US3779948A - Vitreous compounds with bistable electrical characteristics - Google Patents

Vitreous compounds with bistable electrical characteristics Download PDF

Info

Publication number
US3779948A
US3779948A US00166777A US3779948DA US3779948A US 3779948 A US3779948 A US 3779948A US 00166777 A US00166777 A US 00166777A US 3779948D A US3779948D A US 3779948DA US 3779948 A US3779948 A US 3779948A
Authority
US
United States
Prior art keywords
compound
compounds
formula
vitreous
mixture
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.)
Expired - Lifetime
Application number
US00166777A
Other languages
English (en)
Inventor
J Loriers
R Heindl
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bpifrance Financement SA
Original Assignee
Agence National de Valorisation de la Recherche ANVAR
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 Agence National de Valorisation de la Recherche ANVAR filed Critical Agence National de Valorisation de la Recherche ANVAR
Application granted granted Critical
Publication of US3779948A publication Critical patent/US3779948A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former

Definitions

  • the new class of vitreous compounds can be represented by the general formula (1):
  • Vitreous compounds having such characteristics are already known. It is possible, for instance, to mention French patents, 1,445,528 and 1,351,433 as documents illustrating the prior art in this field. Patent 1,445,528 describes binary vitreous compounds. Patent 1,351,433 which is used more particularly as a Bibliographical reference in the present description, describes ternary or quaternary vitreous compounds of the type AsTel, AsTeSe, AsTiSe, VOP, VOPBa, VOPPb or AsBTiO. Such semi-conductive compounds are used in electrical elements where they are combined with an electrical signal source to take advantage of their two states of resistance at least. Said electric elements are used in the technique of switching, in solid state electronic amplifiers and oscillators as well as storage elements, among other things, as the aforesaid French patent explains in detail.
  • Swiss patent No. 490,728 (SIEMENS A.G.) relates to a semi-conductive switching device without a junction.
  • a vitreous compound is formed from a mixture of V 0 and SrCO United Kingdom Pat. No. 1,168,107 (HITACHI Ltd.) can also be mentioned it relates to a process for manufacturing a thermistor consisting of a sintered mixture of V 0 and a combination of various oxides such as Na, Ca, Al (page 4, example 4), and United States Pat. No. 3,258,434 assigned to (GENERAL ELECTRIC Co) relating to a semi-conductive glass containing CaO'2B O V O Fe o -Al- O (column 6, example X) as a constituant.
  • the new class of vitreous compounds can be represented by the general formula (1) 2-z-2: 2+1+z t-u ll II IZ-ar -T y O.5 and
  • the compound of formula (II) has bistable electrical characteristics suited to the requirements of the invention. Its mechanical and electrical properties are superior to those of the known compounds. For example, the difference in resistivities between the conductive and resistant states is at least 10 times as great as that corresponding to the prior compounds.
  • the other compounds of the invention can be obtained from the basic matrix of formula (ll) by the introduction of the rare earth Ln and/or iron Fe or fluorine F.
  • bistable glasses can also be obtained by combining several compounds corresponding to formula (I), one of which is, for instance, the basic compound of formula (ll). The products obtained no longer correspond to formula (I) but they retain bistable electrical characteristics.
  • the new vitreous compounds are prepared under critical conditions for precursor products of the chemical elements of formula (l), notably oxides and salts such as carbonates.
  • the mixture of said precursor products in substantially stoichiometric proportions corresponding to formula (I) should be heated at high temperature for along period of time to obtain vitreous compounds.
