Patent Publication Number: US-2003227009-A1

Title: Metal oxide materials

Description:
[0001] The invention comprises certain novel metal oxide materials which exhibit superconductivity at elevated temperatures and/or which are useful as electrodes or electrolytes in electrochemical cells, sensors, and as catalysts.  
       [0002] It is known that certain classes of metal oxide will exhibit the phenomenon of superconductivity below a particular critical temperature referred to as T c . These include as prototypes BaPb 2-x Bi x O 3-d , Ba 2-x Sr x CuO 4-d , YBa 2 Cu 3 O 7-d  as described in The Chemistry of High Temperature Superconductors, ed. by Nelson et al, American Chem. Soc. 1987, and Bi 2 Sr 2 CaCu 3 O 5-d  as described by subramanian et al, Science 239, 1015 (1988). We have identified this last material as the n=2 member in a homologous series of approximate formula  
       Bi 2 (Sr,Ca) n+1 Cu n O 2n+4+d , n=0, 1, 2, 3, . . . , 
       [0003] obtained by inserting an additional layer of Ca and an additional square planar layer of CuO 2  in order to obtain each higher member. These materials often exhibit intergrowth structures deriving from a number of these homologues as well as Bi substitution on the Sr and Ca sites. T c  is observed to rise as n increases from 1 to 2 to 3. The material YBa 2 Cu 4 O 8+d  has a layered structure similar to the n=2 member of this series Bi 2 Sr CaCu 2 O 8+d  and we expect therefore that YBa 2 Cu 4 O 8-d  belongs to similar series. One such seril es could be obtained by insertion of extra Y—CuO 2  layers resulting in the series of materials R n Ba 2 Cu n+3 O 3.5+2.5n-d , n=1, 2, 3, . . . and another by insertion of extra Ca—CuO 2  layers resulting in the series RBa 2 Ca n Cu n+4 O 8+2n-d , n=1, 2, . . . By analogy it slay be expected that T c  in these two series should rise with the value of n.  
       [0004] Binary, ternary or higher metal oxide materials containing as cations one or more alkali earth elements, such as these materials and having high oxygen-ion mobility ray also be used as electrodes, electrolytes and sensors for electrochemical applications. The oxygen-ions will move through such an electrolyte material under an applied electrical field allowing the construction of oxygen pumps for catalysis and other oxidising or reduction processes involving the supply or extraction of atomic oxygen. The oxygen-ions will also move through such an electrolyte material under a concentration gradient allowing the construction of batteries, fuel cells and oxygen monitors. For these materials to act effectively as electrolytes in such applications it is necessary that they have high oxygen-ion mobility through the atomic structure of the materials and at the same time have a low electronic conductivity so that the dominant current flow is by oxygen-ions and not electrons. For these materials to act effectively as electrodes in such applications it is necessary that they have a high electronic conductivity as well as a high oxygen-ion mobility so that electrons which are the current carried in the external circuit may cou  oxygen-ions w  are the current carrier in the internal circuit. Electrochemical cells including fuel cells, batteries, electrolysis cells, oxygen pumps, oxidation catalysts and sensors are described in “Superionic Solids” by S Chandra (North Holland, Amsterdam 1981).  
       [0005] Solid electrolytes, otherwise known as fast-ion conductors or superionic conductors have self diffusion coefficients for one species of ion contained within their crystalline structure ranging from 10 −7  to 10 −5  cm 2 /sec. A diffusion coefficient of about 10 −5  m 2 /sec is comparable to that of the ions in a molten salt and thus represents the   limit for ion mobility in a solid and is tantamount to the sublattice of that particular ion being molten within the rigid sublattice of the other ions present. Such high diffusion mobilities translate to electrical conductivities ranging from 10 −2  to 1 S/cm, the latter limit corresponding to that commonly found in molten salts. The n=0 member of the series Bi 2+e-x Pb x (Sr,Ca) n+1-s Cu n O 2n+4+d  and various substituted derivatives are identified as solid electrolytes with high oxygen-ion mobility. The n=1, 2 and 3 members of the series may have high oxygen-ion mobility as well as high electron conductivity and thus are potentially applicable as electrode materials.  
       [0006] The invention provides certain novel metal oxide materials which exhibit superconductivity at low temperatures and/or which are useful in such electrode, electrolyte, cell and sensor applications, or as electrochemical catalysts.  
       [0007] In broad terms the invention comprises metal oxide materials within the formula  
       R n+1-u-s A u M m+e Cu n O w   (1) 
       [0008] where n≧0 and n is an integer or a non-integer, 1≦m≦2, 0≦s≦0.4, 0≦e≦4, and 2n+(1/2)≦w≦(5/2)n+4, with the provisos that u is 2 for n≦1, u is n+1 for 0≦n&lt;1  
       [0009] and where  
       [0010] R and A are each any of or any combination of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Ca, Sr, Ba,  , Na, K, Rb or Cs,  
       [0011] M is any of or any combination of Cu, Bi, Sb, Pb, Tl or  y other transition metal,  
       [0012] Cu is Cu or Cu partially substituted by any of or any combination of Bi, Sb, Pb, Tl or any other transition metal  
       [0013] O is O or O partially substituted by any of N, Se, or F,  
       [0014] and wherein the structure of the materials is characterised by distorted or undistorted substantially square planar sheets of CuO 2  when n&gt;0 and distorted or undistorted substantially square sheets of R for n&gt;1.  
       [0015] excluding where M is Bi, R is Ca and Sr, A is Sr and Ca, and s and e are 0 and where n=1, the material Bi 2 (Sr 1-x Ca x ) 2 CuO 8-d  with 0≦x≦0.3, and where n=2 the material Bi 2 (Sr 1-x Ca x ) 3 Cu 2 O 10-d  with 0.16≦x≦0.33  
       [0016] and excluding RBa 2 Cu 3 O 7-d    
       [0017] and excluding, where R is as above excluding Ca, Sr, Ba, Li, Na, K, Rb or Cs, the material having formula  
       RBa 2 Cu 4 O 8-d . 
