td><td> Mn<sub>2</sub>O </td><td> NiO </td><td> SnO<sub>2</sub></td><td> AgNO<sub>3</sub></td><td> Al(NO<sub>3</sub>)<sub>3</sub></td><td> 崩潰電壓(V<sub>1mA</sub>) </td><td> 非線性 係數(α) </td><td> 最大峰值電流 </td><td> 抗ESD性 </td></tr><tr><td> 20 </td><td> 97.498 </td><td> 2.0 </td><td> 0 </td><td> 0.1 </td><td> 0.1 </td><td> 0.1 </td><td> 0.1 </td><td> 0.1 </td><td> 0.001 </td><td> 0.001 </td><td> 20.3 V </td><td> 34.2 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 21 </td><td> 93.898 </td><td> 2.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.1 </td><td> 0.001 </td><td> 0.001 </td><td> 28.2 V </td><td> 44.4 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 22 </td><td> 77.898 </td><td> 2.0 </td><td> 0 </td><td> 5.0 </td><td> 5.0 </td><td> 5.0 </td><td> 5.0 </td><td> 0.1 </td><td> 0.001 </td><td> 0.001 </td><td> 42.6 V </td><td> 36.8 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 23 </td><td> 92.998 </td><td> 2.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.001 </td><td> 0.001 </td><td> 36.1 V </td><td> 42.7 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 24 </td><td> 92.498 </td><td> 2.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.5 </td><td> 0.001 </td><td> 0.001 </td><td> 36.8 V </td><td> 41.2 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 25 </td><td> 92.9 </td><td> 2.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.05 </td><td> 0.05 </td><td> 35.2 V </td><td> 45.6 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 26 </td><td> 91 </td><td> 2.0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 36.0 V </td><td> 38.4 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 27 </td><td> 97.498 </td><td> 0 </td><td> 2.0 </td><td> 0.1 </td><td> 0.1 </td><td> 0.1 </td><td> 0.1 </td><td> 0.1 </td><td> 0.001 </td><td> 0.001 </td><td> 18.6 V </td><td> 32.1 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 28 </td><td> 93.898 </td><td> 0 </td><td> 2.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.1 </td><td> 0.001 </td><td> 0.001 </td><td> 27.8 V </td><td> 42.2 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 29 </td><td> 77.898 </td><td> 0 </td><td> 2.0 </td><td> 5.0 </td><td> 5.0 </td><td> 5.0 </td><td> 5.0 </td><td> 0.1 </td><td> 0.001 </td><td> 0.001 </td><td> 40.3 V </td><td> 36.3 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 30 </td><td> 92.998 </td><td> 0 </td><td> 2.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.001 </td><td> 0.001 </td><td> 34.6 V </td><td> 41.5 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 31 </td><td> 92.498 </td><td> 0 </td><td> 2.