Patent Publication Number: US-2016243289-A1

Title: MEDICAL Ti-Ni ALLOY

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application is a continuation of PCT international application Ser. No. PCT/JP2014/071338 filed on Aug. 12, 2014 which designates the United States, incorporated herein by reference, and which claims the benefit of priority from Japanese Patent Applications No. 2013-177285, filed on Aug. 12, 2013, incorporated herein by reference. 
    
    
     BACKGROUND OF THE DISCLOSURE 
     1. Field of the Disclosure 
     The present disclosure relates to a medical alloy which can be used in a human body, and a medical catheterization device including the medical alloy. 
     2. Description of the Related Art 
     An endovascular treatment, which is also referred to as a catheter treatment, involves inserting a tube called a catheter into an affected area through a blood vessel at a groin or wrist to perform percutaneous transluminal angioplasty. In recent years, this medical technology is rapidly advancing as less-invasive medical treatments become popular in view of reducing patient burden. Main devices for the catheter treatment are a guide wire, a catheter and a stent. 
     A guide wire is first inserted into the body, and serves as a guide for introducing a catheter into an affected area. The main required functions are the softness of a front end part for not causing damage to a blood vessel, the pushability of a base part to allow passage through a curved blood vessel and the shape restorability after passing a branched blood vessel. A core may be a stainless steel wire subjected to severe plastic deformation or a superelastic Ti—Ni alloy. Stainless steel is better in terms of stiffness/pushability while a Ti—Ni alloy is better in terms of softness/restorability. In recent years, a guide wire with a hybrid core including a base part of stainless steel and a front end part of a Ti—Ni alloy has been used for medical use. 
     A catheter is a tube for delivering a medical liquid and device required to diagnose/treat an affected area. Pressure resistance to flush of a medical liquid against blood flow and plasticity for not causing damage to a blood vessel wall are required as its functions. A relatively thick-walled tube is used as a core in which stainless steel wires are woven (braided) into a relatively soft resin such as polyester. However, a metal tube is preferred in view of obtaining a pressure-resistant catheter with a small diameter and a thinner wall while a superelastic Ti—Ni alloy having high plasticity is suitable in view of functionality. The present inventors conducted studies for aiming practical use of a catheter including a Ni-rich Ti—Ni-alloy (Ti-51 at % Ni) tube which can readily show superelasticity at a body temperature. However, problems remain to be solved such as ensuring softness for passing through a branched blood vessel, formation of a knife-edged fracture surface upon fracture and the like. Therefore, it is not yet available commercially (Japanese Patent Application Laid-Open No. H2-144074, Japanese Patent Application Laid-Open No. H4-28375, and U.S. Pat. No. 4,733,665). 
     A stent is a mesh-like metal pipe to be indwelled inside the body in order to prevent restenosis after expanding a narrowed segment of a blood vessel and the like. A collapsed stent accommodated in a front end part of a catheter is first introduced to a narrowed segment, and then operated to be released from the catheter and expanded to engage against the inner wall of a lumen such as a blood vessel. 
     A narrowed segment in the coronary artery which may cause myocardial infarction and the like can be expanded according to the vasodilation procedure through inflating a balloon placed in the storage inner wall of a stent. This is called a balloon expandable type, in which stainless steel and a cobalt-chromium alloy are used as a metal therein. There are a large number of prior literatures, including U.S. Pat. No. 4,733,665 in which Palmaz yielded the first practical application in the world in 1988, and subsequent documents in which balloon-expandable types were put into practical use. Meanwhile, a self-expandable stent, which can spontaneously restore the shape immediately after released from a catheter, is used for expanding a narrowed segment in the carotid artery which may trigger cerebral infarction. For a metal therein, used is a superelastic Ti—Ni alloy material having excellent spring properties (U.S. Pat. No. 4,733,665, Japanese Patent Application Laid-Open No. H06-054913, Japanese Patent Application Laid-Open No. H08-000738, Japanese Patent Application Laid-Open No. H11-99207, Japanese Patent Application Laid-Open No. 2005-245848, and Japanese Patent Application Laid-Open No. 2006-325613). 
     Shape memory alloys including a Ti—Ni alloy are well known to show significant shape memory effects associated with reverse transformation of the martensitic transformation. Further, they are also well known to show good superelasticity associated with the stress-induced martensitic transformation caused by deformation after reverse transformation. These functionalities are manifested in connection with temperature cycles of cooling/heating, and the shape recovery temperatures in the case of heating are classified into the starting temperature (the As temperature) and the finish temperature (the Af temperature). The functionality manifestation of superelasticity finishes at a temperature of the Af temperature or above. Among many shape memory alloys, Ti—Ni alloys and Ti—Ni—X alloys (X=V, Cr, Co, Nb, Cu and the like) in particular can show significant superelasticity of this type. The practical uses of Ti—Ni alloys are increasing not only in the medical field related to the present application but also in a wide range of fields such as appliance, automobile, clothes and construction. Moreover, many of the technologies related to Ti—Ni-alloys have matured to the point of the establishment of standard engineering specifications, and are utilized for describing important specifications. As an example, the scope of Ti—Ni alloys is defined as Ni: 53.5 to 57.5 mass % (48.5 to 52.5 mol %) alloys according to JIS H-7107 “Wires, tapes and tubings of Ti—Ni shape memory alloy”. 
