EP2599760A1 - Keramik, Monolith mit abgestuftem Widerstand mit der Keramik und Herstellungsverfahren - Google Patents

Keramik, Monolith mit abgestuftem Widerstand mit der Keramik und Herstellungsverfahren Download PDF

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Publication number
EP2599760A1
EP2599760A1 EP20120194916 EP12194916A EP2599760A1 EP 2599760 A1 EP2599760 A1 EP 2599760A1 EP 20120194916 EP20120194916 EP 20120194916 EP 12194916 A EP12194916 A EP 12194916A EP 2599760 A1 EP2599760 A1 EP 2599760A1
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EP
European Patent Office
Prior art keywords
cassette
ceramic composition
percent
monolithic
resistive
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.)
Granted
Application number
EP20120194916
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English (en)
French (fr)
Other versions
EP2599760B1 (de
Inventor
Padmaja Parakala
Sundeep Kumar
Mohandas Nayak
Sudhakar Eddula Ruddy
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General Electric Co
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General Electric Co
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Publication of EP2599760A1 publication Critical patent/EP2599760A1/de
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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C8/00—Non-adjustable resistors consisting of loose powdered or granular conducting, or powdered or granular semi-conducting material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
    • C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0021—Matrix based on noble metals, Cu or alloys thereof

Definitions

  • Embodiments presented herein relate generally to monolithic structures, and more particularly to electrically resistive monolithic structures.
  • rheostats may be used for equipment startup and shutdown.
  • brushed DC motors may have a manual rheostat starter, a three point rheostat starter, a four point rheostat starter, or the like, to gradually increase armature current from a small value to the rated operational value to protect the DC motor.
  • the rheostat switches from one resistance branch to another in a step manner. Such switching operation may result in arcing between the moving contact and the resistance branches, due to the high voltage and/or current supplied to the electrical equipment.
  • Another known solution includes multiple discrete resistive layers assembled in a stack, with the moving contact designed to slide over the stack.
  • sliding surface the surface of the stack in contact with the moving contact
  • the moving contact may not maintain adequate contact pressure over the length of the stack.
  • the different resistive layers of the stack may be ground down to different levels based on the hardness of the resistive layer, thereby forming 'steps' on the sliding surface. This may result in the possibility of the moving contact being stuck at a step between successive resistive elements. Uneven contact pressure and the stepped profile of the sliding surface may both lead to arcing between the moving contact and the sliding surface.
  • such assembled stacks are difficult to machine and polish to obtain a smooth sliding surface. Often, the assembled stacks crack or break during machining.
  • a monolithic cassette with graded electrical resistivity is presented.
  • the monolithic cassette has a continuous grain structure between a first end and a second end; wherein electrical resistivity of the monolithic cassette is graded such that the resistance varies continuously from the first end to the second end.
  • Methods and compositions for forming the monolithic cassette are also presented.
  • an electrically resistive composition comprises 45 to 58 percent by weight of a ceramic composition, wherein the ceramic composition comprises a substantially homogenous mixture of 99.5 to 99.7 percent zinc oxide powder, and 0.3 to 0.5 percent aluminum oxide powder.
  • the composition contains 42 to 55 percent by weight of silver powder wherein electrical resistivity of the composition varies from 1 micro ohm-m to 1 mega ohm-m based on a ratio of the ceramic composition to silver powder.
  • a method of forming a monolithic cassette is presented.
  • a plurality of resistive powders are introduced into a die to form a stack of layers.
  • Each of the plurality of resistive powders comprises a ceramic composition and a conductive composition.
  • Each layer comprises a distinct weight ratio of the ceramic composition and the conductive composition.
  • the plurality of resistive powders are compacted into a green cassette at pressures between 10 mega pascal and 1 giga pascal, and at temperatures between 15 degree Celsius and 1600 degree Celsius.
  • the green cassette is then sintered at a temperature between 800 degree Celsius and 2000 degree Celsius for a duration of 2 to 100 hours.
  • a monolithic cassette that exhibits a graded resistivity over the length of the monolithic cassette.
