Amorphous Alloys on the Base of Zr and their Use

Abstract

An alloy is disclosed which contains at least four components. The alloy has a bulk structure containing at least one amorphous phase. The alloy composition follows an “80:20 scheme”, i.e., the alloy composition is [(A x D 100−x )a(E y G 100−y ) 100−a ] 100−b Z b with the number “a” being approximately 80. Preferably, component A is Zr. The other components D, E, G and, optionally, Z are all different from each other and different from component A. A preferred system is Zr—Cu—Fe—Al. Further disclosed are Cu-free systems of the type Zr—Fe—AI-Pd/Pt. Importantly, the alloy is substantially free of nickel. This makes the alloy especially suitable for medical applications. Methods of preparing such an alloy, uses of the alloy and articles manufactured from the alloy are also disclosed.

1 - 42 . (canceled) 
     
     
         43 . An alloy having a structure containing at least one amorphous phase, the alloy being represented by the general formula
   [(Zr x Cu 100−x ) a (E y G 100−y ) 100−a ] 100−b Z b ,   
       wherein a, b, x and y are real numbers signifying atomic percentages with 70≦a≦90, x≧50, y>0, and 0≦b≦6,
 wherein E is selected from the group consisting of Fe and Co, 
 wherein G and Z are components each consisting of at least one element, 
 wherein all elements in E, G and Z are mutually different and different from Zr and Cu, and 
 wherein said alloy is substantially free of nickel, 
 with the proviso that, if E=Al, then G≠Pd. 
 
     
     
         44 . The alloy according to  claim 43 , wherein G is at least one element selected from the group consisting of Al (aluminum) and the metalloids. 
     
     
         45 . The alloy according to  claim 43 , wherein E is Fe (iron) and G is Al (aluminum). 
     
     
         46 . The alloy according to  claim 43 , wherein 30≦y≦50. 
     
     
         47 . The alloy according to  claim 43 , wherein 62≦x≦83. 
     
     
         48 . The alloy according to  claim 43 , wherein the alloy is essentially represented by the formula (Zr x Cu 100−x ) 80 (Fe 40 Al 60 ) 20  with 62≦x≦83. 
     
     
         49 . The alloy according to  claim 48 , wherein x is substantially selected from the numbers 62, 64, 66, 68, 72.5, 77, 79, 81 or 83. 
     
     
         50 . An alloy substantially represented by one of the formulas (Zr 95 Ti 5 ) 72 Cu 13 Fe 13 Al 2 , Zr 70 Cu 13 Fe 13 Al 3 Sn 1 , Zr 70 Cu 13 Fe 13 Al 2 Cr 2 , Zr 70 Cu 13 Fe 13 Al 2 Nb 2 , Zr 70 Cu 13 Fe 13 Al 2 Zn 2 , (Zr 72 Cu 13 Fe 13 Al 2 ) 98 Mo 2 , (Zr 72 Cu 13 Fe 13 Al 2 ) 98 P 2 , (Zr 95 Hf 5 ) 72 Cu 13 Fe 13 Al 2 , Zr 70 Cu 11  Fe 11 Al 8 , Zr 71 Cu 11 Fe 10 Al 8 , (Zr 74 Cu 13 Fe 13 ) 90 Al 10 , Zr 72 Cu 13 Fe 13 Al 2 , (Zr 74 Cu 13 Fe 13 ) 98 Al 2 , Zr 73 Cu 13 Fe 13 Al 1 , Zr 72 Cu 13 Fe 13 Al 2 , Zr 71 Cu 13 Fe 13 Al 3 , Zr 72 Cu 12 Fe 12 Al 4 , Zr 70 Cu 13 Fe 13 Al 4 , Zr 72 Cu 11  Fe 11 Al 6 , Zr 72 Cu 11.5 Fe 11 Al 5.5 , Zr 73 Cu 11 Fe 11 Al 5 , Zr 71 Cu 11 Fe 11 Al 7 , Zr 69 Cu 11 Fe 11 Al 9 , Zr 70 Cu 10.5 Fe 100.5 Al 9 , Zr 70 Cu 10 Fe 11 Al 9 , Zr 70 Cu 11 Fe 10 Al 9 , Zr 69 Cu 10 Fe 10 Al 11 , Zr 69 Cu 10 Fe 11 Al 10 , Zr 70 Cu 13 Fe 13 Al 2 Sn 2 , Zr 72 Cu 13 Fe 13 Sn 2 , (Zr 74 Cu 13 Fe 13 ) 98 Sn 2 , (Zr 79 Cu 21 ) 80 (Fe 40 Al 60 ) 20 , (Zr 81  Cu 19 ) 80 (Fe 40 Al 60 ) 20 , (Zr 83 Cu 17 ) 80 (Fe 40 Al 60 ) 20 , (Zr 66 Cu 34 ) 80 (Fe 40 Al 60 ) 20 , (Zr 64 Cu 36 ) 80 (Fe 40 Al 60 ) 20 , and (Zr 62 Cu 38 ) 80 (Fe 40 Al 60 ) 20 . 
     