       [0018] The n=1, 2, 3, 4, 5, . . . materials have pseudo-tetragonal structures with lattice parameters a, b and c given by 5.3 Å&lt;a,b≦5.5 Å and c=18.3±v+(6.3±v′)n Å where 0≦v,v′≦0 . . . The n=0 material extends over the solubility range 0≦e≦4 and has orthorhombic or rhombohedral symmetry with lattice parameter c=19.1±v Å.  
       [0019] Preferred materials of the invention are those of formula (1) wherein m is 2 and R is Ca and R is predominantly Bi and having the formula  
       Bi 2+e-x L x Ca n+1-u-s A u Cu n O w   (2) 
       [0020] where L is any of or any combination of Pb, Sb, or Tl, and 0&lt;x&lt;0.4.  
       [0021] More preferred materials of the invention are those of formula (2) where n≦1 and 0≦e≦0.4 and having the formula  
       Bi 2+e-x L x Ca n+y-1-s Sr 2-y A z Cu n O 2n+4+d   (3) 
       [0022] and where 0≦z≦0.4, −2≦y≦2, and −1≦d≦1.  
       [0023] Materials of formula (3) of the invention wherein n is 3 have the formula  
       Bi 2+e-x L x Ca 2+y-s Sr 2-y A z Cu 3 O 10+d .  (4) 
       [0024] Preferably in the n=3 materials of formula (4) L is Pb  d 0≦x≦0.4 and −1≦y,d≦1. A may preferably be Y or Na and  ≦z≦0.4 and preferably 0, with preferably 0.5≦y≦0.5 and −1≦d≦1. Preferably d is fixed in a range determined by annealing in air at between 300° C. and 550° C., or by annealing in an atmosphere at an oxygen pressure or partial pressure  d temperature equivalent to annealing in air at between 300° C. and 550° C. Most preferably 0.2≦e,s≦0.3, 0.3≦x≦0.4 and −0.1≦y≦0.1.  
       [0025] Especially preferred n=3 materials of the invention are Bi 1.9 Pb 0.35 Ca 2 Sr 2 Cu 3 O 10+d , Bi 2.1 Ca 2 Sr 2 Cu 3 O 10+d , preferably wherein d is fixed in a range determined by annealing in air at between 300° C. and 550° C., or by annealing in an atmosphere at any oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 300° C. and 550° C.  
       [0026] Materials of formula (3) of the invention wherein n is 2 have the formula  
       Bi 2+e-x L x Ca 1+y-s Sr 2-y A z Cu 2 O 8+d   (5) 
       [0027] where −1≦d≦1.  
       [0028] Preferably in the n=2 materials of formula (5) L is Pb And 0&lt;x and most preferably 0≦x≦0.4, z is 0, and −1≦y, d≦1. A may preferably be Y or Na, where A is Y preferably 0&lt;z≦0.4 and most preferably 0&lt;z≦0.1 and where A is Na preferably  &lt;z≦0.4, x is 0, and −1≦y, d≦1; in both cases preferably d is fixed in a range determined by annealing in air at between 700° C. and 830° C. or in 2% oxygen at between 600° C. and 800° C., or by annealing in an atmosphere at an oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 700° C. and 800° C.  
       [0029] A preferred n=2 material is that of formula (5) wherein L is Pb, and where 0&lt;x≦0.4, z is 0, 0≦e,s≦0.25, y is −0.5, and d is fixed in a range determined by annealing the material in air between 600° C. and 800° C., or by annealing in an atmosphere at an oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 700° C. and 800° C.  
       [0030] A further preferred n=2 material is that of formula (5) wherein L is Pb, and where 0&lt;x≦0.4, z is 0, 0≦e,s≦0.25, y is 0, and d is fixed in a range determined by annealing in air at between 700° C. and 830° C. or in 2% oxygen at between 600° C. and 800° C. or by annealing in an atmosphere and at an oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 700° C. and 830° C.  
       [0031] A further preferred n=2 material is that of formula (5) wherein L is Pb, and where 0≦e,s≦0.25, 0≦x≦0.4, y is 0.5, z is 0, and d is fixed in a range determined by annealing in air at between 450° C. and 700° C. or by annealing in an atmosphere at an oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 450° C. and 700° C.  
       [0032] A further preferred n=2 material is that of formula (5) having the formula Bi 2.1+e Pb 0.2 Ca 1-s Sr 2 Cu 2 O 8+d  and where 0≦e,s≦0.2 and d is fixed in a range determined by annealing in 2% oxygen at between 770° C. and 830° C. or in an atmosphere at an oxygen pressure or partial pressure and temperature equivalent to annealing in 2% oxygen at between 770° C. and 830° C.  
       [0033] A further preferred n=2 material is that of formula (5) having the formula Bi 2+e Ca 1+y-s Sr 2-y Cu 2 O 8+d  where −0.5≦y≦0.5 and 0&lt;e,s≦0.25 and most preferably wherein y is −0.5 or most preferably O, and d is fixed in a range determined by annealing in air at between 600° C. and 800° C. or by annealing in an atmosphere at an oxygen partial pressure and temperature equivalent to annealing in air at between 600° C. and 800° C.; of the above formula or wherein y is 0.5, and d is fixed in a range determined by annealing the material in air at between 450° C. and 700° C. or in an atmosphere other than air at an oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 450° C. and 700° C.  
       [0034] Materials of formula (1) of the invention wherein n is 1 have the formula  
       Bi 2+e-x L x Ca y-s Sr 2-y A z CuO 6+d   (6) 
       [0035] where 0≦y≦1 and −1&lt;d≦1  
       [0036] Preferably in the n=1 materials of formula (6) L is Pb and 0&lt;x&lt;0.4. A is preferably Na and 0&lt;z≦0.4.  