  • the monolithic cassette may be employed, for example, in arcless switchgear. Electric arcing is common in circuit breakers when circuit breakers trip due to electrical faults. In circuit breakers, contacts must carry the load current without excessive heating, and must also withstand the heat of the arc produced when circuit is opened. Contacts are made of highly conductive materials. Service life of the contacts is limited by the erosion of contact material due to arcing while opening the circuit. An arc might be a potential cause of fire in some cases especially during leakage of inflammable gases.
  • the monolithic cassette may be used in circuit breakers to substantially suppress or completely eliminate electrical arcing.
  • the monolithic cassette may be disposed in the arcless switchgear such that a moving contact of the switchgear slides over the monolithic cassette during a switching operation. While switching off, the moving contact may slide from a low resistivity end to a high resistivity end of the monolithic cassette, while switching from a closed circuit position to an open circuit position. Such a controlled increase of resistance during switching prevents sudden changes in electric potential difference between the fixed contact and the moving contact, thereby substantially suppressing or completely eliminating electrical arcing. While switching on, the moving contact may slide from the low resistivity end to the high resistivity end, while switching from the open circuit position to the closed circuit position.
  • the monolithic cassette may be formed by first stacking multiple layers of resistive powders, such that each layer exhibits a different resistivity. The stacked layers are then compacted to form a green cassette.
  • FIG. 1 illustrates an example green cassette 100.
  • the green cassette 100 includes 4 layers 102, 104, 106, and 108, of resistive powders, each exhibiting a different resistivity. An example composition of the resistive powders is described below, in conjunction with FIG. 3 .
  • the green cassette may also have physical interfaces (i.e. physical boundaries) between successive layers owing to different proportion of compositions in the various resistive powders.
  • the green cassette may then be sintered to form the monolithic cassette that exhibits graded resistivity over the length of the monolithic cassette.
  • the monolithic cassette has a continuous grain structure, without physical boundaries between layers, and may have a graded electrical resistivity such that the resistance varies continuously between the ends of the monolithic cassette.
  • FIG. 2 illustrates an example monolithic cassette 200, according to one embodiment.
  • the monolithic cassette 200 formed after sintering does not include physical boundaries, however, exhibits a continuous grain structure between ends 202, and 204.
  • the dotted lines indicate representative regions of ends 202 and 204.
  • the ends 202 and 204 may be as thin as top and bottom surfaces of the monolithic cassette 200, or may have a finite thickness, greater than, for instance, 0.01 mm.
  • the resistive powders may be a mixture of a high resistivity material (e.g. ceramic materials) and a low resistivity (e.g. metals and metal alloys) material.
  • the resistivity of the resistive powder may be controlled by controlling the proportion of the high resistivity material and low resistivity material in the mixture.
  • multiple layers exhibiting different resistivity may be obtained using mixtures of varying proportions of the same high resistivity material and the same low resistivity material.
  • Such use of the same family of mixtures may typically result in substantially same shrinkage and substantially same sintering temperature of each of the multiple layers, which in turn may reduce or substantially eliminate uneven shrinkage, formation of cracks, airgaps, and voids during sintering of the multi-layered green cassette.
  • the high resistivity material may be a ceramic composition including, for example, zinc oxide, aluminum oxide, aluminum nitride, boron nitride, silicon dioxide, indium tin oxide, and combinations thereof.
  • the ceramic compositions may impart properties such as high thermal stability, high temperature resistance, surface hardness, mechanical strength, and so forth, to the monolithic cassette.
  • the low resistivity material may be a conductive composition including, without limitation, silver, copper, gold, aluminum, indium, tin, gallium, nickel, titanium, zinc, lead, carbon, iron, tungsten, molybdenum, alloys thereof, and mixtures of the metals.
  • the low resistivity material may impart the desired electrical properties to the monolithic cassette.
  • the high resistivity material may be a ceramic composition powder including, for example, zinc oxide and aluminum oxide
  • the low resistivity material may be a conductive metal powder, such as silver.
  • Zinc oxide is less vulnerable to suffer from hot spot or hot cracking. Hot spotting is a phenomenon of formation of an irreversible deformity or crack during compaction.