     Further, Ni-rich Ti—Ni alloys are well known to generate precipitates of TiNi 3 , Ti 3 Ni 4  and the like when aging treatment is performed, affecting transformation properties and mechanical properties of an element. For example, the transformation temperature of a Ti-51 at % Ni alloy material subjected to aging treatment is shifted to the side of higher temperature because the concentration of Ni in a matrix is decreased due to the generation of excessive Ni precipitates. The Af temperature of a TiNi single phase is 0° C. or less when solution treatment is performed whereas the Af temperature increases to approximately 25° C. when aging is performed at 500° C. for 2 hours. In this regard, the mechanical properties thereof are improved, showing good superelasticity (excellent in repetition with less significant hysteresis). It is known that precipitation of TiNi 3 , Ti 3 Ni 4  and the like in a Ti—Ni alloy occurs in a case where the concentration of Ni is 50.5 at % or more, and the aging temperature is approximately 400° C. or more (Kazuhiro Otsuka, “Martensitic transformation and shape memory effects of alloys” Uchida Rokakuho Publishing Co., Ltd., (2012), p194). However, a case in which the aging temperature is less than approximately 400° C. has not been particularly described. 
     A Ti—Ni alloy used for a catheterization device typically has an Ni-rich composition and is limited to the Ti-51 at % Ni alloy. In view of the necessity of superelasticity well manifested at the room temperature and body temperature, a core preferably includes a material having a shape recovery temperature equal to or lower than the body temperature when solution treatment is performed. The aforementioned alloy, which can maintain the manifestation of superelasticity at the body temperature regardless of heat treatment conditions, is widely used as a base material of the above device, and used in virtually every commercial product currently available for practical use. 
     A guide wire includes a solid wire material as its core, which can be manufactured in the same way as common steel materials according to a method selected from many alternatives such as severe plastic deformation and straightening. Properties required for a given application can optionally be provided. However, a front end part, which needs to be flexible not causing damage to a blood vessel, relies on taper processing mainly by grinding and etching. However, the strength of the front end part decreases as the cross sectional area decreases. This brings an issue of fracture. For this reason, a front end part pressed into a ribbon-like shape, in which the cross sectional area is not decreased, has been proposed, but it differs from a non-directional circular cross section having directional softness. Softness is preferably assured in a straight cross section. 
     The cores of catheters and stents are commonly a hollow pipe, and the straightness thereof is essential for manufacturing the devices. Heat straightening is often performed at a temperature near the recrystallization temperature after severe plastic deformation. In that case, it is essentially inevitable that a material which shows superelasticity at the body temperature is limited to the Ti-51 at % Ni alloy. Further, in the case of a catheter, mechanical strength can be controlled by cold working and heat treatment after heat straightening, but disadvantageously, it is susceptible to self-collapsing when U- and V-shape bending deformation upon passing through a curved blood vessel and when pressed and crushed. A breakage surface thereof tends to show a knife-like fracture surface. This trend is particularly significant for the Ti-51 at % Ni alloy. 
     Furthermore, a stent core widely used for practical use as a superelastic material also includes an Ni-rich Ti—Ni alloy (for example; Ti-51 at % Ni), and is subjected to aging treatment at 400 to 500° C. after cold working. This is responsible for the functional manifestation of superelasticity with various characteristics, and satisfies the basic requirements for generating precipitates of Ti 2 Ni 3  and the like. However, repetition fatigue remains problematic as compared with a Ti—Ni single phase material subjected to solution treatment although relatively high yield strength is maintained. 
     BRIEF SUMMARY 
     It is an object of the disclosure to at least partially solve the problems in the conventional technology. 
     In a medical Ti—Ni shape memory alloy, precipitation of a composition other than TiNi into a TiNi phase is restrained. 
     The above and other objects, features, advantages and technical and industrial significance of this disclosure will be better understood by reading the following detailed description of presently preferred embodiments of the disclosure, when considered in connection with the accompanying drawings. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  illustrates examples of tensile tests for Ti—Ni alloys and results from tensile tests in Comparative Example No.4 and Example 17 of the present disclosure in Table 1. 
     