       [0037] A preferred n=1 material is that of formula (6) wherein L is Pb, and where 0&lt;x≦0.4, 0≦e,s≦0.25 y is 0.7, and z is 0.  
       [0038] A further preferred n=1 material is that of formula (6) wherein L is Pb, and where 0≦e,s≦0.25, 0≦x≦0.4, y is 1 and z is 0.  
       [0039] A further preferred n=1 material is that of formula (6) wherein L is Pb, and where z is 0, 0≦e,s≦0.25 0.3≦x≦0.4, and 0.5≦y≦0.7.  
       [0040] A preferred n=1 material is  
       [0041] Bi 1.85 Pb 0.35 Ca 0.4 Sr 1.4 CuO 6+d .  
       [0042] A preferred n=1 material is Bi 2+e Ca y-s Sr 2-y CuO 6+d  whe  0&lt;e,s≦0.25 and y is 1 and d is fixed in a range determined by annealing in air at between 300° C. and 500° C. or by annealing in an atmosphere at an oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 300° C. and 500° C.  
       [0043] A further preferred n=1 material is that of formula (6) where y is 0.67, and d is fixed in a range determined by annealing in air at between 400° C. and 600° C. or by annealing in an atmosphere at an oxygen pressure or partial pressure and temperature equivalent to annealing in air at between 400° C. and 600° C.  
       [0044] Materials of formula (1) of the invention where n is 0 have the formula  
       Bi 2+e-x L x A 1-z A′ z O w   (7) 
       [0045] where 0≦x≦0.4 and 0≦z≦1 with the proviso that z is not 0 when x is 0, and where 0≦e≦4.  
       [0046] Preferably in the n=0 materials of formula (7) wherein L is Pb and preferably A is Ca, Sr, or Ba or any combination thereof. Where A is Ca preferably A′ is Sr, Ba, Na or Y, or any combination thereof. Where A is Sr preferably A′ is Ba, Na or K, or any combination thereof. Most preferably A is Ba and A′ is K.  
       [0047] Specific materials of the invention include  
       [0048] Bi 2+e Sr 0.8 Na 0.2 O 4+d , Bi 2+e Ba 0.5 K 0.2 O 4+d ,  
       [0049] Bi 2+e Ca 0.5 Sr 0.5 O 4+d , Bi 2+e Ba 0.5 Sr 0.5 O 4+d ,  
       [0050] Bi 1.9+e Pb 0.1 SrO 4+d , and Bi 1.9+e Pb 0.1 BaO 4+d , with 0≦e≦4 and 3≦d≦10.  
       [0051] The invention encompasses materials of formula (7) wherein n≧2, s=0 and M is Cu or Cu substituted by any of or any combination of Bi, Sb, Pb, Tl or any other transition metal, and having the formula  
       R n-1 A 2 Cu m Cu n O w   (8) 
       [0052] Preferably in material of formula (8) of the invention A is Ba, m is 1 or 2, and n is 3, 4, . . . A material of this class may be where m=3/2 and n=2 , and having the formula  
       RBa 2 Cu 3.5 O 7+d   
       [0053] where −0.5≦d≦0.5, and where R is Y.  
       [0054] The invention encompasses a material having the formula  
       Y n-1 Ba 2 Cu n+1 O (5/2)n+3/2+d   
       [0055] where −1≦d≦1 and n is 3, 4, 5, . . . ,  
       [0056] a material having the formula  
       Y n-1 Ba 2 Cu n+2 O (5/2)n+5/2+d , and, 
       [0057] a material having the formula  
       RBa 2 Ca n-2 Cu n+2 O (5/2)n+5/2+d   
       [0058] wherein n is 3, 4, 5, . . . preferably where R is Y.  
       [0059] The materials of the invention may be formed as mixed phase or intergrowth structures incorporating structural sequences from a number of the above described materials also including sequences from the material RBa 2 Cu 3 O 7   its derivatives. For example, this includes RBa 2 Cu 3.5 O 7.5-d  comprising, as it does, approximately alternating sequences of RBa 2 Cu 3 O 7-d  and RBa 2 Cu 4 O 8-d . This also includes materials with general formula (1) with n taking non-integral values allowing for the fact that, for example, a predominantly n=2 material may have n=1 and n=3 intergrowths. This also includes materials with general formula (1) with n taking non-integral values allowing for ordered mixed sequences of cells of different n values, for example, n=2.5 for alternating sequences of n=2 and n=3 slabs.  
       [0060] Typically, the materials of the invention may be prepared by solid state reaction of precursor materials such as metals, oxides, carbonates, nitrates, hydroxides, or any organic salt or organo-metallic material, for example, such as Bi 2 O 3 , Pb(NO 3 ) 2 , Sr(NO 3 ) 2 , Ca(NO 3 ) 2  and CuO for BiPbSrCaCuO materials. The materials of the invention may also be prepared by liquid flux reaction or vapour phase deposition techniques for example, as will be known to those in the art. Following forming of the materials oxygen loading or unloading as appropriate to achieve the optimum oxygen stoichiometry, for example for superconductivity, is carried out. The above preparation techniques are described in “Chemistry of High Temperature superconductors”—Eds. D L Nelson, M S Whittingham and T F George, American Chemical Society symposium Series 351 (1987); Buckley et al, Physica C156, 629 (1988); and Torardi et al Science 240, 631 (1988), for example. The materials may be prepared in the form of any sintered ceramic, recrystallised glass, thick film, thin film, filaments or single crystals.  
