GB2054167A - Oxygen concentration detecting element and production thereof - Google Patents

Oxygen concentration detecting element and production thereof Download PDF

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Publication number
GB2054167A
GB2054167A GB8023164A GB8023164A GB2054167A GB 2054167 A GB2054167 A GB 2054167A GB 8023164 A GB8023164 A GB 8023164A GB 8023164 A GB8023164 A GB 8023164A GB 2054167 A GB2054167 A GB 2054167A
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solid electrolyte
oxide
substrate
detecting element
oxygen concentration
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GB2054167B (en
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Nissan Motor Co Ltd
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Nissan Motor Co Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073—Composition or fabrication of the solid electrolyte
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Pathology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Immunology (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

An oxygen concentration detecting element comprises a substrate (1) formed of aluminum oxide, and an oxygen ion conductive solid electrolyte (3) in contact with the substrate and provided with electrodes (2, 4), the solid electrolyte being formed of zirconium oxide and containing one of yttrium oxide or erbium oxide in an amount ranging from 4.0 to 7.0 mol% relative to zirconium oxide, thereby preventing the detecting element from being cracked and the solid electrolyte from being peeled off from the substrate. The solid electrolyte is suitably formed by applying a paste of the zirconium oxide and yttrium oxide or erbium oxide to the substrate and firing it at a temperature of from 1350 to 1550 DEG C. <IMAGE>