  • Zinc oxide has a resistivity of the order of 10e7 ohm meter. Mixing the zinc oxide with about 0.3 to 0.5 percent (by weight of zinc oxide) aluminum oxide yields a ceramic composition with a resistivity of the order of 10e3 ohm meter to 10e4 ohm meter.
  • Addition of silver to the ceramic composition further reduces the resistivity to the order of 10e-4 ohm meter.
  • Silver exhibits an extremely low resistivity of 15.87 x 10 -9 ohm meter.
  • resistivity of the resistive powder may be varied from 10e-4 ohm meter to 10e4 ohm meter.
  • the ceramic composition powder may be prepared, for example by wet mixing zinc oxide powder having a grain size of 4 micron, and 0.4 percent (by weight of zinc oxide powder) aluminum oxide having a grain size of 5.6 micron, in isopropyl alcohol for about thirty minutes. The wet mixture may then be dried at 100 degree Celsius. Post drying, the ceramic composition powder may again be dry mixed or wet mixed in isopropyl alcohol.
  • Various resistive powders may then be prepared by mixing the ceramic composition powder with silver powder.
  • the silver powder may have a grain size between 2 and 3.5 micron.
  • the ceramic composition powder and silver powder may be mixed in isopropyl alcohol for thirty minutes, and then dried. The drying may be carried out at ambient temperature, or in an oven at elevated temperatures.
  • the proportion of the ceramic composition powder to silver powder controls the resistivity of the resistance powder.
  • the resistive powder may include 42 to 45 percent by weight silver.
  • the resistive powder may include 45 to 58 percent by weight ceramic composition.
  • the resistive powders may have an electrical resistivity between 1 micro ohm-centimeter and 1 mega ohm-centimeter.
  • 3 is a table illustrating example proportions of the ceramic composition and silver in the resistance powders for 4 different layers of an example green cassette, according to one embodiment. It should be appreciated that other proportions of the ceramic composition and silver may be used, and additional or fewer layers may be used, as per the requirements of the monolithic cassette.
  • the resistive powders are introduced into a die to form a stack of layers.
  • the resistive powders may be introduced starting with the resistive powder exhibiting highest resistivity, and subsequently over layering with other resistive powders with successively decreasing resistivity.
  • the die may be filled starting with the resistive powder exhibiting the lowest resistivity and subsequently over layering with other resistive powders of successively increasing resistivity.
  • the resistive powder may be settled into the die, for example, by vibrating the die, or by using a plunger to obtain a layer of uniform thickness. The introducing and settling process may be repeated for each subsequent layer.
  • the stack of layers of the resistive powders is then compacted under a suitable pressure to form the green cassette.
  • the pressure may range from 10 mega pascal to 1 giga pascal, based on the desired structural characteristics of the monolithic cassette, such as mechanical strength, porosity, and so forth.
  • the resistive powders including zinc oxide, aluminum oxide, and silver may be compacted at pressures between 10 mega pascal and 60 mega pascal.
  • the resistive powders may be compacted using known compaction techniques such as, but not limited to, uniaxial pressing, cold isostatic pressing, hot isostatic pressing, and so forth. During the pressing operation, temperatures may be set to values between 15 degree Celsius (for example, in cold isostatic pressing) and 1600 degree Celsius (for example, in hot isostatic pressing).
  • the stacked layers may be compacted using extrusion processes such as hot extrusion, cold extrusion, hydrostatic extrusion, and so forth. Even though compaction process brings the powder particles together in the green cassette, the green cassette may exhibit a porosity, and thus limited structural strength. Further, the green cassette may also have physical interfaces (i.e. physical boundaries) between successive layers owing to different proportion of the ceramic composition and silver in the various resistive powders.
  • the green cassette may subsequently be sintered to form the monolithic cassette.
  • the temperature for sintering may be chosen based on the constituents of the resistive powder.
  • the green cassette may be sintered at temperatures between 800 degree Celsius and 2000 degree Celsius, and for a duration between 2 hours and 100 hours.
  • the green cassette may be sintered at a temperature between 850 degree Celsius, and 950 degree Celsius.
