WO2000018189A1 - Element chauffant a film mince - Google Patents

Element chauffant a film mince Download PDF

Info

Publication number
WO2000018189A1
WO2000018189A1 PCT/AU1999/000791 AU9900791W WO0018189A1 WO 2000018189 A1 WO2000018189 A1 WO 2000018189A1 AU 9900791 W AU9900791 W AU 9900791W WO 0018189 A1 WO0018189 A1 WO 0018189A1
Authority
WO
WIPO (PCT)
Prior art keywords
heating element
thin film
solution
rare earth
element according
Prior art date
Application number
PCT/AU1999/000791
Other languages
English (en)
Inventor
Keith Mario Torpy
David M. Gehrig
Original Assignee
Email Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Email Limited filed Critical Email Limited
Priority to KR1020017003505A priority Critical patent/KR20010079859A/ko
Priority to EP99947118A priority patent/EP1120014A4/fr
Priority to BR9913812-3A priority patent/BR9913812A/pt
Priority to JP2000571716A priority patent/JP2002525829A/ja
Priority to AU60712/99A priority patent/AU751515B2/en
Priority to CA002344486A priority patent/CA2344486A1/fr
Priority to NZ510655A priority patent/NZ510655A/en
Publication of WO2000018189A1 publication Critical patent/WO2000018189A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
    • H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
    • H05B3/141—Conductive ceramics, e.g. metal oxides, metal carbides, barium titanate, ferrites, zirconia, vitrous compounds
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00—Ohmic-resistance heating
    • H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
    • H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material