       [0061] In order to achieve maximum strength and toughness for the materials, it is important that they are prepared to a density close to the theoretical density. As prepared by common solid-state reaction and sintering techniques, densities of about 80% theoretical density can readily be achieved. Higher densities may be achieved by, for example, spray drying or freeze drying powders as described for example in Johnson et al, Advanced ceramic Materials 2, 337 (1987), spray pyrolysis as described for example in Kodas et al, Applied Physics Letters 52, 1622 (1988), precipitation or sol gel methods as described for example in Barboux et al J. Applied Physics 63, 2725 (1988), in order to achieve very fine particles of dimension 20 to 100 mm. After die-pressing these will sinter to high density. Alternatively, to achieve higher densities one may hot press, extrude, or rapidly solidify the ceramic material from the melt after solid state reaction or grow single crystals.  
       [0062] Preparation of the materials of the invention may be carried out more rapidly if in preparation of the materials by solid state reaction of precursor material any or all of the cations in the end material are introduced as precursors in the nitrate or hydroxide forms for rapid reaction of bulk material in the nitrate or hydroxide melt. Both the temperature and duration of the preparation reaction may be lowered by using nitrate or hydroxide precursors to introduce the cations. Melting of the nitrate and/or hydroxide precursors allows intimate atomic mixing prior to decomposition and efflux of oxides of nitrogen.  
       [0063] After preparation the materials may be sintered or (re-)ground to small particles and pressed to shape and sintered as desired to form the end material for use, as is known in the art and/or annealed to relieve stresses and increase strength and toughness as is similarly known in the art for the unsubstituted materials. The materials after preparation may as necessary be loaded oh unloaded with oxygen to achieve the optimum stoichiometry for superconductivity, optimised oxygen mobility, or other material properties. As stated, for n=2 BCSCO materials for example this generally requires oxygen unloading into the materials and with known technique this is generally carried out by annealing at 700° C. to 830° C. in air over 1 to 4 hours followed by rapid quenching into liquid nitrogen, for example. Most suitably, oxygen loading or unloading is carried out during cooling from the reaction temperatures immediately after the preparation reaction, where the materials are prepared by solid state reaction for example. Alternatively and/or additionally oxygen loading may be carried out during sintering or annealing in an oxygen containing atmosphere at an appropriate pressure  r partial pressure of oxygen. Without loss of generality the materials may be annealed, cooled, quenched or subjected to any general heat treatment incorporating AgO or Ag 2 O as oxidants or in controlled gaseous atmospheres such as argon, air or oxygen followed by rapid quenching so as to control the oxygen stoichiometry of the novel materials, the said stoichiometry being described by the variables w or d. The materials may be used as prepared without necessarily requiring oxygen loading or unloading for forming electrodes, electrolytes, sensors, catalysts and the like utilising high oxygen mobility property of the materials.  
     
    
    
     [0064] The invention is further described with reference to the following examples which further illustrate the preparation of materials in accordance with the invention. In the drawings which are referred to in the examples:  
     [0065]FIG. 1 shows a graph of electrical conductivity as a function of inverse temperature. Open circles are for heating and closed circles are for cooling when measurements are made at 1592 Hz. The triangles refer to the equivalent conductivity for the mid-frequency relaxation peak (upward pointing triangles) and the high-frequency peak (downward pointing). Open triangles and the circles refer to Bi 2 SrO 4  and the full triangles refer to Bi 2 Sr 0.9 Na 0.1 O 4 .  
     [0066]FIG. 2 shows Cole-Cole plots of Z″ versus Z′ measured at 644° C. for Bi 2 SrO 4  in oxygen, then in nitrogen then in oxygen.  
     [0067]FIG. 3 shows Cole-Cole plots of Z″ versus Z′ measured at 736° C. for Bi 2 SrO 4  in oxygen, then in nitrogen then in oxygen.  
     [0068]FIG. 4 shows V 12 /ln(p 1 /p 2 ) plotted against temperature where V 12  is the potential developed over a concentration cell using Bi 2 SrO 4  as the electrolyte with oxygen partial pressures of p 1  and p 2  on either side of the cell.  
     [0069]FIG. 5 shows a plot of the conductivity measured at 1592 Hz as a function of temperature for Bi 2 Sr 0.5 Ca 0.5 O 4  (solid symbols) and for Bi 2 SrO 4  (open symbols).  
     [0070]FIG. 6 shows a plot of zero resistance T 0  against the annealing temperature in air from which the sample was quenched into liquid nitrogen. (X) Bi 2.1 Ca 2 Sr 2 Cu 3 O 10 ; (O) Bi 2.1 CaSr 2 Cu 2 O 5 ; (+) Bi 2.1 Ca 0.2 Sr 2.   Cu 2 O 6 ; (Δ) Bi 2.1 Ca 1.5 Sr 1.5 Cu 2 O     ; (♦) Bi 2.1 CaSr 2 Cu 2 O     quenched from 2% oxygen; (□) Bi 2.1 Ca 0.67 Sr 1.33 CuO 6 ; (⋄) Bi 2.1 CaSrCuO 6 . Inset: plot of maximum T c  versus n the number of Cu layers.  
     [0071]FIG. 7 shows a plot of the XRD diffraction patterns for Bi 1.   Pb 0.35 Ca 0.4 Sr 1.4 CuO   +d  obtained using CoKa radiation.  
     [0072]FIG. 8 shows the XRD patterns for Pb-substituted compounds (a) n=2 x=0.2 and (b) n=3 x=0.35.  
     [0073]FIG. 9 shows the temperature dependence of the resistivity for Pb-substituted n=2 material x=0.2 (upper plot) and x=0.3 (lower plot).  
     [0074]FIG. 10 shows the zero resistance T c  obtained as a function of anneal temperature for the n=2 and n=3 unsubstituted (open symbols, x=0) and Pb-substituted samples (filled symbols). O:n=2, x=0.2, 21% oxygen; □:n=2, x=0.2 2% oxygen; Δ:n=2, x=0.2 0.2% oxygen; and ⋄:n=3, x=0.35, 21% oxygen.  