  • the rate of change of temperature during sintering may be about 1.5 to 2.5 degree Celsius per minute.
  • the green cassette is heated from room temperature to about 850-950 degree Celsius while controlling the rate of temperature rise between 1.5 and 2.5 degree Celsius per minute.
  • the green cassette may be sintered in an atmosphere of air.
  • the sintering process may be carried out for a duration of 22 to 26 hours.
  • sintering of the green cassette is done at a temperature of 900 degree Celsius in an atmosphere of air for a duration of 24 hours, with the rate of change of temperature set to 2 degree Celsius per minute.
  • the green cassette prior to sintering, includes distinct layers of different resistive powders, each layer exhibiting a distinct resistivity, and where the resistivity may change in discrete steps while moving across layer boundaries.
  • Sintering causes atomic diffusion of silver through the green cassette.
  • the silver atoms migrate along the pores present in the green cassette.
  • new crystallites form at the physical interfaces between the layers, such that the original inter-layer boundaries disappear, thus forming a continuous grain structure in the monolithic cassette.
  • the monolithic cassette may now exhibit a smooth transition of resistivity along the longitudinal surface.
  • a graph of resistivity of the monolithic cassette against longitudinal position will illustrate smooth transitions.
  • One such resistivity graph for an example experimental set-up is illustrated in FIG. 4 .
  • An expanded view of the region marked by a rectangle 402 is shown in FIG. 5 . It will be appreciated that the measured minimum resistivity value that can be measured will limited by the experimental measurement set-up, for example, by contact resistance of contacts used in an experimental measurement set-up.
  • the porosity of the green cassette may decrease, resulting in a monolithic cassette that is denser than the green cassette.
  • the monolithic cassette may then be cooled under controlled temperature decrease, to impart the desired hardness, and structural strength to the monolithic cassette.
  • the rate of cooling may be between 1.5 and 2.5 degree Celsius per minute.
  • the rate of cooling is 2 degree Celsius per minute. Controlling the rate of change of temperature while cooling may substantially reduce or completely eliminate the formation of cracks or other deformities in the monolithic cassette upon solidification.
  • the resulting monolith cassette thus has a continuous grain structure and a resistivity graded from 10e-6 ohm meter to 10e6 ohm meter along the longitudinal surface.
  • FIG. 6 is a snapshot of microstructure for an example monolithic cassette along a vertical axis of the monolithic cassette, according to one embodiment. It can be seen that the monolithic cassette exhibits a uniform crystalline structure with no boundaries. Also no cracks and voids are observable in the magnified image.
  • the monolithic cassette may have a Root Mean Squared (RMS) surface roughness value of less than 100 micron. The hardness of the monolithic cassette may be greater than 3 on the Mohs scale.
  • the monolithic cassette may be thermally stable at temperatures exceeding 300 degree Celsius. Due to the controlled rate of cooling, the monolithic cassette may exhibit mechanical strength exceeding 150 mega pascal.
  • a monolithic cassette may be formed, that exhibits resistivity graded between the two ends of the monolithic cassette.
  • the resistivity may be graded by up to 12 orders of magnitude between the two ends of the monolithic cassette.
  • the resistivity may be graded by at least 12 orders of magnitude between the two ends of the monolithic cassette. The orders of magnitude of resistivity may be chosen based on operating parameters of the switchgear within which the monolithic cassette is to be deployed.
  • Such operating parameters include, for example, operating voltage and current, operating power, and so forth.
  • the monolithic cassette may be designed to have a resistivity graded by 8 orders of magnitude.
  • the monolithic cassette may be designed to have a resistivity graded by, for example, 6 orders of magnitude.
  • the monolithic cassette may be designed to have a resistivity graded by, for example, 12 or 13 orders of magnitude.
  • progression of resistivity in the layers may be tailored based on a mathematical function.
  • Any known mathematical function may be used to design a resistivity profile along the longitudinal surface, for example, parabolic functions, hyperbolic function, exponential functions, combinations thereof, and so forth.
  • the mathematical function may be a combination of two or more mathematical functions.
  • the composition of the resistive powders, thickness of the layers, and thus the grading of resistivity of the monolith block may be designed such that the potential difference between the fixed contact, and the sliding contact is always such that conditions for arcing do not exist.
