Patent Publication Number: US-7223310-B2

Title: Soft magnetic co-based metallic glass alloy

Description:
TECHNICAL FIELD 
     The present invention relates to a soft magnetic Co-based metallic glass alloy having low coercive force and high glass forming ability or ability allowing a larger-size metal cast consisting of a glass phase to be produced from its liquid phase through a cooling/solidification process in a supercooled liquid state. 
     BACKGROUND ART 
     As for amorphous alloys, there have heretofore been known Fe—P—C-based alloy which was first produced in the 1960s, (Fe, Co, Ni)—P—B-based alloy, (Fe, Co, Ni)—Si—B-based alloy, (Fe, Co, Ni)—(Zr, Hf, Nb)-based alloy and (Fe, Co, Ni)—(Zr, Hf, Nb)—B-based alloy which were produced in the 1970s. 
     All of the above alloys are essentially subjected to a rapid solidification process at a cooling rate of 10 4  K/s or more, and an obtained sample is a thin strip having a thickness of 200 μm or less. Between 1988 and 2001, various metallic glass alloys exhibiting high glass forming ability, which have a composition, such as Ln—Al—TM, Mg—Ln—TM, Zr—Al—TM, Pd—Cu—Ni—P, (Fe, Co, Ni)—(Zr, Hf, Nb)—B, Fe—(Al, Ga)—P—B—C, Fe—(Nb, Cr, Mo)—(Al, Ga)—P—B—C, Fe—(Cr, Mo)—Ga—P—B—C, Fe—Co—Ga—P—B—C, Fe—Ga—P—B—C or Fe—Ga—P—B—C—Si (wherein Ln is a rare-earth element, and TM is a transition metal), were discovered. These alloys can be formed as a metallic glass bar having a diameter or thickness of 1 mm or more. 
     The inventor previously filed a patent application concerning a soft magnetic metallic glass alloy of Co—(Fe, Ni)—(Ti, Zr, Nb, Ta, Hf, Mo, W)—(Cr, Mn, Ru, Rh, Pd, Os, Ir, Pt, Al, Ga, Si, Ge, C, P)—B, which has a supercooled-liquid temperature interval (ΔT χ ) of 20 to 45 K and a coercive force (Hc) of 2 to 9 A/m (Japanese Patent Laid-Open Publication No. 10-324939). 
     DISCLOSURE OF INVENTION 
     The inventor has hitherto found out several Co-based soft magnetic metallic glass alloys. However, these metallic glass alloys are formed through a single-roll process in the form of a thin strip (or film, ribbon) having a relatively high coercive force. In view of practical applications, it is desired to provide a soft magnetic metallic glass alloy capable of being formed as a bulk metallic glass with a lower coercive force. 
     Through researches on various alloy compositions with a view to solving the above problem, the inventor found a soft magnetic Co—B—Si-based metallic glass alloy composition which exhibits clear glass transition and wide supercooled liquid region and has higher glass forming ability. 
     Specifically, the present invention provides a soft magnetic Co-based metallic glass alloy with high glass forming ability, which has a supercooled-liquid temperature interval (ΔT χ ) of 40 K or more, a reduced glass-transition temperature (T g /T m ) of 0.59 or more and a coercive force (Hc) of 2.0 A/m or less. The metallic glass alloy is represented by the following composition formula: [Co 1−n−(a+b) Fe n B a Si b ] 100−χ M χ , wherein each of a, b and n represents an atomic ratio satisfying the following relations: 0.1≦a≦0.17; 0.06≦b≦0.15; 0.18≦a+b≦0.3; and 0≦n≦0.08, M representing one or more elements selected from the group consisting of Zr, Nb, Ta, Hf, Mo, Ti, V, Cr, Pd and W, and χ satisfying the following relation: 3 atomic %≦χ≦10 atomic %. 
     In a metallic glass prepared using the alloy with the above composition through a single-roll rapid liquid cooling process in the form of a thin strip having a thickness of 0.2 mm or more, a supercooled-liquid temperature interval (or the temperature interval of a supercooled liquid region) (ΔT χ ), which is expressed by the following formula: ΔT χ =T χ −T g  (wherein T χ  is a crystallization temperature, and T g  is a glass transition (vitrification) temperature), is 40 K or more, and a reduced glass-transition temperature (T g /T m ) is 0.59 or more. 