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.5 </td><td> 0.001 </td><td> 0.001 </td><td> 32.5 V </td><td> 40.4 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 32 </td><td> 92.9 </td><td> 0 </td><td> 2.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.05 </td><td> 0.05 </td><td> 34.0 V </td><td> 42.5 </td><td> 20 A </td><td> 30 kV </td></tr><tr><td> 33 </td><td> 91 </td><td> 0 </td><td> 2.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 35.5 V </td><td> 36.0 </td><td> 20 A </td><td> 30 kV </td></tr></TBODY></TABLE>
表4：比較例之原料的組成比例(單位：wt%)及測試例之測試結果
<TABLE border="1" borderColor="#000000" width="85%"><TBODY><tr><td> </td><td> 原料的組成比例(總合：100 wt%) </td><td> 壓敏電阻特性 </td></tr><tr><td> ZnO </td><td> B-Bi-Zn-Pr glass </td><td> B-Bi-Zn-La glass </td><td> Co<sub>3</sub>O<sub>4</sub></td><td> Cr<sub>2</sub>O<sub>3</sub></td><td> Mn<sub>2</sub>O </td><td> NiO </td><td> SnO<sub>2</sub></td><td> AgNO<sub>3</sub></td><td> Al(NO<sub>3</sub>)<sub>3</sub></td><td> 崩潰電壓(V<sub>1mA</sub>) </td><td> 非線性 係數(α) </td><td> 最大峰值電流 </td><td> 抗ESD性 </td></tr><tr><td> 比較例 </td><td> 95.4 </td><td> 0 </td><td> 0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 1.0 </td><td> 0.5 </td><td> 0.05 </td><td> 0.05 </td><td> 2 V </td><td> 0 </td><td> 0 A </td><td> 0 kV </td></tr></TBODY></TABLE>
測試例：壓敏電阻特性
於電流為1毫安培(mA)之條件下量測各實施例及比較例的積層式壓敏電阻器之崩潰電壓(V
1mA)，並依據實施例3至33中之各實施例及比較例的積層式壓敏電阻器之I-V特性曲線計算出實施例3至33中之各實施例及比較例的積層式壓敏電阻器的非線性係數(α)。
對實施例3至33中之各實施例及比較例的積層式壓敏電阻器之外電極施加一次8/20 μs波形之脈衝電流，當實施例3至33中之各實施例及比較例的積層式壓敏電阻器之電阻變化率在10%以內時，測得實施例3至33中之各實施例及比較例的積層式壓敏電阻器之最大峰值電流(maximum surge current)。
依據國際電工協會(IEC，International Electro-technical Commission)61000-4-2之靜電測試規範(即IEC 61000-4-2)之接觸放電模式(contact discharge mode)，對實施例3至33中之各實施例及比較例的積層式壓敏電阻器之外電極施加十次靜電放電(electrostatic discharge)，測試電壓為8仟伏(kV)至30kV；以實施例3至33中之各實施例及比較例的積層式壓敏電阻器之電阻變化率在10%以內之最高測試電壓評價實施例3至33中之各實施例及比較例的積層式壓敏電阻器之抗靜電放電能力。
實施例3至33中之各實施例及比較例的積層式壓敏電阻器的崩潰電壓、非線性係數、最大峰值電流及抗靜電放電能力之測試結果示於表2至4中。
如前所述，相較於實施例3至33，比較例之原料未含有實施例1之硼鉍鋅鐠玻璃及實施例2之硼鉍鋅鑭玻璃。如表所示：比較例的積層式壓敏電阻器之崩潰電壓僅2 V、非線性係數為0、最大峰值電流為0 A且無法通過本測試例的抗靜電放電能力測試；實施例3至33中之各實施例的積層式壓敏電阻器之崩潰電壓可達6 V以上、非線性係數可達10、最大峰值電流可達15 A以上且抗靜電放電能力可達10 kV。由此可證，實施例3至33中之各實施例的積層式壓敏電阻器係能具有良好的崩潰電壓、非線性係數、最大峰值電流及抗靜電放電能力等壓敏電阻特性。
由上述可知，所述不含銻的壓敏電阻組成物係能與鉑含量為30 wt%以下的銀鉑合金內電極或鈀含量為30 wt%以下的銀鈀合金內電極經低於1200°C之燒結製程製得所述積層式壓敏電阻器，故能令所述積層式壓敏電阻器之製造成本降低。且所述積層式壓敏電阻器係可兼具良好的崩潰電壓、非線性係數、最大峰值電流及抗靜電放電能力等壓敏電阻特性，故具有良好的應用性。
10‧‧‧積層式壓敏電阻器
11‧‧‧燒結體
12、13‧‧‧內電極
14‧‧‧第一外電極
15‧‧‧第二外電極
圖1為本創作的積層式壓敏電阻器之側視剖面示意圖。
10‧‧‧積層式壓敏電阻器
11‧‧‧燒結體
12、13‧‧‧內電極
14‧‧‧第一外電極
15‧‧‧第二外電極
Claims (8)