Description

SPECIFICATION Oxygen concentration detecting element and production thereof This invention relates to an oxygen concentration detecting element employing an oxygen ion conductive solid electrolyte and a method for producing it. More particularly, the invention relates to an oxygen concentration detecting element constructed by laminating the solid electrolyte and electrodes onto a substrate and to the production thereof.
A variety of oxygen concentration detecting elements have been proposed; for example one constructed by successively laminating onto a substrate, a reference electrode, a solid electrolyte and a measuring electrode; and one constructed by laying a solid electrolyte onto a substrate, then laying a reference electrode and a measuring electrode onto the solid electrolyte, and further covering the reference electrode with a dense material. In these cases, the substrate is usually formed of aluminium oxide, and the solid electrolyte is formed of zirconium oxide stabilized with calcium oxide, yttrium oxide or magnesium oxide.
With regard to the solid electrolyte, zirconium oxide is reversely transformed from the monoclinic system to the tetragonal system at about 900--12000C, accompanied with a volume change of 7-9.
Accordingly, when a zirconium oxide solid electrolyte laminated on the aluminium oxide substrate is heated at the above-mentioned temperature, the zirconium oxide undergoes a change in volume and therefore the solid electrolyte is liable to break, raising the problem of low heat resistance for a solid electrolyte made of zirconium oxide. In order to solve this problem, zirconium, oxide is mixed with an additive or stabilizer to produce a thermally stable cubic system solid solution of zirconium oxide, having improved volume change with temperature variation characteristics. Such additives are calcium oxide, yttrium oxide and magnesium oxide as mentioned above.
Many studies have been made to select the additives and the amount of additive to be added as a result of which it has been proposed to employ a decreased amount of the additive so that about 30% monoclinic system zirconium oxide remains, and 2-6 weight % of calcium oxide is used as the additive.
However, even with an oxygen concentration detecting element which is provided with the solid electrolyte prepared as discussed above, when it was subjected to bench tests for detecting oxygen concentration in exhaust gases from an automobile internal combustion engine, the solid electrolyte was cracked and the solid electrolyte peeled off from the substrate relatively early in the test, which test was carried out with repeated thermal shock wherein the temperature was raised from room temperature to about 8000C during a time period of about 2 minutes, and subsequently allowed to recover to room temperature during a time period of 2 minutes.
These problems appear to be caused by the considerable difference in the coefficient of thermal expansion of the aluminum oxide substrate (about 7.8 x 1 O-6/oC in the sintered state) and that of the solid electrolyte (about 9.54 x 1 O-6/0C in the case of a 10 wt. % CaO - ZrO2 solid electrolyte; and about 9.00 x 1 O-6/ C in the case of a 20 wt.% Y203 - Zr02 solid electrolyte).
The oxygen concentration detecting element of the present invention is formed of an oxygen ion conductive solid electrolyte layer carried on a substrate formed of aluminum oxide. The solid electrolyte layer is formed of zirconium oxide and contains yttrium oxide or erbium oxide in an amount of from 4.0 to 7.0 mol% relative to the zirconium oxide. In the production of the detecting element, the solid electrolyte layer is preferably formed by firing a paste of the solid electrolyte printed on the substrate at a temperature of from 1350 to 15500C.
By virtue of the present invention, the thermal coefficient of expansion of the solid electrolyte layer and that of the substrate can be brought closer to each other. Therefore, the oxygen concentration detecting element thus produced has a reduced tendency to crack and the solid electrolyte has a reduced tendency to peel off from the substrate, maintaining good adherence therebetween, even though the detecting element is subjected to repeated severe thermal shocks, as in exhaust gases from an internal combustion engine.
According to the present invention, there is provided an oxygen concentration detecting element comprising: a substrate formed of aluminium oxide; an oxygen ion conductive solid electrolyte layer in contact with the substrate, the solid electrolyte being formed of zirconium oxide and containing yttrium oxide or erbium oxide in an amount of from 4.0 to 7.0 mol% relative to the zirconium oxide; and electrodes in contact with the solid electrolyte.
For a better understanding of the invention reference will be made in the following description to the accompanying drawings in which: Figure 1 is a schematic plan view of a preferred embodiment of an oxygen concentration detecting element in accordance with the present invention; and Figure 2 is a schematic cross-section through the oxygen concentration detecting element of Figure 1.
According to the present invention, in an oxygen detecting element of the type constructed by laminating an oxygen ion conductive solid electrolyte and electrodes onto a substrate plate, the substrate plate is formed of aluminium oxide, and the solid electrolyte is formed of zirconium oxide and contains yttrium oxide or erbium oxide, in an amount of from 4.0 to 7.0 mol% relative to the zirconium oxide, as a stabilizer. Additionally, for producing the oxygen detecting element according to the present invention, the solid electrolyte is fired at a temperature of from 1350 to 155000.
Oxygen concentration detecting elements as schematically shown in Figures 1 and 2 were produced as described below. The oxygen concentration detecting element as shown in Figures 1 and 2 comprises a substrate plate 1, a reference electrode 2 laid on the substrate plate 1, an oxygen ion conductive solid electrolyte 3 laid on the reference electrode 2, and a measuring electrode 4 laid on the solid electrolyte 3. The principle of the present invention is also applicable to another type of oxygen concentration detecting element which is constructed by directly laying the solid electrolyte on the substrate plate, subsequently laying the reference electrode and the measuring electrode on the solid electrolyte, and thereafter covering the reference electrode with a dense material.
The following experiments were carried out using a substrate plate 1 formed of aluminium oxide (alumina), and a solid electrolyte 3 formed of zirconium oxide (zirconia) containing yttrium oxide (yttria) as the stabilizer. In the experiments, four kinds of solid electrolyte powders were prepared by mixing zirconium oxide with various amounts of yttrium oxide as shown in Table 1. These electrolyte powders were mixed with an organic vehicle (a mixture of ethyl cellulose and terpineol) to obtain four kinds of solid electrolyte pastes. Subsequently, the four electrolyte pastes were respectively screen printed on the surfaces of the respective substrate plates formed of aluminium oxide.Thereafter, each substrate plate printed with the solid electrolyte paste was fired at 1 4000C for 2 hours to form a solid electrolyte layer or film having a thickness of from 10 to 20 microns on the surface of the substrate plate, by which four specimens were prepared. Next, the coefficient of thermal expansion was measured for a part of the solid electrolyte layer of each specimen to give the values shown in Table 1. Furthermore, a part of each specimen was subjected to a thermal shock test to evaluate the adhesion between the substrate plate and the solid electrolyte. In the thermal shock test the temperature was repeatedly raised and lowered with a range from 3000C to 80000, to give the results shown in Table 1.
