Patent Publication Number: US-7914628-B2

Title: Magnetic refrigeration material and method of manufacturing thereof

Description:
CROSS-REFERENCE TO THE INVENTION 
     This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2005-085542, filed on Mar. 24, 2005 and the entire contents of which are incorporated herein by reference. 
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to magnetic refrigeration materials and method of manufacturing them, and particularly to magnetic refrigeration materials excellent in magnetic refrigeration characteristics and a method of manufacturing the magnetic refrigeration materials capable of manufacturing the magnetic refrigeration materials with high productivity. 
     2. Description of the Related Art 
     In recent years, clean magnetic refrigeration with high energy efficiency ratio is anticipated increasingly as a technology for realizing environment protection type high efficiency refrigeration. Meeting to the requirement as the magnetic refrigeration, magnetic materials exhibiting a large magnetic entropy change at temperature ranges around room temperature have been found out. 
     Until now, (Hf, Ta)Fe 2 , (Ti, Sc)Fe 2 , (Nb, Mo)Fe 2 , and La(Fe, Si) 13  having NaZn 13  type crystal structure have been proposed as magnetic materials for the magnetic refrigeration. 
     Among these magnetic refrigeration materials, materials having NaZn 13  type crystal structure and La (Fe, Si) 13  type chemical formula have attracted attention. In these materials, Fe mainly occupies the position corresponding to Zn, and La or the like mainly occupies the position corresponding to Na of NaZn 13  type crystal structure (after here, these materials are abbreviated as an LaFe 13  type magnetic material). These materials having Fe as the main constituent, show promising properties as practical magnetic refrigeration materials providing large magnetic entropy change, and moreover, exhibiting no temperature hysteresis in magnetic phase transition (see, for example, Japanese Patent Laid-open Application No. 2002-356748, Japanese Patent Laid-open Application No. 2003-96547). 
     There is a report of a method for manufacturing LaFe 13  type magnetic material (see X. X. Zhang et al., Appl. Phy. Lett., Vol. 77, No. 19 (2000)). According to the method, LaFe 13  type magnetic materials having a phase of NaZn 13  type crystal structure (hereinafter, abbreviated as a NaZn 13  type crystal structure phase) as the main phase were obtained initially making an unified raw material alloy by melting raw materials using an arc melting method, and then heat-treating the unified alloy at 1000° C. for a long heat-treating time of one month. 
     At the unifying step of unifying law metals using the arc, high frequency melting method or the like in this process of manufacturing the LaFe 13  type magnetic material, the unified alloy contains a large fraction of bcc crystal structure phase comprising Fe as the main constituent (after here, abbreviated as a α-Fe phase), and yield of the NaZn 13  type crystal structure phase is hardly seen in the unified alloy. For yielding the LaFe 13  type magnetic material from the unified alloy, therefore, the heat treatment for a long time at a high temperature is needed as described above. 
     Recently, two patent documents, Japanese Patent Laid-open Application No. 2004-100043 and Japanese Patent Laid-open Application No. 2004-99928 concerned with magnetic alloys having the NaZn 13  type crystal structure phase containing Fe as the main constituent and their manufacturing methods were published. The first patent document Japanese Patent Laid-open Application No. 2004-100043 discloses a method for producing magnetic alloys controlling formation of stable α-Fe phase and increasing yield of the NaZn 13  type crystal structure phase by cooling and solidifying a molten alloy succeeded using a single roll method instead of a conventional self cooling and solidifying method. The intended magnetic alloys were obtained by heat-treating the solidified alloys. The document discloses that this method shortens the time for heat treatment. 
