DE2137865A1 - Glasses with bistable electrical characteristics - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. BEAUTIFUL FOREST DR.-ING. TH. MEYER DR. FUES DIPL-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLOPSCH DIPL.-ING. SELTING

July 27, 1971 Ke / Ax

AGENCE NATIONALE DE VALORIZATION DE LA RECHERCHE, Tour Aurore Cedex, Paris-Defense (Hauts-de-Seine) (France)

Glasses with bistable electrical characteristics

The invention relates to a new class of glasses that bistable electrical characteristics, i.e. having two different states of electrical resistance. The er- < finding is also on a method for producing this Glasses as well as their use directed.

Glasses that have these properties are already known. As prior art publications are for example French patents 1,445,528 and 1,351,433. The French patent specification 1 445 528 describes binary glasses. The French patent specification! 351 433 * specifically referred to here describes ternary or quaternary glasses of the type AsTeI, AsTeSe, AsTlSe, VOP, VOPBa, VOPPb or AsBTiO. Half-length terms of this type are used in electrical components, where they are combined with a transmitter for electrical signals in order to make at least their two resistance states usable. These electrical components are used among other things in the technology of commutation, in amplifiers and electronic oscillators in the solid state as well as storage elements, as described in detail in the above-mentioned French patent 1 351 433 ..

The following publications should also be mentioned with regard to the state of the art in this field? The © work by R. and

O. Holzinger "Field-dependent change in resistance in glasses" in "Zeitschrift für angewandte Physik" 28, No. 4, 1969, pages 196 to 201, relates to a glass for electrical components that assume the state of the conductor and the state of the resistance and from one corresponding mixture of oxides BpO- ,,

CaO and V _o 0 _c can exist. 2 5

Swiss Patent 490 728 (Siemens AG) relates to a semiconductor commutator that does not have a barrier layer. A glass is formed from a mixture of VpO ₁ - and SrCO-.

Also to be mentioned are British patent specification 1,168,107, which relates to a process for the production of a thermistor based on a sintered mixture of VpOc and a combination of different oxides, e.g. Na, Ca and Al (page 4, example 4), and US Patent specification 5 258 454, which relates to a semiconductor consisting of a glass, which contains as a component CaO.2B ₂ O ₅ -V ₂ O ₅ Fe ₅ O ^ -Al ₂ O (column 6, example X),

However, the known products are not in all areas of application satisfactory, so that glasses, which in particular have improved mechanical and electrical properties, are desired.

The invention relates to glass masses in their electrical and mechanical properties are far superior to the corresponding known glasses. The new class of Glasses can be represented by the following general formula will:

^Ca 2-x-2z ^IJ1 z ^Na 2 ₊ x ₊ z ^A1 ly ^Pe _y ^V 3 ⁰ 12-x ^P x ^(I >

Here the letters have the usual meanings of the elements of the periodic systems with the exception of Ln, which is a rare earth from the class of lanthanides like La or yttrium Y denotes, while x, y and ζ are numbers respectively are between 0 and 1, which can stand separately or at the same time for 0 and with each other by the relationships of

209814/1401

BATH ORIGINAL

ion equilibrium are connected and preferably the following Inequalities correspond to:

χ <0.15 y «= 0.5 ζ <Ό, 5

The chemical composition of the new glass compounds appears quite complicated at first glance. However, they all contain a common basic matrix of the following Formula:

Ca ₂ Na ₂ Al V ₅ O ₁₂ (II)

This particular compound corresponds to formula (I) in which

The compound of formula (II) has bistable electric Properties that meet the needs of the invention. It is in its mechanical and electrical properties superior to the known compounds. For example, the difference in resistivities is between the conductor state and the resistance state by at least ten times greater than in the corresponding known glasses.

The other compounds according to the invention can be obtained from the basic matrix of the formula (II) by introducing the rare Earth Ln and / or of iron Fe and / or fluorine F can be made.

In certain cases, bistable glasses can also be produced using several compounds of formula (I), one of which is, for example, the basic compound of the formula (II). The products obtained correspond no longer of formula (I), but retain bistable electrical characteristics.

BATH ORIGINAL 2098U / U03

■ The new class of glasses is shown in the following examples Further illustrated. What these masses have in common is that they have bistable electrical characteristics and represent glasses, i.e. they do not show any defined lines on the X-ray diagrams (Debye-Scherrer diagram). In contrast to most known products, these new glasses are very brittle and highly oxidizable Glasses based on As, Te, I or analogous elements have a very high mechanical and chemical resistance.