TABLE 1
stabilizer particle size coefficient content of of solid of thermal evaluation solid electrolyte expansion by thermal total electrolyte (micron) (1/ C) shock test evaluation 2;;0 less than abnormal poor poor 10 expansion 4.0 less than 8.20 x106 excellent excellent 10 7.0 less than 7.65 x 10-6 excellent excellent 10 10.0 less than 9.00 x 10-6 poor poor 10 With respect to the results shown in Table 1, when the stabilizer contents are 4.0 and 7.0 mol% relative to the solid electrolytes, the coefficients of the solid electrolytes are 8.20 x 1 0-6/ C and 7.65 x 1 0-6/oC, respectively.These coefficients of thermal expansion are close to that (7.8 x 1 0-6/ C) of aluminium oxide. Furthermore, after the thermal shock test wherein the temperature was raised and lowered within the range from 3000C to 80000 2,000 times, the specimens whose electrolyte stabilizer contents were 2.0 mol% respectively were cracked and the solid electrolyte was peeled off from the substrate plate. On the contrary, the specimens whose stabilizer contents were 4.0 mol% and 7.0 mol%, respectively, were not seen to be cracked and did not show signs of the solid electrolyte peeling off from the substrate plate.
Thus, when the solid electrolyte formed of zirconium oxide and containing yttrium oxide, in an amount ranging from 4.0 to 7.0 mol % relative to zirconium oxide, as a stabilizer is securely laid on the substrate formed of aluminium oxide, the coefficients of thermal expansion of the solid electrolyte and the substrate are close to each other and the resultant oxygen concentration detecting element can have good thermal shock resistance.
It has been found experimentally that cracking of the solid electrolyte and peeling off of the solid electrolyte from the substrate plate are effectively prevented by adjusting the coefficient of thermal expansion of the solid electrolyte to from 0.9 to 1.1 times that of the substrate plate on which the solid electrolyte is laid or laminated. It was also found that it was preferable that the particle size of the solid electrolyte powder be 5.0 microns in maximum and about 0.7 micron or less on average. Furthermore, the same experiments as mentioned above were carried out using erbium oxide in place of yttrium oxide as stabilizer.As a result, in this case, the coefficients of thermal expansion of the solid electrolyte and of the substrate plate could be brought close to each other by selecting the added amount of the erbium oxide to the solid electrolyte with the range of from 4.0 to 7.0 mol%.
Subsequently, the following experiments were conducted to examine the effect of firing temperature, the amount of stabilizer added being kept consistent. In these experiments, after zirconium oxide solid electrolyte powder had been mixed with 5.0 mol% of yttrium oxide as stabilizer, the solid electrolyte powder was mixed with the same organic vehicle as mentioned above to prepare a solid electrolyte paste. The solid electrolyte paste was screen printed onto the surface of the substrate plate formed of aluminium oxide in order to form an unfired solid electrolyte layer of the desired thickness. By this procedure, seven substrate plates printed with the solid electrolyte pastes were prepared. The resultant substrate plates were fired for 2 hours at the temperatures shown in Table 2, respectively, to give seven specimens.Thereafter, the coefficient of thermal expansion of the solid electrolyte was measured with respect to each specimen. Additionally, each specimen was subjected to a thermal shock test in which its temperature was raised and lowered within the range from 3000C to 8000C 2,000 times. The results obtained are shown in Table 2.
TABLE 2
particle coefficient firing size of of thermal evaluation temp. electrolyte expansion by thermal total ( C) (micron) (1/-C) shock test evaluation 1300 less than 6.90 xlO'b good poor 10 1350 - less than 7.20 x10-6 excellent excellent 10 1400 less than 7.32x1O6 excellent excellent 10 1500 less than 7.42 X 10-6 excellent excellent 10 1550 less than 7.20-x10#6 excellent excellent 10 1680 less than 6.88 x 10-6 good poor 10 1650 less than abnormal poor poor 10 expansion As may be seen from Table 2, in the case of the content of the stabilizer being 5.0 mol% relative to the solid electrolyte, the coefficient of thermal expansion of the solid electrolyte was close to that of' the aluminium oxide substrate plate for those specimens fired at a temperature within the range of 1 350 to 1 5500C.Additionally, no cracking of such specimens or peeling of the solid electrolyte from the substrate plates were noted. On the other hand, satisfactory results in the thermal shock test could not be obtained with those specimens which were prepared by firing at a temperature outside the range 1350 to 15500C.
Furthermore, it was noted also from these experiments, that the particle size of the solid electrolyte powder used for preparing the solid electrolyte layer was preferably 5.0 micron at a maximum and 0.7 micron or smaller on average. The same experiments were carried out using erbium oxide in place of yttrium oxide as the stabilizer. These experiments gave similar results as in the case of yttrium oxide, and consequently it was confirmed also in this case that the firing temperature was preferably within the range from 1350 to 1 5500 C.
In addition, the specimens which were prepared by adding the stabilizer within the range of from 4.0 to 7.0 mol% relative to the solid electrolyte and by firing at a temperature within the range from 1350 to 15500C were subjected to X-ray diffractional analysis. This showed that 40 to 70 volume % of the solid electrolyte could be occupied by a cubic system, and therefore the coefficient of thermal expansion of the solid electrolyte could be close to that of the substrate plate, i.e. the coefficient of thermal expansion of the solid electrolyte could be from 0.9 to 1.1 times that of the substrate plate.
As will be appreciated from the above discussion, the coefficient of thermal expansion of a solid electrolyte of a oxygen concentration detecting element is adjusted to be from 0.9 to 1.1 times that of the substrate plate by using a substrate plate formed of aluminium oxide and a solid electrolyte formed of zirconium oxide and containing yttrium oxide or erbium oxide, in an amount of from 4.0 to 7.0 mol% relative to the zirconium oxide, as stabilizer, and further by firing the above-mentioned solid electrolyte at a temperature of from 1350 to 1 5500 C. Accordingly, cracking of the solid electrolyte and peeling off of the solid electrolyte from the substrate plate can be effectively prevented even when detecting the oxygen concentration in exhaust gases discharged from an intemal combustion engine, in which case the detecting element is subjected to repeated severe thermal shocks. In this regard, the oxygen concentration detecting element according to the present invention can maintain good adherence between the substrate plate and the solid electrolyte for a long period of time.