     [0075]FIG. 11 shows the temperature dependence of resistivity for (a)n=2 and x=0.2 reacted at 800° C. then annealed in air at 800, 700, 600 and 500° C. before quenching into liquid nitrogen. A typical curve for the unsubstituted x=0 material is shown in the inset; (b) for n=3 and x=0.35 with typical behaviour for x=0 shown in the inset.  
     [0076]FIG. 12 shows the temperature dependence of the resistivity for Bi 2.1 ,CaSr 2 Cu 2 O 8  annealed in air at various temperatures shown in ° C. (a) 5% Y substitution and (b) no substitution.  
     [0077]FIG. 13 shows a plot of the zero resistance T c  as a function of air anneal temperature for 5% Y-substituted Bi 2.1 CaSr 2 Cu 2 O 8  (solid hexagons). For comparison, the T c  values for unsubstituted n=1, n=2 and n=3 are also shown (open data points).  
     [0078]FIG. 14 shows a plot of the temperature dependence of the resistivity for the nominal composition Bi 1.9 Pb 0.35 Ca 0.9 Y 0.1 Sr 2 Cu 2 O 5  and quenched at 500° C., 700° C. and 820° C. showing no change in T c .  
     [0079]FIG. 15 shows a series of resistivity plots against temperature for n=3 and n=2 after annealing in air and then quenching into liquid nitrogen. The annealing temperatures are indicated in ° C.  
     [0080]FIG. 16 shows the [5{overscore (5)}1] zone axis electron diffraction patterns for n=1, n=2 and n=3 indexed on a 5.4 Å×5.4 Å×2 cÅ cell where c=18.3+6.3n Å. 
    
    
     EXAMPLE 1  
     (n=0)  
     [0081] Samples of composition Bi 2+e SrO 4+d  with e=0, 0.25, 0.5, 1.25 and 2 were prepared by solid-state reaction of Bi 2 O 3  and SrCO 3  at 740° C. in gold crucibles for 15 hrs. All samples were quenched from the furnace into liquid nitrogen and investigated by x-ray diffraction, electron diffraction and SEM electron-beam x-ray analysis to confirm compositions of crystallites. The e=0 material was white-yellow of orthorhombic structure with lattice parameters a=4.26 Å, b=6.10 Å and c=19.38 Å while the remaining solid-solution compositions were yellow with rhombohedral symmetry and lattice parameters varying smoothly with composition given by a=9.852-0.09e Å and a=23.28+0.2e°.  
     [0082]FIG. 1 shows the electrical conductivity measured at 1592 Hz for the e=0 material. This shows a rapid rise in conductivity above 700° C. towards values typical of solid-state electrolytes. The rapid rise coincides with a broad endothermic DTA peak indicative of a diffuse fast-ion transition. Complex impedance spectroscopy reveals three separate relaxation peaks: a broad low-frequency peak with effective capacitance in the microFarad range which is attributable to inter-granular impedance; and two higher frequency peaks attributable to oxygen-ion relaxation. The conductivities associated with these two high frequency peaks are plotted as the open triangles in FIG. 1. FIG. 2 shows Cole-Cole plots at 644° C. in oxygen, then in nitrogen, then in oxygen while FIG. 3 shows the same sequence at 736° C., in nitrogen a distinct Warburg-type impedance appears with the characteristic 45° slope. This arises from the diffusive depletion or oxygen ions at the surface when in an oxygen-free ambient and confirms the origin of the conductivity in oxygen-ion transport. A concentration cell was constructed using a sintered pellet of e=0 material over which a difference in oxygen partial pressure was maintained while the cell emf was measured. If the transport coefficient is dominated by oxygen-ion mobility rather than electron transport then the emf V 12  is given by the Nernst equation  
       V   12 =( RT/nF ) ln( p   1   /p   2 ) 
     [0083] Here R is the gas constant, T is temperature in degrees Kelvin, F is the Faraday constant and n (=4) is the number of moles of electron charge produced by one mole of O 2  p 1  and p 2  are the partial pressures of oxygen on either side of the cell. FIG. 4 shows V 12 /ln(p 1 /p 2 ) plotted against T and the data follows the ideal theoretical line with slope R/nF, thus confirming that the transport number is dominated by the oxygen-ion transport number.  
     EXAMPLE 2  
     (n=0)  
     [0084] Samples of composition Bi 2 Sr 1-z Na z O 4+d  for z=0.1 and z=0.2 were prepared at 770° C. by reaction or the carbonates or Na and Sr with Bi 2 O 3  for 15 hrs. XRD showed that these were single phase exhibiting the same orthorhombic structure as the unsubstituted e=0 material. The conductivities associated with the two high frequency complex impedance relaxations are plotted as solid triangles and these show enhancements in conductivity above that for unsubstituted material of 10 times and 30 times respectively.  
     EXAMPLE 3  
     (n=0)  
     [0085] Samples of composition Bi 2 Sr 1-z Ca z O 4+d  for z=0.33 and z=0.5 were prepared at 770° C. by reaction of the carbonates of Ca and Sr with Bi 2 O 5  for 15 hrs. XRD showed that these were single phase materials exhibiting the same hexagonal structure as occurs in the unsubstituted e&gt;0 solid-solubility range. Lattice c-parameters obtained were 19.14 Å (z=0.33) and 19.06 (z=0.5). In addition, electrons diffraction reveals the existence of a superstructure in the basal plane as evidenced by hexagonal satellites encircling each principal diffraction spot. For z=0.33 the superstructure length is 2.76 times the a-parameter. FIG. 5 shows conductivity measured at 1592 Hz for z=0.5 (solid symbols) and this is compared with the unsubstituted z=0 conductivity (open symbols) and Y-stabilised zirconia. Over much of the range the conductivity is enhanced by Ca-substitution by a factor of 100 times and is comparable to Y-zirconia.  