  • a rate of change of resistivity of the monolithic cassette may be small at the low resistivity end, and increase progressively over the length of the monolithic cassette, such that the rate of change of resistivity is high at the high resistivity end.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Non-Insulated Conductors (AREA)
  • Semiconductor Memories (AREA)
EP12194916.8A 2011-11-30 2012-11-29 Keramik, Monolith mit abgestuftem Widerstand mit der Keramik und Herstellungsverfahren Active EP2599760B1 (de)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210342508A1 (en) * 1996-11-29 2021-11-04 The Texas A&M University System Systems and methods for designing compositionally graded alloys

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2956255A (en) * 1958-05-28 1960-10-11 Raytheon Co Switching devices
DE3147260A1 (de) * 1981-11-28 1983-06-01 Brown, Boveri & Cie Ag, 6800 Mannheim Elektrischer schalter
FR2581790A1 (fr) * 1985-05-13 1986-11-14 Stopcircuit Sa Interrupteur disjoncteur a coupure propre
EP0517618A1 (de) * 1991-06-07 1992-12-09 Stopcircuit Lasttrenngerät für elektrische Schaltung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2956255A (en) * 1958-05-28 1960-10-11 Raytheon Co Switching devices
DE3147260A1 (de) * 1981-11-28 1983-06-01 Brown, Boveri & Cie Ag, 6800 Mannheim Elektrischer schalter
FR2581790A1 (fr) * 1985-05-13 1986-11-14 Stopcircuit Sa Interrupteur disjoncteur a coupure propre
EP0517618A1 (de) * 1991-06-07 1992-12-09 Stopcircuit Lasttrenngerät für elektrische Schaltung

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Title
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IMAI T ET AL: "Development of High Gradient Zinc Oxide Nonlinear Resistors and Their Application to Surge Arresters", IEEE TRANSACTIONS ON POWER DELIVERY, IEEE SERVICE CENTER, NEW YORK, NY, US, vol. 13, no. 4, 1 October 1998 (1998-10-01), pages 1182 - 1187, XP011049586, ISSN: 0885-8977 *
ITOH Y ET AL: "Thermal stress characteristics of a functionally graded ZnO element with high energy absorption capability", NIPPON KINZOKU GAKKAISHI - JOURNAL OF THE JAPAN INSTITUTE OF METALS, NIPPON KINZOKU GAKKAI, TOKYO, JP, vol. 63, no. 2, 1 January 1999 (1999-01-01), pages 160 - 166, XP009168110, ISSN: 0021-4876, DOI: 10.1063/1.4747942 *
IZAKI M ET AL: "Characterization of functionally graded zinc oxide film prepared from aqueous solution by controlling cathode potential", NIPPON KINZOKU GAKKAISHI - JOURNAL OF THE JAPAN INSTITUTE OF METALS, NIPPON KINZOKU GAKKAI, TOKYO, JP, vol. 62, no. 11, 1 January 1999 (1999-01-01), pages 1063 - 1068, XP009168113, ISSN: 0021-4876 *
IZAKI M ET AL: "Preparation of functionally graded ZnO film by electrochemical reaction from an aqueous solution", MATERIALS SCIENCE FORUM, TRANS TECH PUBLICATIONS LTD- SWITZERLAND, CH, vol. 308-311, 1 January 1999 (1999-01-01), pages 290 - 294, XP009168111, ISSN: 0255-5476 *
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VOLINTIRU I ET AL: "Evolution of the electrical and structural properties during the growth of Al doped ZnO films by remote plasma-enhanced metalorganic chemical vapor deposition", JOURNAL OF APPLIED PHYSICS, AMERICAN INSTITUTE OF PHYSICS. NEW YORK, US, vol. 102, no. 4, 043709, 27 August 2007 (2007-08-27), pages 1 - 9, XP012101527, ISSN: 0021-8979, DOI: 10.1063/1.2772569 *
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210342508A1 (en) * 1996-11-29 2021-11-04 The Texas A&M University System Systems and methods for designing compositionally graded alloys

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