Claims (11)

1. An oxygen concentration detecting element comprising: a substrate formed of aluminium oxide; an oxygen ion conductive solid electrolyte layer in contact with said substrate, said solid electrolyte being formed of zirconium oxide and containing yttrium oxide or erbium oxide in an amount of from 4.0 to 7.0 mol% relative to the zirconium oxide; and electrodes in contact with said solid electrolyte.
2. An oxygen concentration detecting element as claimed in claim 1, in which the solid electrolyte layer has a thickness of from 10 to 20 microns.
3. An oxygen concentration detecting element as claimed in claim 1 substantially as hereinbefore described with reference to the accompanying drawings.
4. A method for producing an oxygen concentration detecting element including a substrate, an oxygen ion conductive solid electrolyte in contact with the substrate and electrodes in contact with the solid electrolyte, which comprises the steps of: preparing said substrate formed of aluminium oxide; preparing said solid electrolyte formed of zirconium oxide and containing one yttrium oxide or erbium oxide in an amount of from 4.0 to 7.0 mol% relative to zirconium oxide; and firing said solid electrolyte at a temperature of from 1350 to 1 55O0C.
5. A method as claimed in claim 4, further comprising the step of forming an unfired layer of said solid electrolyte on said substrate, before the step of firing said solid electrolyte.
6. A method as claimed in claim 5, the unfired layer forming step includes the step of: mixing zirconium oxide powder with yttrium oxide or erbium oxide; mixing an organic vehicle with the mixture of zirconium oxide powder and yttrium oxide or erbium oxide to prepare a solid electrolyte. paste; and applying said solid electrolyte paste onto the surface of said substrate.
7. A method as claimed in claim 6, wherein the particle size of said powdered zirconium oxide is less than 5.0 microns.
8. A method as claimed in claim 7, wherein the average particle size of said powdered zirconium is 0.7 micron or less.
9. A method as claimed in claim 6, wherein said organic vehicle is a mixture of ethyl cellulose and terpineol.
10. An oxygen concentration detecting element as constructed and arranged substantially as described herein with reference to, and as illustrated in, Figures 1 and 2 of the accompanying drawings.
11. A method for producing an oxygen concentration detecting element substantially as herein described with reference to the Experiments.
GB8023164A 1979-07-16 1980-07-16 Oxygen concentration detecting element and production thereof Expired GB2054167B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8924479A JPS5614150A (en) 1979-07-16 1979-07-16 Manufacture of oxygen-concentration detecting element