     During the course of preparing a metallic glass using the alloy represented by the above composition formula through a cupper-mold casting process, heat generation caused by significant glass transition and crystallization is observed in a thermal analysis. A critical thickness or diameter in glass formation is 1.5 mm. This proves that a metallic glass can be prepared through the cupper-mold casting process. In addition, this glass alloy exhibits excellent soft magnetic characteristics, such as a low coercive force (Hc) of 2.0 A/m or less, which are significantly useful as transformers or magnetometric sensors. 
     In the above alloy composition of the present invention, a primary component or Co is an element playing a role in creating magnetism. This roll is critical to obtain high saturation magnetization and excellent soft magnetic characteristics. The alloy composition includes about 56 to 80 atomic % of Co. 
     In the above alloy composition of the present invention, the metal element Fe is added in an amount of about 8 atomic % or less, preferably in the range of 2 to 6 atomic %, to effectively reduce a coercive force to 1.5 A/m or less. 
     In the above alloy composition of the present invention, the metalloid elements B and Si play a role in forming an amorphous phase. This role is critical to obtain a stable amorphous structure. The atomic ratio of Co—Fe—B—Si is set such that the total of n+a+b is in the range of 0.18 to and 0.38, and the remainder is Co. If the total of n+a+b is deviated from this range, it will be difficult to form an amorphous phase. It is required to contain both B and Si. If either one of B and Si is deviated from the above composition range, the glass forming ability will be deteriorated to cause difficulties in forming a bulk metallic glass. 
     In the above alloy composition of the present invention, the addition of the element M is effective to provide enhanced glass forming ability. In the alloy composition of the present invention, the element M is added in the range of 3 atomic % to 10 atomic %. If the element M is deviated from this range and less than 3 atomic %, the supercooled-liquid temperature interval (ΔT χ ) will undesirably disappear. If the element M is greater than 10 atomic %, the saturation magnetization will be undesirably reduced. 
     The alloy with the above composition of the present invention may further contain 3 atomic % or less of one or more elements selected from the group consisting of P, C, Ga and Ge. The addition of the one or more elements allows a coercive force to have a reduced value ranging from 1.5 A/m to 0.75 A/m, or provides enhanced soft magnetic characteristics. On the other hand, if the content of the one or more elements becomes greater than 3 atomic %, the resulting reduced content of Co will cause a decrease in saturation magnetization. Thus, the content of the one or more elements is set at 3 atomic % or less. 
     In the above alloy composition of the present invention, any deviation from the composition ranges defined as above causes deteriorated glass forming ability to create/grow crystals during the process of solidifying liquid metal so as to form a mixed structure of a glass phase and a crystal phase. If the deviation from the composition range becomes larger, an obtained structure will have only a crystal phase without any glass phase. 
     The alloy of the present invention has high glass forming ability. Thus, the alloy can be formed as a metallic glass round bar with a diameter of 1.5 mm through a casting process in a supercooled liquid state using a copper-mold having a low cooling rate. Further, at the same cooling rate, the alloy can be formed as a metallic glass thin wire with a maximum diameter of 0.4 mm through an in-rotating-water spinning process or a metallic glass powder with a maximum particle diameter of 0.5 mm through an atomization process. 
    
