WO1990008739A1 - Mixed-valency copper oxide containing lead and barium and process for its production - Google Patents

Abstract

A mixed-valency copper oxide having a perovskite-derived structure. This oxide is based on the following formula: PbxBaySrzTr1-tCatCu3O8+δ, where Tr is chosen from the rare earth group including yttrium, x is a number included in the half-closed interval ]0.2] preferably higher than 0.1, whereby y is included in the half-closed interval ]0.2], preferably higher than 0.1, whereby z is included in the half-closed interval ]0.2] preferably high than 0.1 provided that x + y + z « 3, but preferably between 2.5 and 3, t is included in the half-closed interval ]0.1/2] and where delta is included between 0 and 1/4. Application: the electrical industry and electronics.

Description

 COMBINED VALENCE COPPER OXIDE CONTAINING LEAD AND BARIUM AND PROCESS FOR PRODUCING THE SAME.

The present invention relates to new copper oxides with mixed valence of structure derived from perowskite containing lead and barium.

It relates more particularly to superconductive compositions having at least partially a structure derived from perowskite.

During the last luster, these oxides, which result from an intergrowth of a structure of the perowskite type and of a structure of the sodium chloride type, we have been the subject of very numerous studies, all the more so since their electrical and more particularly superconductive properties have been demonstrated at temperatures above 60 /

70.

These copper oxides have structures generally qualified as oxygen deficient, which means that there is not enough oxygen to fill all the available sites of the perowskite. In fact, they have oxygen superstoichiometric zones compared to cupric copper. This overstoichiometry is undoubtedly linked to their characteristic of being superconductive at relatively high temperatures. The structures of these copper oxide compounds are described in numerous publications. Among the latter, it should be mentioned: A) Article by B. RAVEAU "Many oxide structures can be constructed from the basic type ReO," - Proc. Indian Natn.

Sci Acad., 52, A, n ° 1, 1986, pages 67-101; B) Article by L. ER-RAKHO, C. MICHEL, 3. PROVOST and B.

RAVEAU "Perowskite series lacking oxygen containing CuII, CuIII" -

Journal of Solid State Chemistry 37, 151-156 (1981);

C) Article by C. MICHEL and B. RAVEAU "Oxidation of oxygen in mixed valence copper oxides related to perovskites" - Revue de Chimie Minérale, t 29, 1984, page 407;

D) Article by C. MICHEL, F. DESLANDES, 3. PROVOST, CRAcadémie des Sciences, Tome 304, II, N ° 17, p.1059 (1987); E) Article by C. MICHEL, F. DESLANDES, 3. PROVOST, P. LE3AY, R. TOURNIER, M. HERVIEU and B. RAVEAU, report to the Académie des Sciences, t 304, II, n ° 19, p. 1,169 (1987);

F) The review article, which in addition to the structural properties describes electrical and magnetic properties and which is published in the

Research n ° 195 in January 1988, vol. 19, pages 53-60, entitled "The discovery of high temperature superconductivity" by K. Alex MULLER and 3. Georg BEDNORZ.

Furthermore, such structures and their industrial applications have been, for example, described in patent applications whose objects are inventions made at the CRISMAT Laboratory in Caen, attached to the C.N.R.S., in particular those under the numbers 87 03717 and 87 03975.

Over the past year, numerous sub-families of mixed valence copper oxide with a structure derived from perowskite have been studied, in particular with a view to obtaining a range of superconductors with specific and better adapted characteristics. than others to certain applications.

The number of elements used in these structures and the variability of the proportions lead to an almost infinite number of combinations. Only a very small fraction of these compounds has interesting electrical properties.