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Precipitates, which otherwise favorably affect mechanical properties of an alloy, are actually responsible for breakage/formation of a knife-edged fracture surface in a medical device such as a catheterization device. A core element largely includes a Ti—Ni single phase to reduce the influences of precipitates. 
     That is, according to the present disclosure, superelasticity can be manifested at the body temperature under conditions where precipitates are not formed even in a case where aging treatment is performed. One embodiment of the present disclosure is a Ti—Ni alloy subjected to thermomechanical treatment in which precipitates such as Ti 3 Ni 4  are not easily formed, or a Ti—Ni alloy having a composition of Ti-50.0 to 50.5 at % Ni. Further, the Ti—Ni alloy according to the present disclosure is a material having an Af temperature of more than 37° C. due to solution treatment of a TiNi single phase. 
     According to the present disclosure, a Ti—Ni alloy largely including a TiNi single phase in which precipitation of compositions other than that is restrained is used as a core that is superelastic at the body temperature. As shown in Kazuhiro Otsuka, “Martensitic transformation and shape memory effects of alloys” Uchida Rokakuho Publishing Co., Ltd., (2012), p194, Ti 3 Ni 4  precipitates in a Ti—Ni alloy in a case where the concentration of Ni is more than 50.5 at %, and the aging temperature is approximately 400° C. or more. Therefore, the key to the present disclosure is to form a core outside the above conditions. 
     Therefore, in order to obtain a Ti—Ni alloy largely including a TiNi single phase, it is specifically necessary that various processing treatments are performed on a composition of a Ti—Ni alloy in a range of Ti-50.0 to 50.5 at % Ni, or aging treatment after solution treatment of a Ti—Ni alloy is performed at less than 400° C. 
     Further, the mechanical properties of a Ti—Ni alloy having a composition of Ti-50.0 to 50.5 at % Ni are extremely dependent on a heat treatment temperature, and the strength at initial deformation (for example, at 2% stretching) necessary for a catheterization device may optionally be provided. Further, a core which is excellent in shape straightness, high radial force and sheath accomodability and operatability may be obtained by subjecting a TiNi single phase element to processing strain and relaxation treatment sufficient to achieve superelasticity with a yield plateau at the body temperature regardless of Ti—Ni alloy compositions. 
     In the present disclosure, solution treatment refers to a heat treatment in which an alloy is heated to a specific temperature, and quenched from a state in which alloy elements are in solid solution, and then a high temperature composition is directly brought to ordinary temperature. In solution treatment for transforming a Ti—Ni alloy into a TiNi single phase, a temperature of around 800° C. is sufficient for the aforementioned heating temperature. 
     In the present disclosure, aging treatment refers to a heat treatment in which an alloy is again heated after solution treatment. Depending on heating conditions and the composition of an alloy, precipitates may be formed in the alloy, allowing the mechanical properties thereof to be altered. In the present disclosure, aging treatment is preferably performed under conditions of at less than 400° C. and for relatively a short time (in the present Example, 30 minutes or less), but the conditions are not limited to these in a case where the composition of a Ti—Ni alloy is Ti-50.0 to 50.5 at % Ni. 
