Metal oxide 247 superconducting materials

Abstract

The present invention comprises novel oxide materials exhibiting bulk superconductivity up to and exceeding 85K and processes for their synthesis. The oxides are within the formula R a Ba b Cu c O d wherein 1.9<a<2.1, 3.9<b<4.1, 6.8<c<7.2, 14.4<d<15.2 and wherein R is Y or any of the lanthanide rare earth elements. Certain substitutions such as Ca and La on the R and Ba sites are included.

We claim: 
     
       1. Oxide materials which exhibit bulk superconductivity at .[.temperatures exceeding 85K.]. .Iadd., temperature of at least 88K.Iaddend., within the formula   R.sub.a B.sub.b Cu.sub.c O.sub.15δ     wherein:     1.9<a<2.1,       3.9<b<4.1,       6.8<c≦7.2,       .[.-0.2<δ<0.6.]. .Iadd.-0.2<δ<0.1.Iaddend.,     R is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm or Yb, or any combination thereof, and   B is Ba or Ba plus a minor amount of Sr or La or a combination thereof.   
     
     
       2. The material of claim 1, wherein a=2, b=4, c=7 and having the formula   .[.R.sub.2 R.sub.4 Cu.sub.7 O.sub.15-δ     and wherein -0.2<δ<0.6.]. .Iadd.R 2  B 4  Cu 7  O 15- δ .Iaddend..   
     
     
       3. The material of claim 2, wherein .[.-0.2<δ<0.1.]. .Iadd.-0.2<δ<0.0.Iaddend.. 
     
     
       4. The material of claim 2, wherein δ is about 0 and R is Y, Nd, Sm, Eu, Gd, Dy, Ho, Er or Tm or any combination thereof. 
     
     
       5. The material of claim 2 wherein R consists essentially of Y or Er. 
     
     
       6. Oxide materials which exhibit bulk superconductivity at temperatures exceeding 85K, within the formula   R.sub.a-p B.sub.b-q A.sub.p+q Cu.sub.c O.sub.15-δ     wherein:     1.9<a<2.1,       3.9<b<4.1,       6.8<c≦7.2,       .[.O<p+q<1.]. .Iadd.0<p+q<1.Iaddend., .Iadd.p>0 .Iaddend.       -0.2<δ0.6,     R is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm or Yb, or any combination thereof,   B is Ba or Ba plus a minor amount of Sr or La or a combination thereof, and   A is Ca, Li, Na, K, Cs or Rb or any combination thereof, or La or La in combination with any of Ca, Li Na, K, Cs and Rb.   
     
     
       7. The material of claim 6, wherein A is Ca. 
     
     
       8. Oxide materials which exhibit bulk superconductivity at temperatures exceeding 85K within the formula   R.sub.2-ax B.sub.4-(1-a)x Ca.sub.x Cu.sub.7 O.sub.15-δ     wherein:   a is 0.75,   x is 0.025, 0.05, 0.1 or 0.2,   -0.2<δ<0.6,   R consists essentially of Y or Er, and   B is Ba or Ba plus a minor amount of Sr or La or a combination thereof.   
     
     
       9. Oxide materials which exhibit bulk superconductivity at temperatures exceeding 85K within the formula   R.sub.2-p Ca.sub.p B.sub.4-q La.sub.q Cu.sub.7 O.sub.15-δ     wherein:     -0.2<δ<0.6,       .[.0≦p+q<1.]. .Iadd.0<p+q<1, g>0.Iaddend.,     R is Y, La, Nd, Sm, Eu, Gd, Dy, Er, Tm, or Yb, or any combination thereof, and   B is Ba or Ba plus a minor amount of Sr.   
     
     
       10. The materials of claim 9 wherein R is Y, Nd, Sm, Eu, Gd, Dy, Ho, Er or Tm. 
     
     
       11. The materials of claim 9 having the formula R 2  Ba 4-q  La q  Cu 7  O 15- δ, wherein -0.2<δ<0.6 and O≦p+q<1. 
     
     
       12. The material of claim 11, having the formula Y 2  Ba 3 .8 La 0 .2 Cu 7  O 15- δ  wherein -0.2<δ<0.6. 
     
     
       13. A process for preparing oxide materials which exhibit bulk superconductivity at .[.temperatures exceeding 85K.]. .Iadd.a temperature of at least 88K .Iaddend.within the formula   R.sub.a B.sub.b Cu.sub.c O.sub.15-δ     wherein:     1.9<a<2.1,       3.9<b<4.1,       6.8<c≦7.2,       .[.-0.2<δ<0.6.]. .Iadd.-0.2<δ<0.1.Iaddend.,     R is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm or Yb, or any combination thereof, and   B is Ba or Ba plus a minor amount of Sr or La or a combination thereof,   comprising reacting precursor materials for between 1 and 300 hours at a temperature T (in units of °C.) and oxygen partial pressure Po 2  (in units of Pa) satisfying the equation   1210-180L+21L.sup.2 <T<2320-581.5L+58.5L.sup.2 where L=log.sub.10 Po.sub.2.       
     