     In the rapidly cooled alloy obtained using this method, however, the α-Fe phase remains as the main phase. Therefore, heat treatment is indispensable for obtaining an alloy comprising the NaZn 13  type crystal structure phase as the main phase. In addition, when the alloy is milled for use as particulate type magnetic refrigeration material, there arises a problem of notable decrease in composition uniformity among the material particles due to existing large amount of α-Fe phase material. Then, there occur particles consisting almost of α-Fe phase, other than the particles composed of NaZn 13  type crystal structure phase. Furthermore, with increasing fraction of the α-Fe phase, there happens a problem of increasing difficulty in milling. 
     It is generally known that cooling speed of a molten metal is about 1×10 2 ° C./second in a conventional cooling after melting by a typical method of high-frequency melting or arc melting or the like, and the cooling speed of the molten metal increases up to 1×10 4 ° C./second or higher by using a typical rapid liquid cooling method represented by a single roll cooling apparatus. In this specification and claims, cooling at a speed of 1×10 4 ° C./second or higher is expressed as forced cooling. 
     The second patent document Japanese Patent Laid-open Application No. 2004-99928 discloses yield of the NaZn 13  type crystal structure phase immediately after casting obtained by comprising 1.8 to 5.4 atomic percent of boron B or the like in the raw material composition. The document further discloses that heat treatment for obtaining the NaZn 13  type crystal structure phase is facilitated by comprising B or the like. For the alloys comprising B or the like obtained by casting this method, however, there happens another problem of forming compounds containing B or the like. 
     Furthermore, A. Yan et al J. Appl. Phys. 97, 036102 (2005) reports structure and magnetic properties of La(Fe, Si) 13  prepared by a melt-spinning method. O. Gutfleisch et al J. Appl. Phys. 97, 10M305 (2005) reports a study on large magneto-caloric effect of La (Fe, Si) 13  material prepared by a melt-spinning method. Japanese Patent Laid-open Application No. 2005-15911 discloses an invention of material strength enhancement by introducing a phase that structurally reinforces the NaZn 13  crystal structure phase of a magnetic refrigeration material. Further, Japanese Patent Application No. 2005-141410 proposes a new production process of a magnetic refrigeration material comprising the NaZn 13  type crystal structure phase. 
     SUMMARY OF THE INVENTION 
     As described above, there has-been a problem of low productivity in manufacturing LaFe 13  type magnetic materials useful as magnetic refrigeration materials because a large fraction of α-Fe phase is formed and it takes a long heat treatment time for yielding the NaZn 13  type crystal structure phase from the α-Fe phase. The purpose of the present invention is to solve the problem and to provide a LaFe 13  type magnetic materials comprising large fraction of NaZn 13  type crystal structure phase and providing excellent characteristics as magnetic refrigeration materials, and also to provide a method of manufacturing magnetic refrigeration materials with high productivity, not requiring a long heat treatment time for obtaining an NaZn 13  type crystal structure phase by controlling α-Fe phase formation and by making the metal alloy microstructure smaller. 
     A magnetic refrigeration material of an embodiment of the present invention comprises a chemical composition including at least one element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, at least one element selected from the group consisting of Fe, Co, Ni, Mn and Cr, at least one element selected from the group consisting of Si, C, Ge, Al, Ga and In, and 0.5 atomic percent to 1.5 atomic percent of B, and the magnetic refrigeration material comprises material phases including NaZn 13  type crystal structure phase and an α-Fe phase (bcc crystal structure phase having Fe as the main constituent), and the size of the α-Fe phase regions is not more than 20 μm. 
     The magnetic refrigeration material of an embodiment of the present invention is preferable to be a LaFe 13  type magnetic material comprising NaZn 13  type crystal structure phase regions and α-Fe phase regions having the α-Fe phase region size of not more than 20 μm, and to comprise at least one element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb in a total of 4 to 15 atomic percent, at least one element selected from the group consisting of Fe, Co, Ni, Mn and Cr in a total of 60 to 93 atomic percent, at least one element selected from the group consisting of Si, C, Ge, Al, Ga and In in a total of 2.5 to 23.5 atomic percent, and B of 0.5 to 1.5 atomic percent. 