     In the present disclosure, restraining precipitation of a composition into a TiNi phase means reducing generation of precipitates of TiNi 3 , Ti 3 Ni 4  and the like in the core of an alloy, and also means obtaining a state close to a TiNi single phase. Treatments required to achieve these include, for example, making Ti—Ni alloy with a composition within a range of Ti-50.0 to 50.5 at % Ni and performing aging treatment on a under temperature conditions of less than 400° C. after solution treatment; and the like. 
     In the present disclosure, the body temperature refers to body temperatures of homeothermal animals such as birds and mammals, and in particular preferably the body temperature of humans. The range of the temperature can be any within a range of body temperatures which these animals can usually have. For example, it is preferably within a range of from 35° C. to 42° C., and more preferably the temperature is 37° C. 
     EXAMPLE 
     [Evaluation of Wire] 
     Table 1 shows transformation profiles and trial manufacture conditions of each wire of Ti-51 at % Ni, Ti-50.5 at % Ni and Ti-50 at % Ni, and the results therefrom. 
     Each transformation temperature shown in Table 1 results from DSC (differential scanning calorimetry) measurements after performing heat treatment at 800° C. where a TiNi single phase is obtained. The Af temperature of the Ti-51 at % alloy from Comparative Examples was found to be −15° C., which is below the body temperature while those of Ti-50.5 at % Ni and Ti-50 at % Ni alloys from Examples of the present disclosure were found to be 48° C. and 105° C., respectively, which are above the body temperature. 
     Since straightness is necessary for use in devices, trial wires were subjected to tensile treatment at 200° C. to 600° C. 
     Comparative Examples 1, 2, 3 and 4 all show good superelasticity at the body temperature, but a straight wire for use in devices is not obtained unless the treatment temperature is near recrystallization, and variations in tensile strength (s=2%) were less significant under the treatment conditions. This means that stable superelasticity can easily be obtained regardless of manufacturing methods, but options for properties are limited, and the strength is dictated by selection of a wire cross section. 
     The table shows that bending fracture is significant for Comparative Examples 2, 3 and 4, showing that they are not suitable for medical use. Further, not shown in the table, Comparative Example 1 has inferior durability due to the absence of transition as compared with other Comparative Examples and Examples of the present disclosure. Therefore, it is not suitable for medical use although bending fracture (formation of a knife-edged fracture surface) is less significant. 
     In contrast, Examples 5 to 16 of the present disclosure show superior processability, and thus suitable straight wires can be obtained by performing a treatment such as straightening treatment at 200° C. after cold working. Further, in terms of properties, a variety of superelasticity at 37° C. profiles, selections of shape memory and tensile strengths can be selected depending on conditions of the heat treatment. Moreover, these trends are significant for the equiatomic composition Ti-50 a t% Ni alloy. Furthermore, fracture/formation of a knife-edged fracture surface when bending are not observed or less significant for all test pieces, showing remarkable difference from Comparative Examples. Further, No. 17 and 18 according to the present disclosure, which are products obtained by subjecting the Ti-51 at % Ni alloy from Comparative Example to SW (swaging) processing where straightness can be obtained relatively easily, satisfy requirements of the present disclosure such as finishing shapes and strength. 
       FIG. 1  illustrates examples of tensile tests for Ti—Ni alloys and results from tensile tests in Comparative Example No.4 and Example 17 of the present disclosure in Table 1. The Example 17 of the present disclosure shows superelasticity with a yield plateau whereas Comparative Example No.4 does not show clear yield. 
     