Among the mixed valence copper oxides obtained by the intergrowth of a perowskite type network and a sodium chloride type network, which has been symbolized by the formula (ACuO,) (A'O), the members having superconductive properties where n = l are extremely few. In the above formula the ACuO- group. represents the perowskite layers, m indicating the number of layers, while the group A'O denotes the sodium chloride layers, n marking the number, A and A 'represent metals, for example A represents divalents such as alkalinos -terreux and A 'trivalents such as bismuth. There is however no precise rule, each new perowskite being a particular case. Only the perowskite network and the sodium chloride networks are maintained. Apart from the compound of formula La_CuO. (m = l, n = l) synthesized a few years ago, we simply isolated the oxide La _? AT . Cu ₂ 0 ₆ (where A is calcium or strontium) which, moreover, are not superconductive, and more recently, Pb-Sr-Y oxide. , Ca _n , -Cu, 0 ,, but with a fairly low critical temperature of zero resistance (cf.

R.3. Cava et al, the article "Superconductivity Near 70K in a New Family of Layered Copper Oxides" in the journal Nature).

One of the aims of the present invention is to find a subfamily of previous structure or n = 1 and whose critical temperatures of zero resistance are at least equal to approximately 50K.

This object and others which will appear subsequently are achieved by means of a mixed valence copper oxide, characterized in that it has the following formula I:

Pb x Ba y Sr z Tr 1. - ₊ tCa t. Cu 3, O 8 ₀ + <≈ < ^• , 'Tr is chosen from the group of rare earths including yttrium, x is a number included in the semi-closed interval] 0.2], preferably greater than 0.1, including in the semi-closed interval] 0.2] preferably greater than

0.1, z being in the semi-closed interval] 0.2] preferably greater than

0.1, with the condition x + y + z _ £ 3, preferably between 2.5 and 3, t is in the semi-closed interval] 0, l / 2] preferably greater than

About 0.1; and where delta is between 0 and 1/4. Advantageously x is between 1/3 and 4/3 preferably between 1/2 and

1. is advantageously between 2/3 and 5/3, preferably between 1 and

3/2. z is advantageously between 1/3 and 4/3, preferably between 1/2 and 1. The delta value is difficult to control and depends above all on the structure of the compound. It also depends on the value of t and on the operating conditions for the synthesis of this mixed valence copper oxide. It should be noted that when t is equal to 0, and that delta is zero, there is already a phenomenon of overstoichiometry of the oxide compared to the other elements, it being understood that the lead remains in the divergent state. It should finally be noted that the compound of formula PbBaYSrCu, O _χ is not superconductive. To be superconductive, it is necessary that the value of t is at least equal to about 1/5. Thus for the value of t = 1/3 (and x = 2/3, y = 4/3, z = 2/3), it was found a superconductivity up to a critical temperature R = 0 of 50K (value corresponding to the temperature below which a negative magnetic moment is observed (see figures). The structures according to formula I correspond to the structures of the oxide PbBaYSrCu-O _g in which the calcium atoms replace the yttrium or where appropriate other rare earths.

Advantageously, Tr is chosen from the group consisting of rare earths (that is to say Ianthanides, lanthanum, scandium and yttrium) with the exception of rare earths having a valence IV. Preferably, we choose

Tr in the group consisting of the group of yttrium and yttric lands, that is to say, of yttrium plus the Ianthanides of gadolinium to lutetium including neodymium.

The structure shown in Figure 1 shows the typical limit structure of copper oxides according to the invention, when the network is perfect.

This structure comprises in succession: O

. un plan (4) Tr ., _.,_ Ca_{fc / 2} Sr., ^ Pb v

. a plan (4) Tr., _., _ Ca _{fc / 2} Sr., ^ Pb v

. a plane (5) ~ Cu0 ₂ ~ 2 ²

. a plane (6) Tr ^ Ca _{t / 2} Sr ^ _{pb ∑} . a plan (7) 2 Cu0 ₂ 2 2

plans 2 et 1 ' participent la fois à la couche type chlorure de sodium et à la triple couche pérowskite, cependant que le plan 1 participe à la fois à la couche de type chlorure de sodium et à la triple couche pérowskite du motif précédent, v représente un échange partiel possible entre le plomb de la couche de type NaCl avec du strontium situé à l'intérieur de la triple couche pérowskite (plans (4) et (6)). v est compris entre 0 et 1/3, en général entre 0 et 1/4.. a plan (V) Pbx-v Bay_ Sr. _{j Q} Planes 1 and 2 constitute an insulating sodium chloride monolayer. The planes 2, 3, 4, 5, 6, 7 and l constitute a triple layer ^Tr lt ^Ca _t ^Cu 3 ° 5 " ^l - ^are to note that the