- 一種不含銻的壓敏電阻組成物，其中包含：一氧化鋅；第一添加劑，其係選自於下列構成的群組：硼鉍鋅鐠玻璃、硼鉍鋅鑭玻璃及其混合物；以所述硼鉍鋅鐠玻璃中所含有的硼、鉍、鋅及鐠之總量為基準，所述硼鉍鋅鐠玻璃的硼含量為20at%至70at%，所述硼鉍鋅鐠玻璃的鉍含量為2at%至30at%，所述硼鉍鋅鐠玻璃的鋅含量為10at%至60at%，所述硼鉍鋅鐠玻璃的鐠含量為5at%至30at%；以所述硼鉍鋅鑭玻璃中所含有的硼、鉍、鋅及鑭之總量為基準，所述硼鉍鋅鑭玻璃的硼含量為20at%至70at%，所述硼鉍鋅鑭玻璃的鉍含量為2at%至30at%，所述硼鉍鋅鑭玻璃的鋅含量為10at%至60at%，所述硼鉍鋅鑭玻璃的鑭含量為5at%至30at%；第二添加劑，其係選自於下列構成的群組：含鈷化合物、含鉻化合物、含鎳化合物、含錳化合物及其混合物；第三添加劑，其包含二氧化錫；以及第四添加劑，其係選自於下列構成的群組：含鋁化合物、含銀化合物及其混合物；其中，以所述不含銻的壓敏電阻組成物之整體為基準，所述第一添加劑的總含量為0.05wt%至20wt%，所述第二添加劑之個別含量為0.1wt%至5.0wt%，所述第三添加劑的含量為0.1wt%至1.5wt%，所述第四添加劑之鋁化合物的含量為0.001wt%至1.0wt%，且所述第四添加劑之個別含量為0.001wt%至1.0wt%。
- 如請求項1所述之不含銻的壓敏電阻組成物，其中所述第二添加劑的含鈷化合物選自於下列構成之群組：鈷氧化物、鈷的氫氧化物、高鈷酸鹽、碳酸鈷、磷酸鈷及其組合，所述第二添加劑的含鉻化合物選自於下列構成 之群組：鉻氧化物、重鉻酸鹽、鉻硼化物、鉻氮化物及其組合，所述第二添加劑的含鎳化合物選自於下列構成之群組：鎳氧化物、碳酸鎳、硝酸鎳及其組合，所述第二添加劑的含錳化合物選自於下列構成之群組：錳氧化物、碳酸錳、硝酸錳、硼氫化錳及其組合。
- 如請求項1所述之不含銻的壓敏電阻組成物，其中所述第四添加劑的含鋁化合物包含鋁氧化物或硝酸鋁，所述第四添加劑的含銀化合物包含銀氧化物或硝酸銀。
- 如請求項1至3中任一項所述之不含銻的壓敏電阻組成物，其中所述第二添加劑為含鈷化合物、含鉻化合物、含鎳化合物及含錳化合物之組合，且該第二添加劑之總含量為0.4wt%至20.0wt%。
- 如請求項1至3中任一項所述之不含銻的壓敏電阻組成物，其中所述第四添加劑為含鋁化合物及含銀化合物之組合，且該第四添加劑之總含量為0.002wt%至2.0wt%。
- 如請求項1至3中任一項所述之不含銻的壓敏電阻組成物，其中所述第一添加劑的粒徑介於50nm至500nm之間。
- 一種積層式壓敏電阻器，其中包含：一燒結體，其具有一第一端及一位置相對於該第一端的第二端；數個內電極，該等內電極間隔設置於該燒結體內，且相鄰的兩內電極分別與該第一端及該第二端相接；一第一外電極，其包覆設置於該第一端上且與相對應的內電極接觸；以及一第二外電極，其包覆設置於該第二端上且與相對應的內電極接觸；其中，該燒結體係由如請求項1至6中任一項所述的不含銻的壓敏電阻組成物所製成。
- 如請求項7所述之積層式壓敏電阻器，其中該等內電極包含鈀含量為30wt%以下的銀鈀合金或鉑含量為30wt%以下的銀鉑合金。
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| TW105132868A TWI605029B (zh) | 2016-10-12 | 2016-10-12 | 不含銻的壓敏電阻組成物及積層式壓敏電阻器 |
| CN201611027276.4A CN107068311B (zh) | 2016-10-12 | 2016-11-16 | 一种低温烧结制成的不含锑成分压敏电阻器及其制备方法 |
| US15/368,729 US10233123B2 (en) | 2016-10-12 | 2016-12-05 | Varistor compositions and multilayer varistor |
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| TW105132868A TWI605029B (zh) | 2016-10-12 | 2016-10-12 | 不含銻的壓敏電阻組成物及積層式壓敏電阻器 |
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| US20210327617A1 (en) * | 2019-04-15 | 2021-10-21 | Panasonic Intellectual Property Management Co., Ltd. | Laminated varistor |
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| TW201234394A (en) * | 2011-02-09 | 2012-08-16 | Yageo Corp | Multi-layer varistor component |
| TW201212051A (en) * | 2011-11-29 | 2012-03-16 | Ching-Hohn Lien | Process for producing ZnO varistor with higher potential gradient and non-coefficient value |
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| US11935674B2 (en) * | 2019-04-15 | 2024-03-19 | Panasonic Intellectual Property Management Co., Ltd. | Laminated varistor |
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| Publication number | Publication date |
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| CN107068311A (zh) | 2017-08-18 |
| US20180099910A1 (en) | 2018-04-12 |
| US10233123B2 (en) | 2019-03-19 |
| TW201813943A (zh) | 2018-04-16 |
| CN107068311B (zh) | 2018-10-16 |
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