     
         51 . An alloy having a structure containing at least one amorphous phase, the alloy being represented by the general formula
   [(Zr x Fe 100−x ) a (Al y G 100−y ) 100−a ] 100−b Z b ,   wherein a, b, x and y are real numbers signifying atomic percentages with 70≦a≦90, x≧50, y>0, and 0≦b≦6,   wherein G is at least one element selected from the group consisting of Pt and Pd,   wherein Z is a component consisting of at least one element,   wherein all elements in G and Z are mutually different and different from Zr, Fe and Al, and   wherein said alloy is substantially free of copper and nickel.   
     
     
         52 . The alloy according to  claim 51 , wherein G is Pd (palladium). 
     
     
         53 . The alloy according to  claim 51 , wherein the atomic percentages of Fe and Al are substantially equal. 
     
     
         54 . The alloy according to  claim 51 , wherein 68≦x≦89 and 73≦a≦87. 
     
     
         55 . The alloy according to one  claim 51 , wherein 40≦y≦82. 
     
     
         56 . The alloy according to  claim 51 , wherein 81≦x≦85, 80≦a≦83, and 65≦y≦80. 
     
     
         57 . The alloy according to one of  claims 43  and  51 , wherein 0≦b≦2. 
     
     
         58 . The alloy according to one of  claims 43  and  51 , wherein b>0, and wherein Z is at least one element selected from the group consisting of Ti, Hf, V, Nb, Y, Cr, Mo, Fe, Co, Sn, Zn, P, Pd, Ag, Au and Pt. 
     
     
         59 . The alloy according to one of  claims 43  and  51 , wherein b=0. 
     
     
         60 . An alloy having a structure containing at least one amorphous phase, the alloy being substantially represented by the general formula
   Zr i (Fe 50+ε Al 50−ε ) j X k ,   wherein X is one or more elements selected from the group consisting of Pd and Pt, wherein i, j, k and ε are real numbers signifying atomic percentages, and wherein −10≦ε≦10, i≧50, j≧19, k≧0.5 and i+j+k=100.   
     
     
         61 . The alloy according to  claim 60 , wherein X is Pd (palladium). 
     
     
         62 . The alloy according to  claim 60 , wherein 62≦i≦77. 
     
     
         63 . The alloy according to  claim 60 , wherein 19≦j≦34. 
     
     
         64 . The alloy according to  claim 60 , wherein −2≦ε≦2. 
     
     
         65 . The alloy according to  claim 60 , wherein ε is substantially zero, 66≦i≦70, 25≦j≦29 and 4≦k≦7. 
     
     
         66 . An alloy having the features of both  claim 51  and  claim 60 . 
     
     
         67 . An alloy substantially represented by one of the formulas Zr 67 Fe 13.2 Al 113.2 Pd 6.6 , Zr 69.7 Fe 12.95 Al 12.95 Pd 4.4 , Zr 66.7 Fe 14.45 Al 14.45 Pd 4.4 , Zr 68.3 Fe 13.4 Al 113.4 Pd 4.9 , Zr 65.4 Fe 14.85 Al 14.85 Pd 4.9 , Zr 62.3 Fe 16.7 Al 16.7 Pd 4.3 , Zr 59.2 Fe 18.3 Al 18.3 Pd 4.2 , Zr 72 Fe 11.5 A 11.5 Pd 5 , Zr 73.4 Fe 10.9 Al 10.9 Pd 4.8 , Zr 75.2 Fe 10.2 Al 10.2 Pd 4.3 , Zr 77 Fe 9.5 Al 9.5 Pd 4 , Zr 67.9 Fe 11.8 Al 11.8 Pd 8.5. Zr   65 Fe 11.4 Al 11.4 Pd 12.2 , Zr 62.5 Fe 10.75 Al 10.75 Pd 16 , Zr i (Fe 50 Al 50 ) 30 Pd 70−i  with 62≦i≦69.5, Zr 69.5 Fe 15 Al 15 Pd 0.5 , Zr 69 Fe 115 Al 15 Pd 0.5 , Zr 68 Fe 15 Al 15 Pd 2 , Zr 67 Fe 15 Al 15 Pd 3 , Zr 66 Fe 15 Al 15 Pd 4 , Zr 65 Fe 15 Al 15 Pd 5 , Zr 64 Fe 115 Al 15 Pd 6 , Zr 63 Fe 15 Al 15 Pd 7 , Zr 62 Fe 15 Al 15 Pd 8 , Zr 71 Fe 12 Al 12 Pd 5 , Zr 69 Fe 12.85 Al 12.85 Pd 5.3 , Zr 66.8 Fe 13.7 Al 13.7 Pd 5.8 , Zr 65 Fe 14.5 Al 14.5 Pd 6 , Zr 61.9 Fe 16.2 Al 16.2 Pd 5.7 , Zr 50 Fe 12 Al 12 Pd 26 , Zr 53.2 Fe 12.6 Al 12.6 Pd 21.6 , Zr 57.6 Fe 13.95 Al 13.95 Pd 14.5 , and Zr 60 Fe 14.3 Al 14.3 Pd 11.4 . 
     