       
         
           
               
             
               
                 TABLE 1 
               
             
            
               
                   
               
               
                 Evaluation results of trial Ti—Ni-alloy wires 
               
            
           
           
               
               
               
            
               
                   
                 Trial wire 
                 Property 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                   
                   
                   
                   
                 Tension 
                   
                   
                   
                   
                 Tensile 
               
               
                   
                   
                   
                   
                 treatment 
                   
                   
                   
                   
                 strength 
               
               
                   
                   
                   
                 Processing 
                 (Aging 
                   
                 Yield 
                 Straight- 
                   
                 MPa 
               
               
                   
                 No 
                 Alloy 
                 rate 
                 treatment) 
                 37° C. profile 
                 plateau 
                 ening 
                 Bending fracture 
                 (ε 2%) 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Comparative 
                 1 
                 Ti-51 at % Ni 
                 30% 
                 600° C./5 min 
                 Super elastic 
                 Good 
                 Good 
                 Less significant** 
                 500 
               
               
                 Examples 
                 2 
                 Af: −15° C. 
                 Die 
                 400° C./10 min 
                 Super elastic 
                 Good 
                 Good 
                 Significant 
                 500 
               
               
                   
                 3 
                 (Solution 
                 processing 
                 300° C./30 min 
                 Super elastic 
                 Bad 
                 Bad 
                 Significant 
                 600 
               
               
                   
                 4 
                 treatment) 
                   
                 200° C./30 min 
                 Super elastic 
                 Bad 
                 Bad 
                 Significant 
                 800 
               
               
                 Examples of 
                 5 
                 Ti-50.5 at % Ni 
                 30% 
                 600° C./5 min 
                 Shape memory 
                 — 
                 Good 
                 Less significant 
                 300 
               
               
                 Present 
                 6 
                 Af: 48° C. 
                 Die 
                 400° C./10 min 
                 Super elastic 
                 Good 
                 Good 
                 Less significant 
                 320 
               
               
                 Disclosure 
                 7 
                 (Solution 
                 processing 
                 300° C./30 min 
                 Super elastic 
                 Good 
                 Good 
                 Less significant 
                 320 
               
               
                   
                 8 
                 treatment) 
                   
                 200° C./30 min 
                 Super elastic 
                 Bad 
                 Good 
                 Less significant 
                 500 
               
               
                   
                 9 
                 Ti-50 at % Ni 
                 40% 
                 500° C./5 min 
                 Shape memory 
                 — 
                 Good 
                 Less significant 
                 150 
               
               
                   
                 10 
                 Af: 105° C. 
                 Die 
                 400° C./10 min 
                 Shape memory 
                 — 
                 Good 
                 Less significant 
                 200 
               
               
                   
                 11 
                 (Solution 
                 processing 
                 300° C./30 min 
                 Super elastic 
                 Good 
                 Good 
                 Less significant 
                 350 
               
               
                   
                 12 
                 treatment) 
                   
                 200° C./30 min 
                 Super elastic 
                 Bad 
                 Δ* 
                 Less significant 
                 600 
               
               
                   
                 13 
                   
                 60% 
                 600° C./5 min 
                 Shape memory 
                 — 
                 Good 
                 Less significant 
                 150 
               
               
                   
                 14 
                   
                 Die 
                 400° C./10 min 
                 Shape memory 
                 — 
                 Good 
                 Less significant 
                 300 
               
               
                   
                 15 
                   
                 processing 
                 300° C./30 min 
                 Super elastic 
                 Good 
                 Good 
                 Less significant 
                 600 
               
               
                   
                 16 
                   
                   
                 200° C./30 min 
                 Super elastic 
                 Bad 
                 Δ* 
                 Less significant 
                 1000 
               
               
                 Present 
                 17 
                 Ti-51 at % Ni 
                 40% 
                 350° C./1 min 
                 Super elastic 
                 Good 
                 Good 
                 Less significant 
                 900 
               
               
                 Disclosure 
                 18 
                 Af: −15° C. 
                 SW 
                 300° C./30 min 
                 Super elastic 
                 Good 
                 Good 
                 Less significant 
                 900 
               
               
                   
                   
                 (Solution 
                 processing 
               
               
                   
                   
                 treatment) 
               
               
                   
               
               
                 Δ* Depends on the finishing shape. 
               