     A method of manufacturing a magnetic refrigeration material of an embodiment of the present invention comprises a melting process melting a raw material composition comprising at least one element selected from a group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, at least one element selected from a group consisting of Fe, Co, Ni, Mn and Cr, at least one element selected from a group consisting of Si, C, Ge, Al, Ga and In, and 0.5 to 1.5 atomic percent of B, and a forced cooling process forcefully cooling and solidifying the molten metal and obtaining a rapidly cooled alloy comprising an NaZn 13  type crystal structure phase. 
     In the method of manufacturing the magnetic refrigeration material of an embodiment of the present invention, the magnetic refrigeration material is preferable to comprise at least one element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb in a total of 4 to 15 atomic percent, at least one element selected from the group consisting of Fe, Co, Ni, Mn and Cr in a total of 60 atomic percent to 93 atomic percent, at least one element selected from the group consisting of Si, C, Ge, Al, Ga and In in a total of 2.5 to 23.5 atomic percent, and B of 0.5 to 1.5 atomic percent. 
     Based on an embodiment of the present invention, manufacturing of LaFe 13  type magnetic material having the NaZn 13  type crystal structure phase is achieved controlling formation of α-Fe phase regions and the size of the α-Fe phase regions to extremely small size, by melting the raw material composition described above comprising 0.5 atomic percent to 1.5 atomic percent including B in the raw material composition, and by rapidly cooling the molten metal artificially. The alloy manufactured using the forced cooling and solidification process based on the embodiment of the present invention shows uniform microstructure comprising the LaFe 13  type magnetic material regions formed all over the alloy and other phase regions such as α-Fe phase regions with reduced sizes. By heat-treating the alloy, further increased microstructure uniformity and further increased characteristics as the magnetic refrigeration material is obtained in a short heat-treating time. The LaFe 13  type magnetic material having uniform microstructure accompanied with very small α-Fe phase regions at very small fraction is suitable for magnetic refrigeration material providing a large magnetic entropy change by applying a magnetic field. According to embodiments of present invention, manufacturing of LaFe 13  type magnetic materials with high productivity is realized. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a flow chart showing an example of a manufacturing process according to an embodiment of the method of manufacturing magnetic material of the present invention. 
         FIG. 2  is an optical microscope photograph showing cross section microstructure of sample 1 as a comparative example (Comparative Example 1) with respect to the present invention. 
         FIG. 3  is an optical microscope photograph showing cross section microstructure of sample 2 as a comparative example (Comparative Example 2) with respect to the present invention. 
         FIG. 4  is an optical microscope photograph showing cross section microstructure of sample 3 as a comparative example (Comparative Example 3) with respect to the present invention. 
         FIG. 5  is an optical microscope photograph showing cross section microstructure of sample 4 as a comparative example (Comparative Example 4) with respect to the present invention. 
         FIG. 6  is an optical microscope photograph showing a cross section microstructure of sample 5 as a comparative example (Comparative Example 5) with respect to the present invention. 
         FIG. 7  is an optical microscope photograph showing cross section microstructure of sample 6 as an example (Example 1) according to an embodiment of the present invention. 
         FIG. 8  is an optical microscope photograph showing a cross section microstructure of sample 7 as a comparative example (Comparative Example 6) with respect to the present invention. 
         FIG. 9  is an optical microscope photograph showing cross section microstructure of sample 8 as a comparative example (Comparative Example 7) with respect to the present invention. 
     