  • the invention therefore also relates to a process for obtaining vitreous compounds corresponding to the aforesaid formula (I) by the intimate contacting of precursor products with the formation of a mixture providing the elements of said compounds in substantially stoichiometric proportions and a thermal treatment, wherein the said mixture is heated for at least 5 hours at a temperature higher than 1,300C.
  • periods of heating from 6 to 12 hours are suitable, at temperatures of 1,300 to 'l,400C, at 1,350C for example. Melting at insuffciently high temperatures, or for too short periods of time, does not enable vitreous products to be obtained. lf the conditions provided for in the invention are not respected, products which crystallize on cooling are finally obtained.
  • the total weight of the mixture is therefore 720.95 g.
  • the mixture is then heated open to the air in a platinum crucible at 650C for 2 hours, at 750C for 2 hours and then at 1,350C for 6 hours.
  • the product obtained is a vitreous body corresponding to the aforesaid formula (II) and having two different states of electric resistance Electric measurements were carried out to determine the properties of the new product.
  • FIGS. 1 to 3 show the assembly conditions and results obtained.
  • FIG. 1 is a general diagram of the electric circuit permitting voltage-current characteristics to be obtained.
  • FIG. 2 is a detailed view showing the assembly of the sample containing product (II).
  • FIG. 3 is the voltage-current curve obtained.
  • FIG. 1 shows, diagramatically, the assembly used.
  • a continuous 300 volts power supply 1 is connected to a throw-over switch 2 by a potentiometer 3.
  • the throwover switch 2 is connected, on the one hand, to earth through a resistor 4 or read resistor (100.) and a voltmeter 5, as well as to the input of a voltage-current curve tracer 6 and, on the other hand, to sample 7 to be tested through a resistor 8 (501(0).
  • the other terminal of sample 7 is connected to earth by a resistor 9 and a conductor 10 connects the other input of tracer 6 to one of the terminals of resistor 8.
  • FIG. 2 shows a detail of the assembly or sample 7.
  • Pellet 13 is maintained between the graphite cylinders by a conductive coating such as a silver paint put on the market by the German firm DEGUSSA. Pellet 13 is about 0.1 mm in thickness.
  • portion (A) corresponds to the resistive state and portion (B) to the reducer state.
  • EXAMPLE 2 which sodium fluoride is incorporated in the amounts 6 given, are subjected to the same thermal treatment as described in example 1.
  • the mixture corresponds to the compound Ca Na Fe V3012 0.5 mole Fe; 0 79.85 g
  • EXAMPLE 4 EiiAMbLES To Obtain the product Ca Y Na V 0,
  • This example illustrates a variant of the vitreous comp iti n which can be Ob ed by m x ng a mpou containing yttrium and the basic produce of example 1.
  • This mixture is heated at 650C for 2 hours and at 800C for 2 hours.
  • Precursor compounds (amounts in moles and in g) co caff 2T13'" 0.1.0., 16.29 g. Y.o,, 11.29 g. 1.12. (30.1%,, 118.72 g. I. AI(N0..),,. 911.0. 375.14 g. 1 v,o,. 272.85 g.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)
  • Luminescent Compositions (AREA)
  • Manufacture, Treatment Of Glass Fibers (AREA)
US00166777A 1970-07-31 1971-07-28 Vitreous compounds with bistable electrical characteristics Expired - Lifetime US3779948A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR7028387A FR2098953A5 (enrdf_load_stackoverflow) 1970-07-31 1970-07-31

Publications (1)

Publication Number Publication Date
US3779948A true US3779948A (en) 1973-12-18

Family

ID=9059618

Family Applications (1)

Application Number Title Priority Date Filing Date
US00166777A Expired - Lifetime US3779948A (en) 1970-07-31 1971-07-28 Vitreous compounds with bistable electrical characteristics

Country Status (4)