               
                 **Durability was inferior due to the absence of transition. 
               
            
           
         
       
     
     [Guide Wire and Catheter] 
     Basic functional tests were performed on guide wires and catheters including alloys shown in Table 1. The results are shown in Table 2. 
     Finishing treatment for the materials in the table is cold working of approximately 30%. End part processing of a trial core means a treatment for reducing a diameter in order to obtain the plasticity of the front end part of a guide wire. Moreover, in the property evaluation, breakage represents a fracture profile upon V-bend press-crushing, and end part reshaping represents a reforming profile without superelasticity. 
     
       
         
           
               
             
               
                 TABLE 2 
               
             
            
               
                   
               
               
                 Evaluation of trial cores for guide wire and catheter 
               
            
           
           
               
               
               
            
               
                   
                 Trial Core 
                 Property 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Base part 
                 End part 
                 End part 
                 Base Part 
                 EndPart 
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                   
                 No. 
                 Alloy 
                 Material 
                 treatment 
                 treatment 
                 processing 
                 Function 
                 Breakage 
                 Plasticity 
                 Reshaping 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
               
            
               
                 Comparative 
                 17 
                 Ti-51 
                 φ0.5 mm 
                 400° C. 
                 400° C. 
                 φ 0.1 
                 Super 
                 Significant 
                 Bad 
                 X 
               
               
                 Example 
                   
                 at % Ni 
                 Wire 
                   
                   
                   
                 elastic 
               
               
                   
                 18 
                 Ti-51 
                 φ0.5 mm 
                 400° C. 
                 600° C. 
                 — 
                 Super 
                 Significant 
                 Bad 
                 Bad 
               
               
                   
                   
                 at % Ni 
                 Wire 
                   
                   
                   
                 elastic 
               
               
                   
                 19 
                 Ti-51 
                 φ1.0 mm 
                 400° C. 
                 400° C. 
                 — 
                 Super 
                 Significant 
                 Bad 
                 Bad 
               
               
                   
                   
                 at % Ni 
                 Tube 
                   
                   
                   
                 elastic 
               
               
                 Present 
                 20 
                 Ti-50.5 
                 φ0.5 mm 
                 300° C. 
                 600° C. 
                     0.1 
                 Super 
                 Less 
                 Good 
                 Δ* 
               
               
                 Disclosure 
                   
                 at % Ni 
                 Wire 
                   
                   
                   
                 elastic 
                 significant 
               
               
                   
                 21 
                 Ti-50 
                 φ0.5 mm 
                 300° C. 
                 600° C. 
                 φ 0.2 
                 Super 
                 Less 
                 Good 
                 Good 
               
               
                   
                   
                 at % Ni 
                 Wire 
                   
                   
                   
                 elastic 
                 significant 
               
               
                   
                 22 
                 Ti-50 
                 φ1.0 mm 
                 300° C. 
                 600° C. 
                 — 
                 Super 
                 Less 
                 Good 
                 Good 
               
               
                   
                   
                 at % Ni 
                 Tube 
                   
                   
                   
                 elastic 
                 significant 
               
               
                   
               
               
                 Δ* Characteristics of spring somewhat remain. 
               
            
           
         
       
     
     [Stent] 
     Basic functional tests were performed on stents including alloys shown in Table 1. 
     The results are shown in Table 3. Finishing treatment for the materials in the table is cold working of approximately 30%. A trial core was obtained by performing an expanding/shape-fixing treatment in which a raw tube with a diameter of 2 mm was processed into a body-indwelled diameter of 10 mm. The term “sequential expansion” in the property items means a stepwise treatment from φ2 to φ10 considering the risk of fracture and completed after about 5 steps for Comparative Examples while completed after about 2 to 3 steps for Examples of the present disclosure. Further, the presence or absence of shape memory properties at the end part intended whether stimulation of the inner wall of a blood vessel by the end part of an indwelled stent, due to partial superelastic loss, is reduced or whether delivery properties are enhanced. 
     
