WO2011129678A1 - Composition céramique, varistance à basse tension en oxyde de zinc obtenue à partir de la composition céramique et procédé de fabrication de la varistance à basse tension en oxyde de zinc - Google Patents

Composition céramique, varistance à basse tension en oxyde de zinc obtenue à partir de la composition céramique et procédé de fabrication de la varistance à basse tension en oxyde de zinc Download PDF

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WO2011129678A1
WO2011129678A1 PCT/MY2010/000051 MY2010000051W WO2011129678A1 WO 2011129678 A1 WO2011129678 A1 WO 2011129678A1 MY 2010000051 W MY2010000051 W MY 2010000051W WO 2011129678 A1 WO2011129678 A1 WO 2011129678A1
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mole
ceramic composition
zinc oxide
low voltage
oxide varistor
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Bin Mahmud Shahrom
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Universiti Sains Malaysia (USM)
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Universiti Sains Malaysia (USM)
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Priority to PCT/MY2010/000051 priority Critical patent/WO2011129678A1/fr
Priority to MYPI2010003812A priority patent/MY165272A/en
Priority to TW100112706A priority patent/TW201210987A/zh
Publication of WO2011129678A1 publication Critical patent/WO2011129678A1/fr
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    • 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
    • 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
    • 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
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/112—ZnO type
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3232—Titanium oxides or titanates, e.g. rutile or anatase
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • C04B2235/3265—Mn2O3
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3275—Cobalt oxides, cobaltates or cobaltites or oxide forming salts thereof, e.g. bismuth cobaltate, zinc cobaltite
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3409—Boron oxide, borates, boric acids, or oxide forming salts thereof, e.g. borax
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5409—Particle size related information expressed by specific surface values
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient
    • C04B2235/9615—Linear firing shrinkage