    
    
     DESCRIPTION OF THE EMBODIMENTS 
       FIG. 1  is a flow chart showing an example of a manufacturing process according to an embodiment of the method of manufacturing the LaFe 13  type magnetic material of the present invention. In  FIG. 1 , alloy raw materials  101  comprising 0.5 atomic percent to 1.5 atomic percent of B are melted in a unifying process  102  for forming a unified alloy  103 . The unified alloy  103  is melted again in a melting process  104  and then a molten metal  105  is obtained. The molten metal  105  is rapidly cooled in a forced cooling process  106 , and then, a magnetic material  107  having a NaZn 13  type crystal structure phase is obtained. The magnetic material  107  can be pulverized into small particles, molded in a pulverizing/molding process  108 , and heat-treated in a heat-treating process  109 . Then, a heat-treated magnetic material  110  comprising more the NaZn 13  type crystal structure phase regions is obtained. 
     For attaining uniformity of the molten metal  105  at the melting process  104 , this flow chart shows an example of using the unified alloy  103  obtained after melting the alloy raw materials  101  once at the unifying process  102  by using a melting method such as arc melting or high frequency melting. Although the example of using the unified alloy  103  is shown as a suitable raw material alloy for obtaining the molten metal  105  with ensured uniformity in the forced cooling process  106 , the raw material alloy for obtaining the molten metal  105  is not limited to the unified alloy as long as uniformity of the molten metal  105  is ensured. Therefore, the unifying process  102  and the unified alloy  103  in the flow chart can be omitted for the case. 
     The magnetic material  107  obtained in the forced cooling process  106  shown in this flow chart is applicable as a magnetic material for magnetic refrigeration, magnetostrictiive application and so on when the magnetic material comprises sufficient fraction of the NaZn 13  type crystal structure phase at the step after forced cooling. 
     The magnetic material yielding more fraction of the NaZn 13  type crystal structure phase applying the heat-treating process  109  can also be applicable. The magnetic material yielding more fraction of the NaZn 13  type crystal structure phase can also be obtained by pulverizing the magnetic material  107  obtained by the forced cooling process  106 , molding into a desired shape at the pulverizing/molding process  108 , and heat-treating the molded magnetic material. The heat-treated magnetic material is also used as a magnetic refrigeration material. 
     The heat-treating process  109  in an embodiment of the present invention is preferably performed in a temperature range between 900° C. and 1100° C. for example. The effect of heat treatment in the embodiment is obtained in a short heat-treating time of 150 hours or less, and the effect is also obtained even in a heat-treating time of 100 hours or less. 
     In the method of manufacturing the magnetic material of an embodiment of the present invention, the composition comprising at least an element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb in a total of 4 to 15 atomic percent, at least an element selected from the group consisting of Fe, Co, Ni, Mn and Cr in a total of 60 to 93 atomic percent, at least an element selected from the group consisting of Si, C, Ge, Al, Ga and In in a total of 2.5 to 23.5 atomic percent, and B in 0.5 to 1.5 atomic percent is applied as the composition of the above described alloy raw material  101 . 
     Applying the process described above, the LaFe 13  type magnetic material of an embodiment of the present invention comprising the NaZn 13  type crystal structure phase is obtained controlling the size of the α-Fe phase regions to 20 μm or less, and controlling also region sizes of single phase or multiple phases formed accompanied with the α-Fe phase other than the NaZn 13  type crystal structure phase and the α-Fe phase (hereinafter, abbreviated as the third phase) appearing to small values. 
     The magnetic material of an embodiment of the present invention obtained above is a LaFe 13  type magnetic material comprising the NaZn 13  type crystal structure phase and the size of the α-Fe phase regions comprised in the magnetic material is very small and not more than 20 μm. Therefore, a sufficient heat treatment effect on the magnetic material is obtained in a short time as described above. 
     The LaFe 13  type magnetic materials providing very large magnetic entropy changes suitable as the magnetic refrigeration materials are obtained applying the above raw material compositions of an embodiment of the present invention comprising 5 to 10 atomic percent of La, 70 to 91 atomic percent of Fe, 3.5 to 18.5 atomic percent of Si, and 0.5 to 1.5 atomic percent of B. Larger magnetic entropy changes are obtained especially by preferably comprising 80 atomic percent or more of Fe. Larger magnetic entropy changes are obtained also by preferably comprising Co. 