       
         
           
               
             
               
                 TABLE 3 
               
             
            
               
                   
               
               
                 Evaluation results of stent 
               
            
           
           
               
               
               
            
               
                   
                 Trial Core 
                 Property 
               
            
           
           
               
               
               
               
            
               
                   
                 φ 10 expanding 
                 Sequential 
                   
               
            
           
           
               
               
               
               
            
               
                   
                 treatment 
                 expansion 
                 Property 
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                   
                 No. 
                 Alloy 
                 Material 
                 Base part 
                 End part 
                 φ2 → φ10 
                 Base part 
                 End part 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
            
               
                 Comparative 
                 17 
                 Ti-51 
                 φ2.0 mm 
                 400° C. 
                 400° C. 
                 5 
                 Super 
                 Super 
               
               
                 Example 
                   
                 at % Ni 
                 Slotted 
                   
                   
                   
                 elastic 
                 elastic 
               
               
                   
                   
                   
                 tube 
               
               
                   
                 18 
                 Ti-51 
                 φ2.0 mm 
                 400° C. 
                 600° C. 
                 5 
                 Super 
                 Super 
               
               
                   
                   
                 at % Ni 
                 Slotted 
                   
                   
                   
                 elastic 
                 elastic 
               
               
                   
                   
                   
                 tube 
               
               
                 Present 
                 19 
                 Ti-50.5 
                 φ2.0 mm 
                 400° C. 
                 400° C. 
                 3 
                 Super 
                 Super 
               
               
                 Disclosure 
                   
                 at % Ni 
                 Slotted 
                   
                   
                   
                 elastic 
                 elastic 
               
               
                   
                   
                   
                 tube 
               
               
                   
                 20 
                 Ti-50.5 
                 φ2.0 mm 
                 300° C. 
                 600° C. 
                 3 
                 Super 
                 Shape 
               
               
                   
                   
                 at % Ni 
                 Slotted 
                   
                   
                   
                 elastic 
                 memory 
               
               
                   
                   
                   
                 tube 
               
               
                   
                 21 
                 Ti-50 
                 φ2.0 mm 
                 300° C. 
                 400° C. 
                 2 
                 Super 
                 Shape 
               
               
                   
                   
                 at % Ni 
                 Slotted 
                   
                   
                   
                 elastic 
                 memory 
               
               
                   
                   
                   
                 tube 
               
               
                   
                 22 
                 Ti-50 
                 φ2.0 mm 
                 300° C. 
                 600° C. 
                 2 
                 Super 
                 Shape 
               
               
                   
                   
                 at % Ni 
                 Slotted 
                   
                   
                   
                 elastic 
                 memory 
               
               
                   
                   
                   
                 tube 
               
               
                   
               
            
           
         
       
     
     According to the present disclosure, a shape memory alloy for medical use can be obtained in which both strength and plasticity at the body temperature are maintained. Further, the present disclosure can provide a catheter, guide wire and the like including the above alloy, characterized in that, the formation of a knife-edged fracture surface can be avoided when bending and breaking, and a strength at initial deformation can optionally be provided. 
     The alloy according to the present disclosure can provide a medical Ti—Ni shape memory alloy with a core superelastic at the body temperature, and a medical device such as a catheter made use of the above alloy. The above alloy and medical device have the following advantages as compared with the conventional products: formation of a knife-edged fracture surface can be avoided when bending and braking; a strength at initial deformation can optionally be provided; and the like. 
     Moreover, according to the present disclosure, a catheter, a guide wire in which a part of the device shows superelasticity at the body temperature, and another part shows shape memory at the body temperature can be obtained. Further, the front end part of the device or a portion thereof may have a relatively low stiffness (less than 300 MPa) and can easily be reformed. In addition, the base or a portion thereof may have a relatively high stiffness (500 MPa or more). 
     Although the disclosure has been described with respect to specific embodiments for a complete and clear disclosure, the appended claims are not to be thus limited but are to be construed as embodying all modifications and alternative constructions that may occur to one skilled in the art that fairly fall within the basic teaching herein set forth.