planes 2 and 1 'participate both in the sodium chloride type layer and in the triple perowskite layer, while plan 1 participates in both the sodium chloride type layer and in the perowskite triple layer of the preceding pattern, v represents a possible partial exchange between the lead of the NaCl type layer with strontium located inside the perowskite triple layer (planes (4) and (6)). v is between 0 and 1/3, generally between 0 and 1/4.

Referring to Figure 1, the oxygen atoms are symbolized by a white circle, while in planes 1, 2 and 1 ', lead and barium are symbolized by a black disc struck with a white star; in planes 3, 5 and 7, copper is symbolized by a small black disc; in planes 4 and 6 the rare earth, calcium and strontium or lead are symbolized by a large black disc. It should also be noted that if there are metallic gaps in the network, these gaps essentially take the place of the metals represented in the networks of sodium chloride type.

Another object of the present invention is to provide a process for the synthesis of copper oxides with mixed valence according to the present invention comprising the following steps: a) grinding and mixing of barium peroxide, lead oxide, Sr_CuO ,, CuO, Tr-O- and CaO in the desired proportion, b) compression of the mixtures obtained in a) in the form of pellets, c) subjecting these pellets to heating at a temperature between 700 and 900 ° C, preferably between 750 and 850 ° C under an inert atmosphere containing a small proportion of oxygen for 1/2 to 2 days. d) rapid cooling to room temperature. By rapid cooling is meant cooling between 10 minutes and 1/2 hour (approximately 1/4 hour).

inférieur à 20 micromètres, de préférence à 10 micromètres, en général autours de 5 micromètres. Il est possible de travailler à des mailles de broyage encore plus faible en réalisant un broyage humide, ce qui est relativement favorable au composé final mais qui nécessite une opération de séchage avant l'étape b) ou au cours de l'étape a). C'est pourquoi un broyage à sec est préféré. La compression de l'étape b) est réalisée sous pression usuelle en la matière, telle que des compressions supérieures à 0,5The grinding is carried out so as to obtain a usual particle size in the material, such as a particle size having a

less than 20 micrometers, preferably 10 micrometers, generally around 5 micrometers. It is possible to work with even smaller grinding meshes by carrying out wet grinding, which is relatively favorable to the final compound but which requires a drying operation before step b) or during step a). This is why dry grinding is preferred. The compression of step b) is carried out under usual pressure in the material, such as compressions greater than 0.5

( ^~ 9 ton / cm ² (50.10 Pa) generally between 0.1 and 1.10 Pa.

For a small proportion of oxygen, it is necessary to understand a proportion sufficient for the oxide to be superconductive and insufficient for the lead to pass to the oxidation state IV.

As an indication, the oxygen content must be less than

10% generally between 0.5 and 5%, preferably around

1%.

The term “inert atmosphere” should be understood to mean nitrogen, rare gases, their mixtures or any mixture of gases remaining inert with respect to the mixed valence copper oxides and the starting products described above.

It is also possible to carry out this synthesis at non-atmospheric pressures. In these cases, the conditions on the oxygen content remain identical, expressed as partial pressure of oxygen.