The new glasses are made from precursors of the chemical elements of the formula under critically important conditions (I), in particular oxides and salts, e.g. carbonates. The mixture of these precursors is practically stoichiometric Ratios corresponding to formula (I) must be heated to high temperatures for a long time become to form glasses.

The invention further comprises a process for the production of the glasses of the formula (I) by intimately mixing the precursors forming a mixture which contains the elements of the compounds mentioned in essentially stoichiometric Contains proportions, and heat treatment. The process is characterized in that the mixture is left for at least 5 hours heated to a temperature above 1500 ° C.

In general, it is sufficient to heat the material 6 to 12 hours to temperatures of 1300 ° to l400 ° C, for example 1350 ⁰ C. If melting is carried out at too low a temperature or for an insufficient period of time, no glass masses can be formed. If the conditions according to the invention are not observed, products are always obtained which crystallize during cooling.

BATH ORIGINAL 209 8U / U03

example 1

Making the connection CapNa ^ Al V- ^ O _,? (Molecular weight

588.95).

An intimate mixture is made up of the following components:

50.97 g (0.5 mol) Al ₂ O ₃ 200.18 g (2 mol) CaCO ₃ 106.00 g (1 mol) Na ₂ CO ₃ 36?, 8 g (1.5 mol) V ₂ O ₅

The total weight of the mixture is thus 720.95 g · The mixture is then heated in the open air in a platinum crucible for 2 hours at 65O ⁰ C, 2 hours at 750 ⁰ C and-closing r 6 hours at 125O ° C. The chemical analyzes carried out during the melting show that the sodium content does not change. The product obtained is a glass body which has the above formula (II) and has two different states of electrical resistance.

Electrical measurements were carried out to determine the properties of the new product. The experimental set-ups and the results obtained are shown in Figs.

1 is a general circuit diagram which enables the voltage-current characteristics to be determined.

Fig. 2 is a detailed view showing the arrangement of the sample containing the product (II).

3 shows the voltage-current curve obtained.

Fig. 1 shows schematically the experimental set-up used. A 300 V direct current source 1 is controlled by a potentiometer '*> ■

2098U / U03

BATH ORIGINAL

connected to a reversing switch 2 - The reversing switch 2 is connected on the one hand via an indicating resistor 4 (10.Ω-) and a voltmeter 5 to earth and an input of a recorder 6 of the voltage-current curve and, on the other hand, applied to the sample 7 to be examined via a resistor 8 (50 kiZ). The other terminal of the sample 7 is grounded through a resistor 9. A conductor 10 connects the other entrance of the recorder 6 with one of the terminals of the resistor 8.

Fig. 2 shows a detail of the arrangement of the sample 7 · intermediate the conductors which connect the sample 7 to the resistors 8 and 9 (FIG. 1), two graphite cylinders 11 and 12 are arranged. The sample of the product to be examined is arranged in the form of a disk IJ between these graphite cylinders. The disc 13 is between the graphite cylinders held by a conductive coating, e.g. a silver paint (manufacturer Degussa). The disc 13 has a thickness of about 0.1 mm.

FIG. 3 shows the voltage-current curve which has been recorded with the device shown in FIG. 1 for sample 13 based on the compound Ca ₂ NapAlV ^ 0 ₁₂ (H). The voltages are plotted as the abscissa (V) and the currents as the ordinates (mA). The graph shows that compound (II) has two states:

1. a state of resistance that corresponds to the following values:

V = 14o, I = 0.12 mA corresponding to R .- ^ 1.17.1O ⁶ XL

2. a conductive state that corresponds to the following values:

V = 5.5V I - 4 mA corresponding to R -j 1.37.10 ^ -Ω-

On the curve, part A corresponds to the state as a reflection

2098U / U03

BATH ORIGINAL

- 7 stood and part B the state as a ladder.

Example 2

Manufacture of the product Ca ,, o £ Nap τ ^ Αΐν-, Ο ,, 86 ^F O (formula (i), in which χ = 0.14, y = 0, ζ = 0)

A mixture of oxides and carbonates of the following composition, is added to the sodium fluoride in the specified amount, the heat treatment described in Example 1 is subject to:

1.86 Mole CaCO, 186, I67 G 1.0 Mole Na ₂ CO ₅ 106.00 G 0.5 Mole Al ₂ O ₃ 50.97 G 1.5 Mole V ₂ O ₅ 363.80 G 0.14 Mole NaP 5.88 G total weight 712.817 G

A glass with a molecular weight of 586.977 is obtained as the product. When the content of fluoride ions exceeds 0.14 mol, no glass can be formed.