Country Link
US (1) US3779948A (enrdf_load_stackoverflow)
DE (1) DE2137865A1 (enrdf_load_stackoverflow)
FR (1) FR2098953A5 (enrdf_load_stackoverflow)
GB (1) GB1365917A (enrdf_load_stackoverflow)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674645A (en) * 1996-09-06 1997-10-07 Bell Communications Research, Inc. Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes
WO1998010476A1 (en) * 1996-09-06 1998-03-12 Bell Communications Research, Inc. Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2862891A (en) * 1954-06-26 1958-12-02 Philips Corp Sintered electrical resistor
US3258434A (en) * 1962-08-01 1966-06-28 Gen Electric Semiconducting glass
US3469729A (en) * 1966-06-30 1969-09-30 Westinghouse Electric Corp Sealing compositions for bonding ceramics to metals
US3503902A (en) * 1966-09-14 1970-03-31 Hitachi Ltd Method for producing temperature sensitive resistor comprising vanadium oxide
US3598762A (en) * 1962-03-22 1971-08-10 Hitachi Ltd Vanadium oxide semiconductors and method of manufacturing same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2862891A (en) * 1954-06-26 1958-12-02 Philips Corp Sintered electrical resistor
US3598762A (en) * 1962-03-22 1971-08-10 Hitachi Ltd Vanadium oxide semiconductors and method of manufacturing same
US3258434A (en) * 1962-08-01 1966-06-28 Gen Electric Semiconducting glass
US3469729A (en) * 1966-06-30 1969-09-30 Westinghouse Electric Corp Sealing compositions for bonding ceramics to metals
US3503902A (en) * 1966-09-14 1970-03-31 Hitachi Ltd Method for producing temperature sensitive resistor comprising vanadium oxide

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5674645A (en) * 1996-09-06 1997-10-07 Bell Communications Research, Inc. Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes
WO1998010476A1 (en) * 1996-09-06 1998-03-12 Bell Communications Research, Inc. Lithium manganese oxy-fluorides for li-ion rechargeable battery electrodes

Also Published As

Publication number Publication date
FR2098953A5 (enrdf_load_stackoverflow) 1972-03-10
GB1365917A (en) 1974-09-04
DE2137865A1 (de) 1972-03-30

Similar Documents

Publication Publication Date Title
US4013592A (en) High temperature thermistor composition
DE2006714C3 (de) Elektrisch leitfähige, wismuthaltige Oxide
Coffeen Ceramic and dielectric properties of the stannates
Gopalakrishnan et al. Studies on the La2− xSrxNiO4 (0⩽ x⩽ 1) system
US3996168A (en) Ceramic electrical resistor
US4894361A (en) Superconducting metal oxide Tl-Pb-Ca-Sr-O compositions and processes for manufacture and use
US3779948A (en) Vitreous compounds with bistable electrical characteristics
US5227257A (en) Compositions derived from bi4v2011
US4929594A (en) Superconducting composition Tl2 Ba2 CuO6+x and process for manufacture
US3123748A (en) figure
US3518209A (en) Semiconductive glasses
DE69120840T2 (de) Supraleiter auf Thalliumbasis substituiert durch seltene Erden
DE68913749T2 (de) Supraleitende metalloxid-zusammensetzungen.
US5017554A (en) Superconducting metal oxide Tl-Pb-Ca-Sr-Cu-O compositions and processes for manufacture and use
US3037942A (en) Positive temperature coefficient of resistivity resistor
EP0418244B1 (en) SUPERCONDUCTING Bi-Sr-Ca-Cu OXIDE COMPOSITONS AND PROCESS FOR MANUFACTURE
US3904404A (en) Rhodium and ruthenium compositions
Sainkar et al. X‐ray photoelectron spectroscopic studies on ZnO‐Sb2O3 varistors
Lotgering et al. Crystal structure and magnetic properties of Cu4Mn2Te4
Uemura et al. The Semiconduction in the Molten Tl‐CuTlTe2 System
Fujihara et al. Oxygen deficiency and electrical conductivity of Nd1− xAxNiO3− y (A= alkaline earth) prepared by the low-temperature process
DE68922860T2 (de) Superleitfähige metalloxidzusammensetzungen und verfahren zur herstellung und verwendung.
EP0428630B1 (en) Superconducting metal oxide compositions and processes for manufacture and use
DE69511921T2 (de) Thermoelektrisches Halbleitermaterial
JPH0558708A (ja) 酸化物超伝導体