Definitions

  • This invention relates to heating elements of the kind including an electrically conductive metal oxide film on an electrically insulating substrate.
  • Such devices are known, and may for example consist of a thin film of tin oxide deposited on a glass substrate by means of pyrolitic deposition.
  • Such thin film heating elements are to be used in electrical appliances such as cooktops, it is desirable that they be capable of operating at high temperatures, up to 650°C. In applications such as electric kettles where the heating element is small, the element must be capable of handling high power densities, of the order of 10- 20 Watts cm "2 .
  • Prior art devices have not proved satisfactory in these conditions. It has been found by the present applicants that tin oxide layers tend to become unstable with increasing temperature, due to the tendency for the oxide to change state. It has also been found that where fluorine is employed as an electron donor or conductivity carrier the properties of the film change irreversibly with increasing temperature, apparently due to the fluorine tending to leave the film at temperatures above 400°C.
  • US Patent No. 4,889,974 of Auding, et al. describes thin film elements intended for temperatures beyond 600°C, using oxide films doped at high levels with pairs of compensating foreign atoms.
  • the metal oxide films are doped with, maximally, 10 mol % of each of the foreign atoms compensating each other in pairs, the quantity of said acceptor-forming elements and said donor- forming elements differing maximally by 10%.
  • the Auding patent describes the use of indium, boron, aluminium or zinc as the acceptor- forming dopant, and antimony or fluorine as the donor-forming dopant.
  • a metal oxide layer of satisfactory stability in high power density applications may be obtained by doping with at least one and preferably two rare earth elements.
  • the rare earth dopants are preferably cerium and lanthanum. Preferably these two rare earths are present in substantially equal concentrations.
  • the presence of the rare earth dopants in the thin film layer has been found by the present applicants to have the effect of stabilising the oxidation state of the metal.
  • the invention resides in a thin film electrical heating element including a layer of an electrically conducting metal oxide on an electrically insulating substrate, said metal oxide layer being doped with at least one rare earth element.
  • the metal oxide is deposited on the substrate by pyrolysis of an organometallic base solution containing the at least one rare earth element.
  • the metal oxide layer is tin oxide and contains two rare earth elements such as cerium and lanthanum.
  • This aspect of the invention provides a thin film heating element which is capable of withstanding power densities of up to 10-20 Watts cm “" and/or temperatures in excess of 600°C.
  • the invention resides in a method for the manufacture of a thin film heating element including the step of depositing a layer of metal oxide onto an electrically insulating substrate by pyrolysis of an organometallic base solution containing at least one rare earth element.
  • the base solution contains both cerium and lanthanum in concentrations up to 5 mol %.
  • Fig. 1 is graph showing the power dissipation versus time relationship for a thin film heating element made according to the invention.
  • Fig. 2 shows the relationship between temperature and power at steady state for five elements having power ratings between 500 and 1330 watts.
  • concentrations in the pyrolysis solution of 0.01 mol % preferred concentrations of each of the cerium and lanthanum are between approximately 1.25 mol % and approximately 3.75 mol %.
  • concentrations in the pyrolysis solution of 0.01 mol % preferred concentrations of each of the cerium and lanthanum are between approximately 1.25 mol % and approximately 3.75 mol %.
  • concentration of these rare earths will be chosen as that which contributes to film stability at the power densities for which the film is intended. Best results for films intended for operation at 20 Watts cm " " have been obtained using equal concentrations of approximately 2.5 mol %.
  • the film is preferably doped with substantially equal quantities of donor and acceptor elements, the preferred dopants being antimony and zinc.
  • concentrations of both antimony and zinc will be influenced by the resistivity which is required. We have found base solution concentrations for these materials in the region of 2.8 mol % to be suitable for heating element applications.
  • a useful characteristic of such films in their application as heating elements arises from the positive temperature coefficient resistance of the film. This enables elements to be produced which are self-regulating, in that they will initially operate at a higher wattage and, with increasing temperature, stabilise at the lower design wattage.
  • Suitable substrates include glass ceramics, silicon nitrides and other ceramic substrates as well as metallic substrates coated with high-temperature stable, electrically-insulating materials.
  • the preferred substrate temperatures for applying the base solution with dopants range from 500 to 750°C.
  • post annealing at approximately 600°C for at least one hour is carried out to assist in stabilising the film.
  • Films according to this invention were manufactured from a solution using the spray pyrolysis process.
  • monobutyl tin trichloride was used as a base solution, with 2.8 mol % antimony chloride, 2.8 mol % zinc chloride, 2.5 mol % cerium and 2.5 mol % lanthanum.
  • These films were fabricated with effective resistances of 26 ohm, 30 ohm and 45 ohm to enable heaters of 2.2 kW, 1.8 kW and 1.2 kW respectively to be used, powered by a 240V mains supply voltage.
  • the films were selectively deposited using high temperature masking inks which were removed by brushing after deposition of the film.
  • the films deposited had a high degree of transparency.
  • the resistive properties of the heating elements remained unchanged after 3500 cycles (40 minutes on and 20 minutes off) at 650°C.
  • Fig. 1 shows the typical behaviour of the elements, where power dissipation is plotted against time of operation.
  • the dissipation of the element commences at a high level and decreases as the resistance of the element increases with temperature, until a steady state condition is achieved at the design power consumption.
  • power dissipation will temporarily increase, assisting in achieving rapid heating.
  • Fig. 2 shows the relationship between temperature and power at steady state for five elements having power ratings between 500 and 1330 watts.
  • Sheet resistances varying from around 60 ohms to above 400 ohms have been fabricated by varying the number of spray passes.
  • the thin film thickness could be varied between 2000 Angstrom Units to around 14000 Angstrom Units by varying the number of spray passes.
  • the films were deposited on various substrates including glass ceramics, alumina, silica glass and silicon nitride.
  • films made in accordance with the invention may be used in low temperature applications, such as comfort heating, refrigerating defrost, and general heating.
  • Heating elements of tubular shape manufactured using the above technology can be used in heat exchangers for flow applications, air-conditioning re-heaters, hair dryers, washing and drying appliances, and can also be used as radiating surfaces.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Resistance Heating (AREA)
  • Surface Heating Bodies (AREA)

Abstract

L'invention concerne un élément chauffant à film mince, pouvant résister à des densités de puissance de 10-20 watts cm-2 et/ou à des températures pouvant atteindre 650 °C. Dans sa forme préférée, ledit élément chauffant se compose d'une couche d'oxyde d'étain dopée à l'aide de quantités relativement importantes de cérium et de lanthanum, déposée sur un substrat isolant, par pyrolyse d'une solution de trichlorure de monobutylétain contenant les éléments du groupe des terres rares. La solution et la couche d'oxyde subséquente comprennent, par ailleurs, des éléments donneurs et accepteurs tels que l'antimoine et le zinc, ce qui a pour effet d'augmenter la conductivité dudit élément chauffant.
PCT/AU1999/000791 1998-09-18 1999-09-17 Element chauffant a film mince WO2000018189A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
KR1020017003505A KR20010079859A (ko) 1998-09-18 1999-09-17 박막형 가열소자
EP99947118A EP1120014A4 (fr) 1998-09-18 1999-09-17 Element chauffant a film mince
BR9913812-3A BR9913812A (pt) 1998-09-18 1999-09-17 Elemento aquecedor de filme fino
JP2000571716A JP2002525829A (ja) 1998-09-18 1999-09-17 薄膜加熱素子
AU60712/99A AU751515B2 (en) 1998-09-18 1999-09-17 Thin film heating element
CA002344486A CA2344486A1 (fr) 1998-09-18 1999-09-17 Element chauffant a film mince
NZ510655A NZ510655A (en) 1998-09-18 1999-09-17 Thin film heating element having a metal oxide layer doped with one rare earth element and being deposited on to a substrate from an organometallic base solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPP5995A AUPP599598A0 (en) 1998-09-18 1998-09-18 Self-regulating nanoscale heating element
AUPP5995 1998-09-18