     EXAMPLE 4  
     (n=0)  
     [0086] Samples of composition Bi 2+x-y Pb y SrO w  with 0≦x≦0.2 and y=0.2 and y=0.4 were prepared by stoichiometric reaction of Bi 2 O 3 , SrCO 3  and PbO at 770° C. and quenched into liquid nitrogen producing a bright yellow sintered material.  
     [0087] The structure as prepared was predominantly orthorhombic with the same structure as the unsubstituted material. When annealed and quenched from 500° C. the rhombohedral structure of the unsubstituted solid-solution was adopted and the colour became brown/green. Additional phases were not evident indicating complete substitution at the y=0.4 level. Impedance spectroscopy showed that the mid-and high-frequency relaxation peaks overlapped, producing a single broadened relaxation peak. The conductivity associated with this peak measured during heating of the as prepared material increased with Pb-substitution but on cooling the conductivity remained high.  
     EXAMPLE 5  
     (n=1)  
     [0088] Samples corresponding to the starting composition Bi 2 Sr 2-x Ca x CuO 6+d  were prepared by reacting carbonates of Sr and Ca with the oxides or Bi and Cu at temperatures between 780 and 830° C. for periods of time ranging from 1 to 12 hrs. The n=1 phase is promoted by short reaction times (1 to 2 hrs), temperatures near 800° C. and lower calcium content. We could not prepare the calcium-pure phase x=2, but nearly single-phase material was obtained for s=0, 0.67 and 1.0. The structure was pseudotetragonal with lattice parameters, respectively of a=5.414 Å and c=24.459 Å, a=5.370 Å and c=24.501 Å, and a=6.370 Å and c=24.287 Å. For s=0.67 and s=1.0 incommensurate superlattice structures in the b-direction were observed with dimension ranging from 4.3 to 5.3 times the a-parameter.  
     [0089] Samples were annealed to equilibrium oxygen stoichiometry at various temperatures in air, then rapidly quenched from the furnace into liquid nitrogen. The DC electrical resistivity was measured with a four terminal technique and the zero-resistance T c  is plotted in FIG. 6 with squares and diamonds as a function of anneal temperature. T c  evidently passes through a maximum corresponding to the optimum oxygen stoichiometry.  
     [0090] The true c-axis length may he twice the figure quoted above due to a two-times c-axis superstructure. Electron diffraction patterns interpreted as [5{overscore (5)}1] zone-axis patterns may be uniquely indexed on a 5.4 Å×5.4 Å×49 Å unit cell. The same applies to all other n=1, 2 and 3 electron diffraction patterns investigated suggesting a general unit cell of 5.4 Å×5.4 Å×2c Å where c is approximately 18.3+6.3 nÅ.  
     EXAMPLE 6  
     (n=1)  
     [0091] Samples of nominal composition Bi 1.   Pb 0.2 Sr 1.3 Ca 0.7 CuO 6+d , Bi 1.6 Pb 0.2 SrCaCuO   +d , and Bi 1.9 Pb 0.3   Sr 1.3 Ca 0.7 CuO   +d , were prepared by reacting stoichiometric proportions of Bi 2 O 3 , Pb(NO 3 ) 2 , Ca(NO 3 ) 2  and CuO. The n−1 materials are favoured by short reaction times and as a consequence the nitrates are advantageous as they allow homogeneous and rapid mixing in the nitrate melt. The precursor materials were milled, pressed into pellets and reacted at 800° C. for 15 minutes, remilled, pressed into pellets and sintered for 1 hr at the same temperature. The resultant materials were very nearly single phase n=1 materials. The first of the compounds listed above was apparently tetragonal with parameters a=5.355 Å and c=24.471, but this material and even more predominantly the third material with x=0.35 and y=0.7 showed the presence of particles of composition Bi 1.65 Pb 0.35 Sr 1.4 Ca 0.4 CuO 6+d . By reacting precursors of this composition good phase-pure material was obtained as shown by FIG. 7. Impurity peaks are indicated by dots. This material is orthorhombic with parameters a=5.313 Å, b=5.391 Å and c=24.481 Å, and, moreover it is semiconducting.  
     EXAMPLE 7  
     (n=2)  
     [0092] Samples of nominal composition Bi 2.1 Sr 2-y Ca 1+y Cu 2 O   +d , with y=0.5, −0.25, 0 and 0.5 were prepared using stoichiometric proportions of the carbonates of Sr and Ca and the oxides of Bi and Cu reacted at temperatures between 860 and 870° C. for 8 to 15 hrs. The resulting material was ground, milled, pressed into pellets and sintered for another 8 to 15 hrs at 860 to 870° C. in air. This procedure produced very nearly single-phase material with a systematic variation in lattice parameters as shown in the table below confirming the intersubstitution of Sr and Ca. As lattice parameters are dependent upon oxygen stoichiometry determined by annealing temperature and ambient oxygen partial pressure, all these XRD measurements were carried out on materials quenched into liquid nitrogen after annealing for up to 12 hrs at 400° C. in air.  
                                       y   a   c                                            −0.5   5.415   30.908       −0.25   5.410   30.894       0   5.405   30.839       0.5   5.402   30.683                  
 
     [0093] The structure is centred pseudotetragonal as described by Subramanian et al for the y=0 material in Science 239, 1015 (1988). Electron diffraction shows that a 4.75 times incommensurate superstructure exists in the b-direction and as indicated in example 5 there may be a two times superlattice in the c-direction as indicated by the [5{overscore (5)}1] zone axis electron diffraction pattern.  
     [0094] As discussed in example 5 the zero-resistance T c  was measured for samples annealed at various temperatures and oxygen partial pressures. The data for anneals in air is plotted in FIG. 6 for the y=−0.5, y=0 and y=0.5 samples by plusses, circles and squares respectively. Again T c  maximises at an optimum oxygen stoichiometry for each composition. The solid circles are obtained for anneals of the y=0 material in 2% oxygen and the displacement of the curve confirms that the optimisation is associated with oxygen stoichiometry. We find that the lattice c-parameter varies with anneal temperature but for two different pairs of oxygen partial pressure and anneal temperature which give the same T c  the lattice parameters are also the same.  