     
         68 . The alloy according to one of  claims 43 ,  51  and  60 , wherein the alloy has a structure comprising at least one amorphous phase and at least one crystalline phase. 
     
     
         69 . The alloy according to one of  claims 43 ,  51  and  60 , wherein said at least one amorphous phase is obtainable by cooling from a temperature above the melting point of the alloy to a temperature below the glass-transition temperature of the amorphous phase at a cooling rate of 1000 K/s or less. 
     
     
         70 . A method of manufacturing an alloy, the method comprising:
 preparing a melt of aliquots of all components of
   (Zr x Cu 100−x ) a (E y G 100−y ) 100−a ] 100−b Z b , 
   and cooling the melt from a temperature above the melting point of the alloy to a temperature below the glass-transition temperature of the amorphous phase with a cooling rate of 1000 K/s or less to obtain a solidified material,   wherein a, b, x and y are real numbers signifying atomic percentages with 70≦a≦90, x≧50, y>0, and 0≦b≦6,   wherein E is selected from the group consisting of Fe and Co,   wherein G and Z are components each consisting of at least one element,   wherein all elements in E, G and Z are mutually different and different from Zr and Cu, and   wherein said alloy is substantially free of nickel,   with the proviso that, if E=Al, then G≠Pd.   
     
     
         71 . A method of manufacturing an alloy, the method comprising:
 preparing a melt of aliquots of all components of
   [(Zr x Fe 100−x ) a (Al y G 100−y ) 100−a ] 100−b Z b , 
   and cooling the melt from a temperature above the melting point of the alloy to a temperature below the glass-transition temperature of the amorphous phase with a cooling rate of 1000 K/s or less to obtain a solidified material,   wherein a, b, x and y are real numbers signifying atomic percentages with 70≦a≦90, x≧50, y>0, and 0≦b≦6,   wherein G is at least one element selected from the group consisting of Pt and Pd,   wherein Z is a component consisting of at least one element,   wherein all elements in G and Z are mutually different and different from Zr, Fe and Al, and   wherein said alloy is substantially free of copper and nickel.   
     
     
         72 . A method of manufacturing an alloy, the method comprising:
 preparing a melt of aliquots of all components of
   Zr i (Fe 50+ε Al 50−ε ) j X k , 
   and cooling the melt from a temperature above the melting point of the alloy to a temperature below the glass-transition temperature of the amorphous phase with a cooling rate of 1000 K/s or less to obtain a solidified material,   wherein X is one or more elements selected from the group consisting of Pd and Pt, wherein i, j, k and ε are real numbers signifying atomic percentages, and wherein −10≦ε≦10, i≧50, j≧19, k≧0.5 and i+j+k=100.   
     
     
         73 . The method according to one of  claims 70 ,  71  and  72 , the method comprising casting the melt into a mold, in particular into a microstructured mold. 
     
     
         74 . The method according to one of  claims 70 ,  71  and  72 , the method comprising heat-treating the solidified material at a temperature below the onset temperature of melting for a time period sufficient for the formation of at least one crystalline phase. 
     
     
         75 . The method according to one of  claims 70 ,  71 , and  72 , the method comprising a step of bringing the alloy into a superplastic state and forming a microstructure in this state. 
     
     
         76 . Use of an alloy according to one of  claims 43 ,  51  and  60  for manufacturing a product intended for being brought into prolonged contact with a human or animal body. 
     
     
         77 . An implant for implantation in the human or animal body comprising an alloy according to one of  claims 43 ,  51  and  60 .