Example 3

Manufacture of the product CapNapFeV-, Ο, ρ (formula I, in which x = 0; y = 1; ζ = 0) and the product ^Ca 2.4 ^Na 2.4 ^A1 0.2 ^FeV 3.6 ° l4.4 ·

This product, which does not have the stoichiometric composition given by the formula (I), can be prepared from the basic _{compound Ca 2} Na ₂ AlV-, O ₁₂ (II) and the compound Ca.

a) The mixture corresponds to the compound Ca ₂ Na ₂ FeV- ^ O ₁₂ and contains

2098U / U03

0.5 Mole Pe ₂ ° 3 79.85 G 2.0 Mole CaCO, 200.00 G 1.0 Mole * 106.00 G 0.5 Mole V ₅ ^ 272.00 ε All in all - 657.85 G

This mixture is heated in a platinum crucible in air for 2 hours at 650 ⁰ C and then for 2 hours at 800 ° C. This gives a reaction product which is finely ground.

b) The product (3a) is mixed with 20 mol of the likewise finely ground product (II). The mixture is heated in a covered platinum crucible ^{to 1350 ° C. for 6 hours.} The glass forms as it cools.

Example 4

This example illustrates a further variant of a glass mass obtained from the products of Examples 2 and 2 (b) can be produced. This product has the gross formula

^ 2.3 ¹ T ^a 2.42 ^AJ -l, 04 ^re 0.2 ^v 3.72 ^u l4.8r0, l4

0.2 mol (105.17 g) of the product produced according to Example j5 (b) are ground and mixed with 1 mol (586.977 g) of the glass produced according to Example 2, which is also ground. The mixture is heated ^{to 1350 °} C. in a covered platinum crucible for 6 hours. The glass forms as it cools.

Example 5

Production of the product Ca ₀ ι, Υ- _o Na _o I ₁ V-, <r0.1 ₁ 1.

This example illustrates a variant of the glass mass obtained by mixing a compound containing yttrium with the basic product prepared according to Example 1 produced

2098U / U03

can be. First, a mixture of the following composition manufactured:

O, 5 Mole Y ₂ O ₃ 112.92 G 2, 0 Mole CaCO-, 200.00 G 1, 0 Mole Na ₂ CO ,, 106.00 G 1, 5 Mole v ₂ o 272.00 G

The mixture is heated for 2 hours at 65O ⁰ C and then for 2 hours at 800 ° C. The product obtained is ground, 0.2 mol (138.18 g) of this finely ground compound is mixed with 1 mol (588.95 g) of the likewise ground glass produced according to Example 1. After mixing, the mixture is ^{heated to 0} ° C. for 6 hours. The glass forms as it cools.

Examples 6- 2h

The following table lists a number of glasses made in the manner described in Example 1 can be. In the first three columns of the table the values of the indices χ, y and ζ are given, those of the formula (I) correspond. The formula of the glass is given in the fourth column, and the quantities are given in the last column of the starting materials used are given in moles and grams.

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(Quantities in moles and g) 6th 0.04 0 0 ^{Ca 1.96 Na} 2.04 A1V 3 ° ll, 96 ^F 0.04 1.96 CaCO ^ 196.17 g
1.00 Na ₂ CO, 10 6 g
1 Al (NO ₅ J ₅ .9H ₂ O 375.14 g
1.5 V ₂ O ₅ 272.65 g
0.04 NaP 1.6788 g 7th 0 0.1 0 ^0a 2 ^Na 2 ^A1 0.90 ^Fe O.1 ^V 3 ° 12 2 CaCO, 260.18 g
1 Na ₂ CO, 10 6 g
0.9 Al (NOj) ₅ ^ H ₂ O 337.62 g
0.05 Fe ₂ O ₅ 7.979 g
1.5 V ₂ O ₅ 272.85 g 8th 0.12 0.1 0 ^Ca 1.88 ^Na 2.12 ^A1 0.90 ^Pe 0. l -
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0.05 ^Fe 2 ° 3 7.979 g
1.5 V ₂ O ₅ 272.85 g
0.12 NaP 5.036 g