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         FIG. 1  is an optical micrograph showing the sectional structure of a cast bar obtained in Inventive Example 2. 
         FIG. 2  is a graph showing thermal analysis curves of ribbons obtained in Inventive Examples 10, 11 and 12 and Comparative Example 2. 
         FIG. 3  is a graph showing thermal analysis curves of the cast bar obtained in Inventive Example 2 and the ribbon obtained in Inventive Example 11. 
         FIG. 4  is a graph showing I-H hysteresis curves of the cast bar obtained in Inventive Example 2 and the ribbon obtained in Inventive Example 11, based on the measurement of their magnetic characteristics using a vibrating-sample magnetometer. 
         FIG. 5  is a schematic side view of an apparatus for use in preparing a cast bar serving as an alloy sample through a metal-mold casting process. 
     
    
    
     BEST MODE FOR CARRYING OUT THE INVENTION 
     INVENTIVE EXAMPLES 1 TO 10 &amp; COMPARATIVE EXAMPLES 1 TO 7 
     With reference to the drawings, the present invention will now be specifically described in connection with examples. 
       FIG. 5  is a schematic side view of an apparatus used in preparing an alloy sample with a diameter of 0.5 to 2 mm through a metal-mold casting process. A molten alloy  1  having a given composition was first prepared through an arc melting process. The alloy  1  was inserted into a silica tube  3  having a front end formed with a small opening (diameter: 0.5 mm)  2 , and heated/melted using a high-frequency coil  4 . Then, the silica tube  3  was disposed immediately above a copper mold  6  formed with a vertical hole  5  having a diameter of 0.5 to 2 mm to serve as a casting space, and a given pressure (1.0 Kg/cm 2 ) of argon gas was applied onto the molten metal  1  in the silica tube  3  to inject the molten metal  1  from the small opening  2  of the silica tube  3  into the hole  5  of the copper mold  6 . The injected molten metal was left uncontrolled and solidified to obtain a cast bar having a diameter of 0.5 mm and a length of 50 mm. 
     Table 1 shows the respective alloy compositions of Inventive Examples 1 to 10 and Comparative Examples 1 to 7, and the respective glass transition temperatures (T g ) and crystallization temperatures (T χ ) of Inventive Examples 1 to 10 measured using a differential scanning calorimeter. Further, the generated heat value of a sample due to crystallization was measured using a differential scanning calorimeter, and compared with that of a completely vitrified thin strip prepared through a single-roll rapid liquid cooling process to evaluate the volume fraction of a glass phase (Vf-amo.) contained in the sample. 
     Table 1 also shows the respective saturation magnetizations (Is) and coercive forces (Hc) of Inventive Examples 1 to 10 measured using a vibrating-sample magnetometer and an I-H loop tracer. Further, the vitrification in each of the cast bars of Inventive Examples 1 to 10 and Comparative Examples 1 to 7 was checked through X-ray diffraction analysis, and the sample sections were observed by an optical microscope. 
     In Inventive Examples 1 to 10, the supercooled-liquid temperature interval (ΔT χ ) expressed by the following formula: ΔT χ =T χ −T g  (wherein T χ  is a crystallization temperature, and T g  is a glass transition temperature) was 40 K or more, and the volume fraction (V f-amo. ) of a glass phase was 100% in the form of a cast bar with a diameter of 1 to 1.5 mm. 
     In contrast, Comparative Examples 1 and 2 which contain the element M in an amount of 3 atomic % or less or contains no element M were crystalline in the form of a cast bar with a diameter of 0.5 mm. While Comparative Example 3 contains Nb as the element M, the content of Nb is 11 atomic % which is deviated from the alloy composition range of the present invention. As a result, it was crystalline in the form of a cast bar with a diameter of 0.5 mm. While Comparative Examples 4 to 7 contain the element M in the range of 1 to 10 atomic %, no Si or B is contained therein or the content of Si or B is deviated from the range of “a” or “b” in the composition formula. Thus, they were crystalline in the form of a cast bar with a diameter of 0.5 mm. 
     
       
         
           
               
               
               
               
               
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                 Diameter 
                 T g   
                 T x   
                 T x  − T g   
                   
                   
                 Is 
                 Hc 
               
               
                   
                 Alloy Composition 
                 (mm) 
                 (K) 
                 (k) 
                 (K) 
                 T g /T m   
                 V f-amo.   
                 (T) 
                 (A/m) 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
               
               
               
               
               
               
               
            
               
                 Inventive Example 1 
                 (Co 0.75 B 0.15 Si 0.10 ) 96 Nb 4   
                 1.0 
                 810 
                 850 
                 40 
                 0.60 
                 100 
                 0.61 
                 1.8 
               
               
                 Inventive Example 2 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 96 Nb 4   
                 1.0 
                 820 
                 862 
                 42 
                 0.61 
                 100 
                 0.60 
                 1.5 
               
               
                 Inventive Example 3 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 94 Nb 6   
                 1.5 
                 850 
                 890 
                 40 
                 0.63 
                 100 
                 0.42 
                 1.2 
               
               
                 Inventive Example 4 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 92 Nb 8   
                 1.5 
                 875 
                 915 
                 40 
                 0.64 
                 100 
                 0.38 
                 1.0 
               
               
                 Inventive Example 5 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 96 Zr 4   
                 1.0 
                 800 
                 845 
                 45 
                 0.59 
                 100 
                 0.70 
                 1.5 
               