Definitions

  • the present invention generally relates to voltage-dependent varistors, and more particularly to a ceramic composition for low voltage zinc oxide varistor, a low voltage zinc oxide varistor made from the ceramic composition, and further to a process for manufacturing the low voltage zinc oxide varistor.
  • ZnO varistors are the electronic components that are most widely used to protect electronic devices and electrical circuits from hazardous electrical transients and surges. They are normally connected in parallel to the devices that are being protected. Under normal steady state operation, a varistor is dormant; it is a state known as the sleep mode. If an electrical transient/surge is present, the varistor detects it in nanosecond speed and switches into a highly conductive state thereby creating a low impedance path to divert the electrical transient/surge away from the electronic devices but into the varistor. Thus, the varistor absorbs the energy of the electrical transient/surge or diverts the electrical transient/surge to ground if the varistor is grounded.
  • ZnO zinc oxide
  • the switch of a varistor occurs at a threshold voltage that is 15%-20% higher than the maximum continuous operating voltage of the device being protected. Above the threshold voltage, the varistor is highly nonlinear and draws in huge currents with little voltage increase. In this nonlinear region, the current-voltage characteristics is commonly expressed as equation (1):
  • the ceramic compositions are optimized to produce low voltage zinc oxide varistors with excellent electrical properties for the full range of the ohmic and nonlinear current- voltage spectra.
  • One embodiment of the present invention provides a ceramic composition comprises zinc oxide and metal oxide additives of Bi, Co, Ni, Ti, Mn, Si, and B, wherein the ceramic composition comprises 0.05 to 7 mole % of Bi, 0.05 to 5 mole % of Co, 0.05 to 6 mole % of Ni, 0.05 to 5 mole % of Ti, 0.05 to 5 mole % of Mn, 0.01 to 0.1 mole % of Si, 0.01 to 0.1 mole % of B, and 90 to 99 mole % of ZnO; wherein the ceramic composition is used to manufacture a sintered body for making a low voltage zinc oxide varistor.
  • the ceramic composition comprises 0.2 to 3 mole % of Bi 2 0 3 , 0.2 to 2 mole % of Co 2 0 3 , 0.2 to 2 mole % of NiO, 0.2 to 2 mole % of Ti0 2 , 0.2 to 2 mole % of Mn 2 0 3 , 0.01 to 1 mole % of Si0 2 , 0.01 to 1 mole % of B 2 0 3 , and 95 to 99 mole % ZnO.
  • the ceramic composition comprises 0.5 to 1 mole % of Bi 2 0 3 , 0.3 to 0.7 mole % of C02O3, 0.3 to 0.7 mole % of NiO, 0.3 to 1 mole % of Ti0 2 , 0.3 to 0.7 mole % of Mn 2 0 3 , 0.02 to 0.05 mole % of Si0 2 , 0.05 to 0.08 mole % of B 2 0 3 , and 95 to 99% ZnO.
  • a low voltage zinc oxide varistor comprising a sintered body, a pair of electrode layers sandwiching the sintered body in ohmic contact, a pair of solder contacts conductively coupling with the electrode layers, and a pair of wire leads conductively coupled with the electrode layers via the solder contact; wherein the sintered body is made of a ceramic composition, and wherein the ceramic composition comprises 0.05 to 7 mole % of Bi, 0.05 to 5 mole % of Co, 0.05 to 6 mole % of Ni, 0.05 to 5 mole % of Ti, 0.05 to 5 mole % of Mn, 0.01 to 0.1 mole % of Si, 0.01 to 0.1 mole % of B, and 90 to 99 mole % of ZnO.
  • the sintered body is any suitable form selected from the group consisting of circular disc, square plate or rectangular plate.
  • the ceramic composition comprises 0.2 to 3 mole % of Bi 2 0 3 , 0.2 to 2 mole % of Co 2 0 3 , 0.2 to 2 mole % of NiO, 0.2 to 2 mole % of Ti0 2 , 0.2 to 2 mole % of Mn 2 0 3 , 0.01 to 1 mole % of Si0 2 , 0.01 to 1 mole % of B 2 0 3 , and 95 to 99 mole % ZnO.
  • the ceramic composition comprises 0.5 to 1 mole % of Bi 2 0 3 , 0.3 to 0.7 mole % of Co 2 0 3 , 0.3 to 0.7 mole % of NiO, 0.3 to 1 mole % of Ti0 2 , 0.3 to 0.7 mole % of Mn 2 0 3 , 0.02 to 0.05 mole % of Si0 2 , 0.05 to 0.08 mole % of B 2 0 3 , and 95 to 99% ZnO.
  • FIG 1 is a partial cross-section view of a varistor in accordance with one embodiment of the present invention.
  • FIG 2 is a graph showing voltage-current characteristics of exemplary varistors in accordance with embodiments of the present invention. Detailed Description of the Invention
  • FIG 1 shows a partial cross-section view of a low voltage zinc oxide varistor in accordance with one embodiment of the present invention.
  • the varistor comprises a sintered body 1, a pair of electrode layers 2 sandwiching the sintered body in ohmic contact, a pair of solder contacts 3 conductively coupling with the electrode layers, and a pair of wire leads 4 conductively coupled with the electrode layers via the solder contact.
  • the sintered body 1 can be any suitable form; for example, circular disc, square plate or rectangular plate.
  • the sintered body 1 is made from a ceramic composition that is comprised of zinc oxide and various metal oxides.
  • the ceramic composition comprises 0.05 to 7 mole % of Bi, 0.05 to 5 mole % of Co, 0.05 to 6 mole % of Ni, 0.05 to 5 mole % of Ti, 0.05 to 5 mole % of Mn, 0.01 to 0.1 mole % of Si, 0.01 to 0.1 mole % of B, and 90 to 99 mole % of ZnO.
  • the ceramic composition preferably comprises 0.2 to 3 mole % of Bi 2 0 3 , 0.2 to 2 mole % of Co 2 0 3 , 0.2 to 2 mole % of NiO, 0.2 to 2 mole % of Ti0 2 , 0.2 to 2 mole % of Mn 2 0 3 , 0.01 to 1 mole % of Si0 2 , 0.01 to 1 mole % of B 2 0 3 , and 95 to 99 mole % ZnO.
  • the ceramic composition preferably comprises 0.5 to 1 mole % of Bi 2 0 3 , 0.3 to 0.7 mole % of Co 2 0 3 , 0.3 to 0.7 mole % of NiO, 0.3 to 1 mole % of Ti0 2 , 0.3 to 0.7 mole % of Mn 2 0 3 , 0.02 to 0.05 mole % of Si0 2 , 0.05 to 0.08 mole % of B 2 0 3 , and 95 to 99% ZnO.
  • the sintered body 1 comprises about 90 to about 99 mole
  • the composition of the metal oxide additives comprises 0.05 to 7 mole % of Bi, 0.05 to 5 mole % of Co, 0.05 to 6 mole % of Ni, 0.05 to 5 mole % of Ti, 0.05 to 5 mole % of Mn, 0.01 to 0.1 mole % of Si and 0.01 to 0.1 mole % of B.
  • the composition of the metal oxide additives comprises 0.2 to 3 mole % of Bi 2 0 3 , 0.2 to 2 mole % of Co 2 0 3 , 0.2 to 2 mole % of NiO, 0.2 to 2 mole % of Ti >, 0.2 to 2 mole % of Mn 2 0 3 , 0.01 to 1 mole % of Si0 2 , and 0.01 to 1 mole % of B 2 0 3 .
  • the composition of the metal oxide additives preferably comprises 0.5 to 1 mole % of Bi 2 0 3 , 0.3 to 0.7 mole % of Co 2 0 3 , 0.3 to 0.7 mole % of NiO, 0.3 to 1 mole % of Ti0 2 , 0.3 to 0.7 mole % of Mn 2 0 3 , 0.02 to 0.05 mole % of Si0 2 , and 0.05 to 0.08 mole % of B 2 0 3 .
  • the ceramic composition for making the sintered body of the low voltage zinc oxide varistor is listed in Table I.
  • Three batches of ZnO (A, B, C) with white seal grade were obtained from three different ZnO manufacturers.
  • the specific surface area of the three ZnO powder types varied from about 4.3 to about 5.7 m 2 /g.
  • Three batches of ceramic compositions of which each containing one batch of ZnO (A, B or C) were homogenously mixed with distilled water and organic binder in a ball mill containing zirconia grinding media. A deflocculant was added to obtain correct slurry viscosity.
  • the ratio of solid content to liquid content was about 65:35.
  • the slurry was dried without, segregation, sieved to less than 200 ⁇ size and pressed into discs at about 15 kpsi.
  • the green varistor discs were sintered at a temperature in the range of about 1100°C to about 1300°C for a time in the range of about 1 h to about 3 h in air. Electrode layers and wire leads were applied to the sintered body via conventional methods.
  • One exemplary varistor was 13-mm diameter low voltage varistor model for testing hereinbelow.
  • FIG 2 shows typical voltage-current characteristics of the tested varistors made in accordance with the present invention.
  • the destructive surge test were done up to 1000 A peak current under a 8 ⁇ 20 ⁇ 5 waveshape and the varistors exhibited extraordinary energy handling capability at 1000 A peak current that are not previously known.
  • These high performance varistors are excellent surge suppressing components for lightning-prone regions with high frequencies of lightning-induced electrical surges.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Thermistors And Varistors (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