Publications (1)

Publication Number Publication Date
WO2000018189A1 true WO2000018189A1 (fr) 2000-03-30

Family

ID=3810212

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/AU1999/000791 WO2000018189A1 (fr) 1998-09-18 1999-09-17 Element chauffant a film mince

Country Status (10)

Country Link
EP (1) EP1120014A4 (fr)
JP (1) JP2002525829A (fr)
KR (1) KR20010079859A (fr)
CN (1) CN1146301C (fr)
AU (1) AUPP599598A0 (fr)
BR (1) BR9913812A (fr)
CA (1) CA2344486A1 (fr)
ID (1) ID29148A (fr)
NZ (1) NZ510655A (fr)
WO (1) WO2000018189A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10110789C1 (de) * 2001-03-06 2002-07-04 Schott Glas Kochgerät mit einer nicht planaren, mehrdimensional geformten Kochfläche aus Glas- oder Glaskeramik
DE10110792B4 (de) * 2001-03-06 2004-09-23 Schott Glas Keramisches Kochsystem mit Glaskeramikplatte,Isolationsschicht und Heizelementen
WO2008101405A1 (fr) * 2007-02-13 2008-08-28 Advanced Materials Enterprises Co., Ltd Appareil de chauffage et son procédé de fabrication
US7926209B2 (en) 2007-02-13 2011-04-19 Advanced Materials Enterprises Company Limited Electric iron
US9493906B2 (en) 2003-11-20 2016-11-15 Koninklijke Philips N.V. Thin-film heating element

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100466865C (zh) * 2005-03-21 2009-03-04 冷同桂 一种复合金属电热膜溶胶及其制备方法
WO2009105945A1 (fr) * 2008-02-28 2009-09-03 Advanced Materials Enterprises Co., Ltd. Fer à repasser électrique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU886328A1 (ru) * 1980-03-28 1981-11-30 Институт Электроники Ан Белсср Токопровод щий материал дл пленочных электронагревателей
US4849252A (en) * 1983-07-08 1989-07-18 Schott-Glasswerke Dipping process for the production of transparent, electrically conductive, augmented indium oxide layers
US4889974A (en) * 1987-02-21 1989-12-26 U.S. Philips Corporation Thin-film heating element
CN1082803A (zh) * 1992-07-09 1994-02-23 连铁军 一种耐高温透明电热膜及其生产方法
US5616266A (en) * 1994-07-29 1997-04-01 Thermal Dynamics U.S.A. Ltd. Co. Resistance heating element with large area, thin film and method

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07105282B2 (ja) * 1988-05-13 1995-11-13 富士ゼロックス株式会社 抵抗体及び抵抗体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU886328A1 (ru) * 1980-03-28 1981-11-30 Институт Электроники Ан Белсср Токопровод щий материал дл пленочных электронагревателей
US4849252A (en) * 1983-07-08 1989-07-18 Schott-Glasswerke Dipping process for the production of transparent, electrically conductive, augmented indium oxide layers
US4889974A (en) * 1987-02-21 1989-12-26 U.S. Philips Corporation Thin-film heating element
CN1082803A (zh) * 1992-07-09 1994-02-23 连铁军 一种耐高温透明电热膜及其生产方法
US5616266A (en) * 1994-07-29 1997-04-01 Thermal Dynamics U.S.A. Ltd. Co. Resistance heating element with large area, thin film and method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; Class L03, AN 1982-85260E/40 *
DATABASE WPI Derwent World Patents Index; Class L03, AN 1995-170973/23 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10110789C1 (de) * 2001-03-06 2002-07-04 Schott Glas Kochgerät mit einer nicht planaren, mehrdimensional geformten Kochfläche aus Glas- oder Glaskeramik
DE10110792B4 (de) * 2001-03-06 2004-09-23 Schott Glas Keramisches Kochsystem mit Glaskeramikplatte,Isolationsschicht und Heizelementen
US9493906B2 (en) 2003-11-20 2016-11-15 Koninklijke Philips N.V. Thin-film heating element
WO2008101405A1 (fr) * 2007-02-13 2008-08-28 Advanced Materials Enterprises Co., Ltd Appareil de chauffage et son procédé de fabrication
EP2111728A1 (fr) * 2007-02-13 2009-10-28 Advanced Materials Enterprises Co., Ltd Appareil de chauffage et son procédé de fabrication
EP2111728A4 (fr) * 2007-02-13 2010-10-27 Advanced Materials Entpr Co Lt Appareil de chauffage et son procédé de fabrication
US7926209B2 (en) 2007-02-13 2011-04-19 Advanced Materials Enterprises Company Limited Electric iron
US8193475B2 (en) 2007-02-13 2012-06-05 Advanced Materials Enterprises Company Limited Heating apparatus and method for making the same