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GB2054167A true GB2054167A (en) 1981-02-11
GB2054167B GB2054167B (en) 1984-03-14

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DE (1) DE3026801A1 (en)
FR (1) FR2461947A1 (en)
GB (1) GB2054167B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0133820A1 (en) * 1983-08-09 1985-03-06 Ngk Insulators, Ltd. An electrochemical device
EP0227996A1 (en) * 1985-12-12 1987-07-08 Drägerwerk Aktiengesellschaft Method for measuring gas partial pressures with a solid electrolyte of tetragonal zirconiumdioxide
US4879904A (en) * 1987-03-25 1989-11-14 Thorn Emi Plc Ionic conductivity accelerometer
US6676817B2 (en) 1999-02-03 2004-01-13 Ngk Spark Plug Co., Ltd. Solid electrolyte containing insulating ceramic grains for gas sensor

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2998584B1 (en) * 2012-11-28 2016-04-01 Areva ELECTROLYSER COMPRISING ANIONICALLY CONDUCTIVE ELECTROLYTIC MEMBRANE AND METHOD OF ELECTROLYSIS OF WATER VAPOR

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3843400A (en) * 1972-09-18 1974-10-22 Westinghouse Electric Corp Solid electrolyte cell
JPS5339789A (en) * 1976-09-22 1978-04-11 Nissan Motor Oxygen sensor
JPS5339791A (en) * 1976-09-22 1978-04-11 Nissan Motor Oxygen sensor
JPS5348594A (en) * 1976-10-14 1978-05-02 Nissan Motor Oxygen sensor
JPS54151089A (en) * 1978-05-18 1979-11-27 Nissan Motor Solid electrolyte paste
JPS5916831B2 (en) * 1978-07-24 1984-04-18 日産自動車株式会社 Manufacturing method of membrane structure type oxygen sensor
JPS5947258A (en) * 1982-09-10 1984-03-16 Mitsui Petrochem Ind Ltd Aromatic polymer composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0133820A1 (en) * 1983-08-09 1985-03-06 Ngk Insulators, Ltd. An electrochemical device
EP0227996A1 (en) * 1985-12-12 1987-07-08 Drägerwerk Aktiengesellschaft Method for measuring gas partial pressures with a solid electrolyte of tetragonal zirconiumdioxide
US4879904A (en) * 1987-03-25 1989-11-14 Thorn Emi Plc Ionic conductivity accelerometer
US6676817B2 (en) 1999-02-03 2004-01-13 Ngk Spark Plug Co., Ltd. Solid electrolyte containing insulating ceramic grains for gas sensor

Also Published As

Publication number Publication date
JPS5614150A (en) 1981-02-10
DE3026801A1 (en) 1981-01-29
FR2461947A1 (en) 1981-02-06
FR2461947B1 (en) 1984-06-15
GB2054167B (en) 1984-03-14

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