     When the content of B does not reach 0.5 atomic percent with respect to the present invention, the size of the α-Fe phase regions tends not to be small enough, even if the cooling speed of the molten metal in the forced cooling process is enhanced. When the content of B does not reach 0.3 atomic percent, the α-Fe phase becomes coarse, and when it does not reach 0.1 atomic percent, the α-Fe phase becomes much coarser. On the other hand, when the content of B exceeds 1.5 atomic percent, the B forms compounds with other constituent elements, and the size of the third phase regions becomes larger with increasing the amount of B. Especially when the material contains La, Fe or Si, these elements form stable eutectoids with B, the third phase regions comprising compounds such as BFe, BFe 2 , B 6 Si, BS 1 , B 6 La, or B 4 La and the α-Fe phase are easily formed. The increase in the sizes of the third phase regions and the α-Fe regions becomes a cause for preventing the yield of the NaZn 13  type crystal structure phase. In this invention, the third phase is always formed when the α-Fe phase is formed. When La, Fe and Si are used as the law materials of an embodiment of the present invention, the third phase comprising La 5 Si 3 , LaSi, LaSi 2 , Fe 2 Si, Fe 5 Si 3 , FeSi 2 , Fe 3 Si, FeSi 2 , FeSi or LaFeSi can be formed. 
     For this reason, the content of B is preferable to be 0.5 atomic percent or more and more preferably 0.8 atomic percent or more. On the other hand, the content of B is preferable to be 1.5 atomic percent or less, and more preferably, 1.2 atomic percent or less. 
     When the content of Fe is less than 78 atomic percent, yield of the NaZn 13  type crystal structure phase is obtained without forced cooling after applying high frequency melting or arc melting. Without forced cooling, however, yield of the NaZn 13  type crystal structure phase decreases gradually with increasing the Fe content. Especially when molten alloy comprising 78 atomic percent or more of Fe is cooled without using forced cooling, the yield of the NaZn 13  type crystal structure phase does not occur but coarse α-Fe phase regions appears. With increasing the Fe content, yield of the NaZn 13  type crystal structure phase tends to be prevented and many α-Fe phase regions tend to appear. 
     Since a large magnetic entropy change is obtained when the Fe content in the NaZn 13  type crystal structure phase is as much as 78 atomic percent or more for example, the beneficial effect of an embodiment of the present invention is especially remarkable for manufacturing the magnetic refrigeration material providing large magnetic entropy change. Therefore, the present invention is especially suitable for manufacturing the LaFe 13  type magnetic material providing a large magnetic entropy change. 
     In alloy compositions comprising La and Fe as the constituent elements, a factor for preventing yield of the NaZn 13  type crystal structure phase is in the fact that no solid solution is formed between La and Fe. When the Fe content is 78 atomic percent or more, the preventing effect is notable and coarse α-Fe phase regions tend to appear. By comprising 0.5 to 1.5 atomic percent of B according to an embodiment of the present invention, yield of the NaZn 13  type crystal structure phase is obtained effectively, suppressing the appearance of the coarse α-Fe phase regions, even if the composition comprises La and Fe. Furthermore, the effect of suppressing the coarse α-Fe phase regions is found also by comprising Co. The effect is found by comprising 0.5 atomic percent or more. The content of 15 atomic percent or less of Co is sufficient for suppressing the appearance of the α-Fe phase. 
     The forced cooling in the method of manufacturing a magnetic material of an embodiment of the present invention is to cool rapidly acting a heat absorbing material artificially to a molten metal. To achieve the forced cooling, the method for rapidly cooling molten metal is not especially limited. Methods of water atomizing, gas atomizing, centrifugal atomizing, and plasma atomizing are available, and further, a rotational electrode method, a RDP method, a single roll rapid cooling method, a twin roll rapid cooling method, and a strip casting method are also available for this purpose. 
     By choosing the single roll rapid cooling method or the twin roll rapid cooling method from these methods, we can take an advantage of performing high-speed forced cooling under a well-controlled cooling condition by choosing parameters of the discharging rate of the molten metal, the circumferential speed of the roll and so on. A cooling speed of 1×10 4 ° C./second or more is attained by decreasing the thickness of the ribbon obtained by this method to 100 μm or less. Magnetic material in a shape of fine particles suitable for the magnetic refrigeration material for example, is obtained directly by using the water atomizing method, the gas atomizing method, the centrifugal atomizing method, the plasma atomizing method, the rotational electrode method or the RDP method. In these methods, higher cooling speed is obtained by decreasing the particle sizes to smaller values. In these methods, higher cooling effect is obtained when the particle size is smaller and the ribbon thickness is thinner. The forced cooling for forming ribbon is preferable to be performed so that the thickness of the ribbons are 50 μm or less and more preferably, so that the thickness of the ribbons are 30 μm or less, and the forced cooling by particle shape is preferable to be performed so that the size of the particles are 2 mm or less, more preferably so that the size of the particles are 1.5 mm or less, and further more preferably so that the particles are 1 mm or less, since higher cooling effect is obtained by decreasing the ribbon thickness or the particle size to smaller values. 
     At the forced cooling process  108 , the cooling speed of artificially cooling the molten metal obtained by melting an alloy is preferably from 1×10 4 ° C./second to 1×10 8 ° C./second in the present invention. 