Also Published As

Publication number Publication date
NZ510655A (en) 2003-05-30
ID29148A (id) 2001-08-02
KR20010079859A (ko) 2001-08-22
EP1120014A1 (fr) 2001-08-01
BR9913812A (pt) 2001-08-14
CA2344486A1 (fr) 2000-03-30
CN1146301C (zh) 2004-04-14
JP2002525829A (ja) 2002-08-13
EP1120014A4 (fr) 2004-06-16
AUPP599598A0 (en) 1998-10-08
CN1317223A (zh) 2001-10-10

Similar Documents

Publication Publication Date Title
MX9700728A (es) Elemento de calentamiento con resistencia con pelicula delgada de gran area, y metodo.
US9493906B2 (en) Thin-film heating element
KR101455065B1 (ko) 세라믹박막 발열체를 이용한 면상 발열장치 및 그 제조방법
EP1120014A1 (fr) Element chauffant a film mince
US6028292A (en) Ceramic igniter having improved oxidation resistance, and method of using same
US2772190A (en) Method of increasing the electrical conductivity of tin oxide films
EP1774571A2 (fr) Element chauffant en ligne couple a utiliser dans un traitement chimique humide de semi-conducteur et sa methode de fabrication
Carlson The Deposition of Tin Oxide Films from a D‐C Glow Discharge
AU751515B2 (en) Thin film heating element
WO2017117873A1 (fr) Élément chauffant à film épais à deux côtés présentant une conductivité thermique élevée
KR100794987B1 (ko) 진공 증착기에서 순간 가열 방식의 기판 가열 장치
JP3317895B2 (ja) 温度自己制御機能ヒータ
US5725912A (en) Method of manufacturing an electric heating film of semiconductor
KR100363062B1 (ko) 웨이퍼 가열장치
KR940010814B1 (ko) 박막 발열체
JP2961466B2 (ja) ヒーター
JPH05326113A (ja) Ｐｔｃヒータ
KR100396092B1 (ko) 카본 발열체 및 그 제조 방법
Miyata et al. Fabrication and characterization of diamond film thermistors
KR950009661Y1 (ko) 면상 원적외선 세라믹 방사체
JP2001357964A (ja) 複層セラミックスヒーター
KR100269860B1 (ko) 가스감지나 습도제거용 피티씨히터의 후막성형방법 및 절연막의 솔코팅방법
Rud' Preparing microcomposite powders doped with antimony dioxide and properties of thick films based on those powders
Jia et al. On the nature of zero temperature coefficient of resistance of RuO2 thin film resistor formation using in situ annealing
GB1563473A (en) Electrical resistors

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 99810772.7

Country of ref document: CN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
ENP Entry into the national phase

Ref document number: 2344486

Country of ref document: CA

Ref document number: 2344486

Country of ref document: CA

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2000 571716

Country of ref document: JP

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2001/02224

Country of ref document: ZA

Ref document number: 60712/99

Country of ref document: AU

Ref document number: 200102224

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 1020017003505

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1999947118

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 510655

Country of ref document: NZ

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWP Wipo information: published in national office

Ref document number: 1999947118

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1020017003505

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 09787496

Country of ref document: US

WWG Wipo information: grant in national office

Ref document number: 60712/99

Country of ref document: AU

WWW Wipo information: withdrawn in national office

Ref document number: 1020017003505

Country of ref document: KR

WWW Wipo information: withdrawn in national office

Ref document number: 1999947118

Country of ref document: EP