La présente invention concerne une composition céramique destinée à la fabrication de varistances à basse tension en oxyde de zinc. L'invention concerne en outre une varistance à basse tension en oxyde de zinc. L'invention concerne également un procédé de fabrication de la varistance à basse tension en oxyde de zinc. Les varistances à basse tension présentent des capacités supérieures de manipulation de l'énergie, c'est-à-dire que les varistances sont capables de supporter des courants de crête très élevés, de plus de deux fois le courant de crête spécifié par les normes internationales.
PCT/MY2010/000051 2010-04-12 2010-04-12 Composition céramique, varistance à basse tension en oxyde de zinc obtenue à partir de la composition céramique et procédé de fabrication de la varistance à basse tension en oxyde de zinc Ceased WO2011129678A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/MY2010/000051 WO2011129678A1 (fr) 2010-04-12 2010-04-12 Composition céramique, varistance à basse tension en oxyde de zinc obtenue à partir de la composition céramique et procédé de fabrication de la varistance à basse tension en oxyde de zinc
MYPI2010003812A MY165272A (en) 2010-04-12 2010-08-13 Ceramic composition, low voltage zinc oxide varistor made from the ceramic composition and process for manufacturing the low voltage zinc oxide varistor
TW100112706A TW201210987A (en) 2010-04-12 2011-04-12 Ceramic composition, low voltage zinc oxide varistor made from the ceramic composition and process for manufacturing the low voltage zinc oxide varistor

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PCT/MY2010/000051 WO2011129678A1 (fr) 2010-04-12 2010-04-12 Composition céramique, varistance à basse tension en oxyde de zinc obtenue à partir de la composition céramique et procédé de fabrication de la varistance à basse tension en oxyde de zinc

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2857374A1 (fr) * 2013-10-02 2015-04-08 Razvojni Center eNem Novi Materiali d.o.o. Procédé de fabrication des varistors céramiques et varistors ayant un faible courant de fuite

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1244745A (en) * 1968-10-01 1971-09-02 Matsushita Electric Industrial Co Ltd Non-linear resistance material
US3962144A (en) * 1973-10-19 1976-06-08 Matsushita Electric Industrial Co., Ltd. Process for making a voltage dependent resistor
GB2242065A (en) * 1990-03-16 1991-09-18 Ecco Ltd Varistor composition
US5973589A (en) * 1997-06-23 1999-10-26 National Science Council Zno varistor of low-temperature sintering ability
US6146552A (en) * 1995-03-06 2000-11-14 Matsushita Electric Industrial Co., Ltd. Zinc oxide ceramics and method for producing the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1244745A (en) * 1968-10-01 1971-09-02 Matsushita Electric Industrial Co Ltd Non-linear resistance material
US3962144A (en) * 1973-10-19 1976-06-08 Matsushita Electric Industrial Co., Ltd. Process for making a voltage dependent resistor
GB2242065A (en) * 1990-03-16 1991-09-18 Ecco Ltd Varistor composition
US6146552A (en) * 1995-03-06 2000-11-14 Matsushita Electric Industrial Co., Ltd. Zinc oxide ceramics and method for producing the same
US5973589A (en) * 1997-06-23 1999-10-26 National Science Council Zno varistor of low-temperature sintering ability

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2857374A1 (fr) * 2013-10-02 2015-04-08 Razvojni Center eNem Novi Materiali d.o.o. Procédé de fabrication des varistors céramiques et varistors ayant un faible courant de fuite

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