     EXAMPLE 8  
     (n=2)  
     [0095] Samples of composition Bi 2.2-x Pb x CaSr a Cu 2 O   +d  with x=0, 0.1, 0.2, 0.3, 0.4 and 0.5 were prepared by solid state reaction of Bi 2 O 3 , CaCO 3  SrCO 3 , CuO and PbO for 12 hours at temperatures between 850 and 865° C. The samples were ground, pressed and sintered at the same temperature for a further 12 hours. FIG. 8 shows the XRD trace for x=0.2 which confirms nearly single phase material. Minor impurity peaks are marked by dots. Pb substitution is confirmed by observing a systematic variation in lattice parameters with x, as follows  
       a= 6.405−0.048×Å 
     and  
       c= 30.830−0.094×Å 
     [0096] Electron beam x-ray analysis or crystallites also confirmed the above compositions. Electron diffraction shows that the b-axis superstructure remains at about 4.75X for 0≦x≦0.2. For 0.2≦x≦0.35 this superstructure contracts to 4.5X and a second b-axis superstructure appears with length 7.3X. Substitution for x&gt;0.35 did not occur under the conditions of preparation. Samples were annealed at various temperatures at oxygen partial pressures of 2.1×10 4  Pa (air), 2×10 3  Pa and 2×10   Pa then quenched into liquid nitrogen. The DC resistivity of these samples was measured using a  4-terminal method and AC susceptibility was also measured. FIGS. 9 a  and  9   b  show the resistivity curves for anneals in air for x=0.2 and x=0.3 respectively. T c  is seen to decrease with decreasing anneal temperature. FIG. 10 shows the zero resistance T c  versus annealing temperature for the three oxygen partial pressures for both x=0 and x=0.2. T c  is seen to pass through a maximum for an optimum oxygen content. The maximum T c  obtained is 93 K. This increase is not due to n=3 material which has a different behaviour also shown in FIG. 10. The optimised T c  is maximised at 93 K for x=0.2 and falls 4 K for x=0.3.  
     [0097] The sharpness or the resistive transitions should be noted in FIG. 9 and compared with the typical best curve obtained for x=0 shown in the inset in FIG. 11 a  which exhibits a typical resistive tail. The resistivity curves shown in the main part of FIG. 11 a  are for a x=0.2 sample prepared at the lower temperature of 800° C. The variation in T c  as a function of anneal temperature is similar to that shown in FIG. 9 a  but the normal state resistivity varies differently. Electron microprobe analysis indicated crystallites which were Pb-rich and deficient in Sr and Ca indicating substitution of Pb on the alkali-earth sites.  
     EXAMPLE 9  
     (n=2)  
     [0098] Samples of composition Bi 2.1 Ca 1-x R x Sr 2 Cu 2 O a+d  were prepared by solid state reaction of Bi 2 O 3 , CaCO 3 , SrCO 3 , CuO and R 2 O 3  where R is Y or one of the rare earth elements. Compositions with x=0, 0.05, 0.1, 0.2, 0.4, 0.9 and 1.0 were reacted at temperatures ranging from 860° C. to 900° C. as the rare earth content was increased. Samples were investigated by x-ray diffraction, electron diffraction, IR spectroscopy, thermal gravimetry, and the temperature dependence of resistivity and AC susceptibility. In the following example we deal exclusively with the results for Y-substitution.  
     [0099] The end member x=1 was XRD phase pure and notably has the same structure as Bi 2.1 CaSr 2 Cu 2 O a+δ  except that the symmetry is reduced from tetragonal to orthorhombic as shown by the splitting of the (200) XRD peak. For Bi 2.1 YSr 2 Cu 2 O a+δ , annealed in air at 400° C. the lattice parameters are a=5.430 Å, b=5.473 Å and c=30.180 Å. Electron diffraction also reveals the presence of an 8X incommensurate superstructure, of 43.5 Å in the b-direction.  
     [0100] Attempts to study the metal to insulator transition at intermediate substitutions (0&lt;x&lt;1) were prevented by the absence of a substitutional solubility range under the conditions of preparation. In this intermediate range samples were a mixed phase or the x=0 and x=1 end-members except at compositions close to x=0 and x=1 where doping appears to be possible. Interestingly, Y substitution for Ca at the 5% level in Bi 2.1 CaSr 2 Cu 2 O   +d  appears to raise T c . FIG. 12 a  shows the temperature dependence of the resistivity for such a sample annealed and quenched at different temperatures in order to vary the oxygen stoichiometry, d. This may be compared with the same data shown in FIG. 12 b  for the x=0 unsubstituted n=2 material. The substitution has both sharpened the resistive transition and raised the zero resistance T c . Otherwise the overall behaviour is similar and quite distinct from the n=3 behaviour.  
     [0101] The zero-resistance T c  is plotted in FIG. 13 as a function of anneal temperature (solid data points) and evidently T c  is maximised at &gt;103 K. FIG. 13 also includes T c  data for unsubstituted n=1, n=2 and n=3 material for comparison. Like unsubstituted n=2 the Y-substituted material appears to exhibit a maximum T c  for anneals in air above 820° . However, above this temperature the effects of annealing and quenching are greatly modified by the proximity of a phase transition. In order to achieve maximum T c  anneals at an oxygen partial pressure less than that of air is required. The highest zero resistance T c  we have observed in this system is 102 K, The elevated T c  does not arise from the presence of n=3 material for several reasons:  
     [0102] i) We are able to prepare single-phase n=3 material by Pb-substitution for Bi. Attempts to substitute Y in this material at the 5% level drives the reacted material completely to the n=2 phase together with the binary Ca 2 CuO 3 . We would therefore hardly expect Y substitution of the n=2 material to promote n=3 material.  