               
                 Inventive Example 6 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 94 Zr 6   
                 1.5 
                 815 
                 865 
                 50 
                 0.60 
                 100 
                 0.64 
                 1.0 
               
               
                 Inventive Example 7 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 96 Hf 4   
                 0.5 
                 820 
                 865 
                 45 
                 0.59 
                 100 
                 0.60 
                 1.5 
               
               
                 Inventive Example 8 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 94 Hf 6   
                 1.0 
                 825 
                 875 
                 50 
                 0.60 
                 100 
                 0.75 
                 1.2 
               
               
                 Inventive Example 9 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 96 Ta 4   
                 0.5 
                 830 
                 875 
                 45 
                 0.59 
                 100 
                 0.58 
                 1.4 
               
               
                 Inventive Example 10 
                 (Co 0.70 Fe 0.04 Ga 0.03 B 0.14 Si 0.09 ) 96 Nb 4   
                 1.5 
                 815 
                 870 
                 55 
                 0.60 
                 100 
                 0.59 
                 0.75 
               
            
           
           
               
               
               
               
            
               
                 Comparative Example 1 
                 Co 70.5 Fe 4.5 B 15 Si 10   
                 0.5 
                 crystalline 
               
               
                 Comparative Example 2 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 98 Nb 2   
                 0.5 
                 crystalline 
               
               
                 Comparative Example 3 
                 (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 89 Nb 11   
                 0.5 
                 crystalline 
               
               
                 Comparative Example 4 
                 (Co 0.8 B 0.2 ) 96 Nb 4   
                 0.5 
                 crystalline 
               
               
                 Comparative Example 5 
                 (Co 0.8 Si 0.2 ) 96 Nb 4   
                 0.5 
                 crystalline 
               
               
                 Comparative Example 6 
                 (Co 0.7 B 0.2 Si 0.1 ) 96 Nb 4   
                 0.5 
                 crystalline 
               
               
                 Comparative Example 7 
                 (Co 0.7 B 0.1 Si 0.2 ) 96 Nb 4   
                 0.5 
                 crystalline 
               
               
                   
               
            
           
         
       
     
       FIG. 1  is an optical micrograph showing the sectional structure of the cast bar with a diameter of 1.0 mm obtained in Inventive Example 2. As shown in  FIG. 1 , except for casting defects and polishing marks, no contrast of crystal particles is observed in the optical micrograph. This clearly proves the formation of a metallic glass. 
     INVENTIVE EXAMPLE 11 
     (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 96 Nb 4    
     INVENTIVE EXAMPLE 12 
     (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 94 Nb 6    
     INVENTIVE EXAMPLE 13 
     (Co 0.705 Fe 0.045 B 0.15 Si 0.10 ) 92 Nb 8    
     A molten alloy having each of the above compositions was rapidly solidified through a conventional melt-spinning process to prepare a ribbon material having a thickness of 0.025 mm and a width of 2 mm.  FIG. 2  shows thermal analysis curves of the ribbon materials obtained in Inventive Examples 11, 12 and 13 and Comparative Example 2. As seen in  FIG. 2 , when the content of Nb is in the range of 4 to 8 atomic %, a wide ΔT χ  of 40 K or more can be obtained. 
       FIG. 3  shows thermal analysis curves of the cast bar obtained in Inventive Example 2, a cast bar having the same composition as that of Inventive Example 2 and a diameter of 0.5 mm, and the ribbon material obtained in Inventive Example 11. As seen in  FIG. 3 , there is not any difference between the ribbon material and the bulk material. 
       FIG. 4  shows I-H hysteresis curves of the cast bar obtained in Inventive Example 2 and the ribbon obtained in Inventive Example 11, based on the measurement of their magnetic characteristics using a vibrating-sample magnetometer. These curves show that both Inventive Examples 2 and 11 exhibit excellent soft magnetic characteristics. 
     INDUSTRIAL APPLICABILITY 
     As mentioned above, the Co-base metallic glass alloy of the present invention has excellent glass forming ability which achieves a critical thickness or diameter of 1.5 mm or more and allows a metallic glass to be obtained through a copper-mold casting process. Thus, the present invention can practically provide a large metallic glass product having excellent soft magnetic characteristics and high saturation magnetization.