     
       14. A process for preparing oxide materials which exhibit bulk superconductivity at temperatures exceeding 85K within the formula   R.sub.a-p B.sub.b-q A.sub.p+q Cu.sub.c O.sub.15-δ     wherein:     1.9<a<2.1,       3.9<b<4.1,       6.8<c≦7.2,       .[.O≦p+q<1.]. .Iadd.0<p+q<1, p>0, and.Iaddend.,       .[.-0.2<δ<0.6.]. .Iadd.-0.2<δ<0.1.Iaddend.,     R is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm or Yb, or any combination thereof,   B is Ba or Ba plus a minor amount of Sr, La, or a combination thereof,   A is Ca, Li, Na, K, Cs or Rb or any combination thereof or La or La in combination with any of Ca, Li, Na, K, Cs, and Rb   comprising reacting precursor materials for between 1 and 300 hours at a temperature T (in units of °C.) and oxygen partial pressure Po 2  (in units of Pa) satisfying the equation   121- 180L+21L.sup.2 <T<2320-581.5L+58.5L.sup.2 where L=log.sub.10 Po.sub.2.       
     
     
       15. The process according to claim 14 wherein .[.0<p+q<1 and.]. A is Ca. 
     
     
       16. The process according to .[.either one of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., wherein Po 2  ≦10 6  Pa. 
     
     
       17. The process according to .[.either of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., wherein Po 2  is substantially 10 5  Pa and 845° C.≦T≦870° C. 
     
     
       18. The process according to .[.either of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., wherein the precursor materials are reacted together with an alkali flux, catalyst, or reaction rate enhancer comprising a nitrate, oxide, chloride, hydroxide or carbonate of any of Li, Na, K, Rb or Cs or any combination thereof. 
     
     
       19. The process according to .[.either of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., wherein the precursor materials are reacted together with an alkali flux, catalyst, or reaction rate enhancer comprising a nitrate, oxide, chloride, hydroxide or carbonate of any of Li, Na, K, Rb or Cs or any combination thereof, and wherein the flux, catalyst or reaction rate enhancer is introduced as a mole fraction of the precursor materials between 0 and 1.0. 
     
     
       20. The process according to .[.either of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., wherein the precursor materials are reacted together with an alkali flux, catalyst, or reaction rate enhancer comprising a nitrate, oxide, chloride, hydroxide or carbonate of any of Li, Na, K, Rb or Cs or any combination thereof, and wherein the flux, catalyst or reaction rate enhancer is introduced as a mole fraction of the precursor materials between 0.1 and 0.3. 
     
     
       21. A process according to .[.either of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., wherein the oxygen partial pressure Po 2  is maintained by means of an electrochemical cell or whereby the effective Po 2  is maintained by controlling the chemical thermodynamic oxygen activity in the material by means of an electrochemical cell. 
     
     
       22. A process according to .[.either of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., wherein periodically during the reaction the reactants are cooled and reground or milled and then recompacted. 
     
     
       23. A process according to .[.either of claims 13 and 14.]. .Iadd.claims 13, 14, or 29.Iaddend., including after forming the cation composition of the material altering or optimising the oxygen content of the material by oxygen diffusion in or out of the material. 
     
     
       24. A process according to .[.either of claims 13 and 14.]. .Iadd.claim 23.Iaddend., wherein the material is prepared to comprise residual substituted alkali or Ca in the material, or is prepared at a low synthesis temperature such that the material is of a small grain size, to an extent that said alteration or optimisation of the oxygen content is accelerated. .Iadd.25. Oxide materials which exhibit bulk superconductivity at temperatures exceeding 85K, within the formula   R.sub.a B.sub.b Cu.sub.c O.sub.15-δ     wherein:     1.9<a<2.1,       3.9<b<4.1,       6.8<c≦7.2,       -0.2<δ<0.0,     R is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm or Yb, or any combination thereof, and   B is Ba or Ba plus a minor amount of Sr or La or a combination thereof. .Iaddend..Iadd.26. The material of claim 25, wherein a=2, b=4, c=7 and having the formula   R.sub.2 B.sub.4 Cu.sub.7 O.sub.15-δ. .Iaddend..Iadd.27. The material of claim 26, wherein δ is about 0 and R is Y, Nd, Sm, Eu, Gd, Dy, Ho, Er or Tm or any combination thereof. .Iaddend..Iadd.28. The material of claim 26 wherein R consists essentially of Y or Er. .Iaddend..Iadd.29. A process for preparing oxide materials which exhibit bulk superconductivity at temperatures exceeding 85K within the formula       R.sub.a B.sub.b Cu.sub.c O.sub.15-δ     wherein:     1.9<a<2.1,       3.9<b<4.1,       6.8<c≦7.2,       -0.2<δ<0.6,       T is Y, La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm or Yb, or any combination thereof, and   B is Ba or Ba plus a minor amount of Sr or La or a combination thereof,   comprising reacting precursor materials for between 1 and 300 hours at a temperature T (in units of °C.) and oxygen partial pressure P 02  (in units of Pa) satisfying the equation   121- 180L+21L.sup.2 <T<2320-581.5L+58.5L.sup.2       where L=log 10  P 02  and P 02  ≠ about 1 atmosphere. .Iaddend.