     When the molten metal is solidified at a low cooling speed of less than 1×10 2 ° C./second in contrast to the present invention, sufficient yield of the NaZn 13  type crystal structure phase is prevented because the α-Fe phase appears prior to the other phases. When the cooling speed is 1×10 4 ° C./second or more on the other hand, yield of the NaZn 13  type crystal structure phase is more stable since appearance of the α-Fe phase is suppressed as a result of very small size metal microstructure formation. This advantageous effect is also obtained in a method realizing extremely high cooling speed such as a vapor explosion method, for example. The suitable cooling speed is from 1×10 4 ° C./second to 1×10 8 ° C./second and the sufficient advantageous effect is obtained at the cooling speed of not higher than 1×10 8 ° C./second. Although the effect is kept of course at higher cooling speed, technically difficult higher cooling speed over 1×10 8 ° C./second is not essentially necessary here. 
     In the present invention, formation of the α-Fe phase is suppressed more and preferential yield of the NaZn 13  type crystal structure phase increases more with increasing cooling speed. For this reason, more preferable cooling speed in the present invention is 1×10 5 ° C./second or higher. 
     In this way, the magnetic material comprising the NaZn 13  type crystal structure phase with small sized α-Fe phase regions of not more than 20 μm is obtained by rapidly cooling the molten metal containing the adjusted quantity of B in the alloy composition. The size of the α-Fe phase in the magnetic material is preferable to reduce to values not more than 10 μm, and is more preferable to reduce to values not more than 6 μm for further increasing the uniformity of the magnetic material. 
     In the LaFe 13  type magnetic material of an embodiment of the present invention manufactured by the procedure described above, the positions corresponding to Na atoms of the NaZn 13  type crystal structure phase are occupied mainly by atoms of at least one element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb, and the positions corresponding to Zn atoms of the NaZn 13  type crystal structure phase are mainly occupied by atoms of at least one element selected from the group consisting of Fe, Co, Ni, Mn, and Cr, and at least one element selected from the group consisting of Si, C, Ge, Al, Ga and In. 
     When much oxygen is contained in the magnetic material of an embodiment of the present invention, oxides having high melting temperature are formed as impurities, and the oxides interrupt yield of the magnetic material having good material quality. For avoiding formation of the oxides, therefore, alloys with small oxygen content are found to be desirable. 
     To attain compositions with no oxygen at all, namely to make the content of oxygen zero atomic percent is difficult and is practically not necessary. Then, we have found that suppressing the oxygen content of the alloy to 2 atomic percent or less is desirable, and suppressing the oxygen content of the alloy to 0.2 atomic percent or less is further desirable. 
     EXAMPLE 1 AND COMPARATIVE EXAMPLES 1-7 
     Example 1 and Comparative Examples 1 to 7 of the LaFe 13  type magnetic material produced based on the present invention is described. 
     First of all, each alloy composition for samples 1 to 3 shown in Table 1 was melted using the arc melting method, and solidified by cooling on a water cooled Cu hearth (cooling speed of lower than 1×10 2 ° C./second), and then sample 1-3 were obtained as a comparative examples (Comparative Examples 1-3) to the present invention. The cross section microstructure of these samples was investigated by optical microscope observation in detail. Further, the crystal structure analysis of these samples was performed using the powder X-ray diffraction method. The main reflection line intensity ratio I of the LaFe 13  type phase having the NaZn 13  type crystal structure of each sample was evaluated and compared each other. At the evaluation, the main reflection line intensity ratio I of the LaFe 13  type phase was defined as I=(I 1 /(I 1 +I 2 +I 3 ))×100 (percent), where I 1  is the main reflection line intensity of NaZn 13  type crystal structure phase, I 2  is the main reflection line intensity of the α-Fe phase, and I 3  is the largest main reflection line intensity of the third phase. Size of phase regions for each phase in this specification and claims is defined as the arithmetic average of the five long diameters for the five phase regions having the most largest to the fifth largest long diameter for each phase in a 200 μm square evaluation zone determined using the element mapping diagram of EPMA, the optical microscope and the reflection electron images, and the values were obtained. Here, the long diameters are defined as the long diameters of ellipsoids that approximate the phase regions. The words of size in the present specification and claims are defined by this description. The white frames in  FIG. 6  to  FIG. 8  show examples of the phase regions. In the compositions of these samples, La and Fe are set at 7.1 atomic percent and 80.8 atomic percent respectively, the total content of Si and B is set at 12.1 atomic percent, and the atomic percentage of B is varied. The phase determination in the optical microscope images was performed comparing the images with reflection electron images, EPMA results and X-ray diffraction patterns. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                 Composition 
                   