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2098U / U03

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(Quantities in moles and g) 18th 0 0.20 0.20 ^{Ca 1.48 Ln} 0.20 ^Na 2.32 ^A1 0.8 ^Fe 0.2 ~
^V 5 ° ll, 88 ^F 0.12 1.48 CaCO, 148.13 g
0.10 YgO, or La ₃ O ₅ La ₂ O, 16.29 g
Y ₂ O ^ 11.29 g
1.10 Na ₃ CO ₅ 116.6 g
0.8 Al (NO ₅ ) ^ H ₃ O 300.11 g
0.1 Fe ₂ O ₅ 15.95 g
1.5 V ₂ O ₅ 272.85 g
0.12 NaF, 5.036 g 19th 0.12 0 0.24 ^{Ca 1.52 Ln} 0.2 » ^Na 2.24 A1V 3 ° 12 ^; 1.52 CaCO ₅ 152.13 S
0.12 Y ₂ O ₅ or La ₃ O ₅ La ₃ O ₅ 16.29 g
Y ₂ O ₅ 11.29 g
1.12 Na ₂ CO, 118.72 g
1.0 Al (NO ₅ ) ₅ .9H ₂ 0 375.14 g
1.5 V ₂ O ₅ 272.85 g 20th 0 0.24 L ^{Ca, Ln} 40 0.24 ^Na 2.56 ^A1V 5 ⁰ ll, ~ 88
^P 0.12 1.40 CaCO- 140.12 g
0.12 La ₃ O ₅ or Y ₃ O ₅ La ₃ O ₅ 16.29 g
Y ₃ O ₅ 11.29 g
1.12 Na ₃ CO ₅ 118.72 g
1.0 Al (NO ₅ ) ₅ .9H ₃ 0 375.14 g
0.12 NaF 5.036 g
1.5 V ₃ O ₅ 272.85 g

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C »^ Ct ^ Y ₂ O ₅ 16.29 G 21st 0.24 1.52 11.29 G 0.12 Na ₂ CO ₅ 118.72 G Al (N0,),. 9H _o 0 337.62 G 1.12 7.97 G 0.90 v ₂ o / 272.85 G 0.05 CaCO, La ₂ O ₅ 140.12 G 0.12 0.10 Approx ₁ , 4O ^Ln O, 24 ^Na 2.36 O ^A1, 9 ^Pe O, l " 1.5 La ₂ O ₅ or Y ₃ O ₅ 16.29
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Cm ^ 118.72 G 0.12 Al (NO ₅ ) -,. 9HgO 337.62 G 1.12 Fe ₂ O, 7.97 G 0.9 272.85 G 0.05 NaF 5.036 G 1.5 CaCO, La ₂ O ₅ 152.13 S. 0 0.20 Ca, , 52 ^Ln 0.24 ^Na 2.24 ^A1 0.8 ^Pe 0.2- 0.12 La ₃ O ₅ or Y ₂ O ₅ ^Y 2 ° 3 16.29 G 23 0.24 V 0 1.52 11.29 G 12th 0.12 Na ₂ CO ₅ 118.72 G Al (N0,),. 9H _o 0 300.11 G 1.12 15.95 G 0.8 v ₂ o / 272.85 G 0.1 1.5

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(Quantities in moles and g) CaCO,
La ₂ O, or Y ₂ O- * La ₂ O,
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1.12 300.11 G 0.8 Fe ₂ O ₃ 15.95 G 0.1 V ₂ O ₅ 181.90 G 1.5 NaF 5.036 G 0.12

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Claims (9)

Pate ntansprüche Glasses with bistable electrical characteristics and the formula ^Ca 2- _X -2z ^Ln ^ ^a 24-x ₊ z ^Al 1 -y ^Pe y ^V 3 ° 12-x ^F x in which the letters in the usual way denote the elements of the periodic table with the exception of Ln, which stands for a rare earth from the class of larithanids or for yttrium Y, and x, y and ζ each stand for numbers between 0 and 1, which individually and simultaneously can be zero and are connected to one another by the relationships of the ionic equilibrium. 2. Glasses according to claim 1, characterized in that Ln in the formula mentioned in claim 1 for lanthanum La ' "stands. 3. Glasses according to claim 1 and 2, characterized in that that x, y and ζ satisfy the following equations: x <0.15 x <0.3 4. Glasses according to claim 1 and 2, characterized in that x, y and ζ stand for zero, the compound of the formula Ca ₂ Na ₂ AlV ^ O ₁₂ corresponds « 5. Glasses consisting of mixtures of at least two Compounds according to Claims 1 and 4. 6. Process for the production of glasses according to claim 1 to 5 by intimate mixing of the starting compounds forming mixtures containing the elements of these compounds in essentially stoichiometric proportions contain, and heat treatment, thus marked * net that the mixture is ^{heated to a temperature above 130O 0} C for at least 5 hours. ■ 209814/1403 7. The method according to claim 6, characterized in that the mixture is heated ^{to temperatures of 130 to HOO 0 C for 6 to 12 hours.} 8. The method according to claim 6 and 7, characterized in that the Gemis-ch of cooling to ambient temperature leaves to form the desired glass. 9. Use of the glasses according to claims 1 to 8 as materials with bistable electrical characteristics, i.e. at least one state of resistance and one Ladder condition. 209 814/1403