In this process, the oxides can be replaced by any body which by thermal decomposition gives the desired oxide. Peroxides can thus be used in place of oxide. The use of carbonate is not recommended due to the affinity of barium for carbonic acid. The following nonlimiting example shows the characteristics of the new superconductors according to the present invention. Example

Various mixtures corresponding to formula II were prepared from Ba0 ₂ , PbO, Sr ₂ Cu0 ₃ , CuO, Tr ₂ 0 ₃ , CaO. These mixtures are put into the form of pellets by compression under a pressure of the order of 1 to

Q 10 tonnes / cm ² (0.1 to 1.10 Pa). The pellets thus obtained are brought to between 750 and 850 ° C. under a nitrogen atmosphere for approximately 15 hours, then are cooled to room temperature in 15 minutes.

The pellets are ground to a particle size between about 10 and about 20 micrometers. The samples used for the physical characterizations are prepared in the form of bars of 12 x 2 x 0.5 mm ³ , the powders with a particle size between 10 and 20 micrometers, are pressed under 4 tonnes / cm ² (0.4 - 10 Pa) and fritted for 4 to 5 hours under the same atmosphere as that used for the synthesis, and at the same temperature. Magnetic measurements

We use a Foner type vibrating sample magnetometer

(model 155 from EGG) equipped with a cryostat and allowing to work up to 4.2K. The sample is a sintered bar a few millimeters in length. It is fixed to the end of a rigid rod whose other end is fixed to the vibrator.

The displacement of the sample, placed in a uniform magnetic field, in front of the captive coils, gives rise to an induced voltage at the displacement frequency.

It is thus possible to determine the magnetic moment of the sample, as a function of the uniform magnetic field applied and of the temperature.

The superconducting volume is measured at 4.2K by comparing the diamagnetic susceptibility observed with that which should be obtained for a totally diamagnetic sample (niobium as reference). To accurately determine the critical temperature, a SQUID magnetometer is used. The sample is placed in a uniform magnetic field. A stepping motor moves the sample in captive coils. The flow inside the coils is precisely determined using a SQUID. The signal measured according to the displacement makes it possible to calculate the magnetic moment, according to the temperature and the applied field.

FIG. 2 represents the magnetic moment measured as a function of the temperature and FIG. 3 represents the magnetic moment as a function of the applied field.

In both cases the sample has the formula Pb, Ba _ _{4 /} SR_ ,, y _2/3 ^Ca l / 3 ^CU 3 # 8 ₊ i ^{Tc = 50K)} -

Claims

1. Copper oxide with mixed valence, characterized in that it has the following formula I: Pb _χ Ba _y Sr _z Tr ₁ _ _t Ca _t Cu ₃ O _{8 +} , where Tr is chosen from the group of rare earths including yttrium, x is a number included in the half-closed interval] 0.2], preferably greater than 0.1, including being included in the half-interval closed] 0.2] preferably greater than 0.1 „z being in the half-closed range] 0.2] preferably greater than 0.1, with the condition x + y + z ^ 3, preferably between 2.5 and 3, t is in the semi-closed interval] 0, l / 2] and where delta is between 0 and 1 / 4. 2. Copper oxide with mixed valence according to claim 1, characterized in that x is between 1/3 and 4/3, preferably between 1/2 and 1. 3. Copper oxide with mixed valence according to one of claims 1 and 2 taken separately, characterized in that y is between 2/3 and 5/3, preferably between 1 and 3/2. 4. Mixed valence copper oxide according to one of the claims 1 to 3 taken separately, characterized in that z is between 1/3 and 4/3, preferably between 1/2 and 1. 5. Process for the synthesis of copper oxides with mixed valence comprising the following stages: a) grinding and mixing of barium peroxide, lead oxide, Sr-CuO ,, CuO, Tr ₂ O, and CaO into desired proportion, b) compression of the mixtures obtained in a) in the form of pellets, c) subjecting these pellets to heating at a temperature between 700 and 900 ° C, preferably between 750 and 850 ° C under an inert atmosphere containing a low proportion of oxygen for 1/2 to 2 days, _k ^~ d) rapid cooling to room temperature.