     [0103] ii) The annealing behaviour of T c  is similar to that for unsubstituted n=2 material with maxima occurring at 820° C. or higher. The maximum T c  for n=3 occurs for anneals at ˜400° C. and for anneals at 820° C. the n=3 T c  in as low as 80 K.  
     [0104] Particle by particle analyses by SEM electron beam x-ray analysis indicates that Ca remains fixed at one per formula unit while Sr is slightly depleted. This suggests Y substitution on the Ca-site accompanied by Ca substitution on the Sr-site with the formula Bi 2.1 (Ca 0.95 Y 0.05 )(Sr 1.9   Ca 0.0   )Cu 2 O     . Starting compositions appropriately depleted in Sr indeed offered the best resistive transitions around 100 K with a minimal tail.  
     [0105] It may be that the substitutional solubility tends to occur only at grain boundaries as the sharp resistive transition to zero at 101 K is accompanied by only a small diamagnetic signal in the AC susceptibility commencing at ˜99 K . A sharp fall does not commence until ˜95 K at which point the diamagnetic signal is only about 5% of its fully developed value. The yttrium should therefore be dispersed more uniformly throughout a sample by reaction of nitrates or by melt processing.  
     [0106] This example and particularly the chemical formula deduced for the active phase responsible for raising T c  is presented by way of example without loss of generality. Because of the small diamagnetic signal appearing at  100 K it may be that the active phase is of another composition and structure incorporating Bi/Ca/Y/Sr/Cu/O.  
     EXAMPLE 10  
     (n=2)  
     [0107] Predominantly single phase Bi 1.9 Pb 0.36 Ca 0.9 Y 0.1 Sr 2 Cu 2 O   +δ  was prepared by solid state reaction of a pressed disc of Bi 2 O 3 , PbO, CaCO 3 , SrCO 3 , Y 2 O 3  and CuO at 860° C. for 12 hours. By annealing in air at various temperatures then quenching into liquid nitrogen, the normal state resistivity is observed to change as shown in FIG. 14. However, the zero-resistance T c  does not change, remaining at just over 90 K for anneals at 500, 700 and 820. This is uncharacteristic of the parent n=2 superconductor as shown in FIG. 12 which required anneals at an oxygen partial pressure less than that of air in order to optimise T c  at Just over 90 K. The combined Pb- and Y-substitution therefore simplifies the processing requirements for n=2 material.  
     EXAMPLE 11  
     (n=3)  
     [0108] A sample of nominal composition BiSrCaCu 3 O x  was prepared from the carbonates of Sr and Ca, CuO and bismuth oxycarbonate by reacting at 820° C. for 9 hrs, then for 10 hrs at 850° C. then for 10 hrs at 860° C. followed by air-quenching from the furnace. The sample was then annealed in air at temperatures ranging between 400° C. and 800° C. and quenched from the furnace into liquid nitrogen. Four terminal electrical DC resistivity and the AC susceptibility was measured for each anneal temperature. FIG. 15 shows   resistivity curves obtained for this sample after each anneal. The resistivity drop which occurs around 110 K is extrapolated to zero and   deduced zero resistance T c  is seen to be maximised at 105 K for anneals at about 400° C. The annealing behavior is seen   be quite different from that of the n  2 material.  
     [0109] This sample was pulverised, ground and investigated by XRD, SEM energy dispersive analysis of x-rays (EDX) and TEM electron diffraction. The EDX analyses indicated a high proportion (&gt;70%) of particles with atomic ratios Bi:Sr:Ca:Cu of 2:2:2:3 though many of these particles showed Cu contents more like 2.8 to 2.9 indicating the occurrence of n=2 intergrowths in the n=3 material. Like the n=2 material, crystals of n=3 are platey and under TEM electron diffraction were found to exhibit a 5.4 Å×5.4 Å subcell in the basal plane with the same 19/4 times incommensurate superlattice structure in the b-direction, The diffraction pattern for the [5{overscore (5)}1] zone axis shown in FIG. 16 can be indexed on a 5.4 Å×5.4 Å×74 Å cell suggesting a sub-cell c-axis of 37 Å with a superstructure which doubles the c-axis. XRD powder diffraction of this sample showed a broad basal reflection corresponding to a c-repeat of about 18 Å. This leads to the natural conclusion that Bi 2 Sr 2 Ca 2 Cu 3 O 10  is structurally related to Bi 2 Sr 2 Ca 1 Cu 2 O 5  by the insertion of an extra pair of Ca—CuO 2  sheets per unit sub-cell.  
     EXAMPLE 12  
     (n=3)  
     [0110] Samples of composition Bi 2.2-x Pb x Ca 2 Sr 2 Cu 3 O 10+d  were prepared by reaction of the oxides of Bi and Cu and the nitrates of Pb, Ca and Sr in stoichiometric proportions for 36 hrs at 860 to 865° C. in air. The XRD pattern shown in FIG. 8 b  indicates nearly single phase pseudo-tetragon  material with lattice parameters a=5.410 Å and c=37.125 Å. Like the n=   −0.2 material, electron diffraction indicates a 4.5 times and a 7.3 times b-axis superlattice structure. The effect on resistivity curves of annealing in air at various temperatures is shown in FIG. 11 b  and the curve for the x=0 material is shown in the inset. The long resistive tail in the unsubstituted material is removed by Pb-substitution. The effect of annealing temperature in air on the zero resistance T c  is shown in FIG. 10 by the diamond shaped points for x=0.35 and x=0.  
     [0111] The foregoing describes the invention including preferred forms and examples thereof. The preparation of derivative materials and forms other than sintered ceramic form, ie. thin films, thick films, single crystals, filiaments and powders other than those specifically exemplified will be within the scope of those skilled in the art in view of the foregoing. The scope of the invention is defined in the following claims.