                 Structure 
                 LaFe 13  type phase 
               
               
                   
                 (atomic percent) 
                   
                 observation 
                 X-ray diffraction 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 La 
                 Fe 
                 Si 
                 B 
                 Treatment 
                 result 
                 intensity (percent) 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Sample 1 
                 7.1 
                 80.8 
                 12.1 
                   
                 Alloying and 
                 α-Fe phase and the 
                 0 
               
               
                 (Comparative 
                   
                   
                   
                   
                 unifying treatment 
                 third phase. 
               
               
                 Example 1) 
                   
                   
                   
                   
                 by arc melting 
                 1-13 phase is not 
               
               
                   
                   
                   
                   
                   
                 without forced 
                 seen 
               
               
                   
                   
                   
                   
                   
                 cooling 
               
               
                 Sample 2 
                 7.1 
                 80.8 
                 11.1 
                 1.0 
                 Alloying and 
                 α-Fe phase and the 
                 0 
               
               
                 (Comparative 
                   
                   
                   
                   
                 unifying treatment 
                 third phase. 
               
               
                 Example 2) 
                   
                   
                   
                   
                 by arc melting 
                 1-13 phase is not 
               
               
                   
                   
                   
                   
                   
                 without forced 
                 seen 
               
               
                   
                   
                   
                   
                   
                 cooling 
               
               
                 Sample 3 
                 7.1 
                 80.8 
                 8.4 
                 3.7 
                 Alloying and 
                 α-Fe phase and the 
                 0 
               
               
                 (Comparative 
                   
                   
                   
                   
                 unifying treatment 
                 third phase. 
               
               
                 Example 3) 
                   
                   
                   
                   
                 by arc melting 
                 1-13 phase is not 
               
               
                   
                   
                   
                   
                   
                 without forced 
                 seen 
               
               
                   
                   
                   
                   
                   
                 cooling 
               
               
                 Sample 4 
                 7.1 
                 80.8 
                 12.1 
                 0 
                 After alloyed and 
                 Fine 1-13 phase, 
                 26 
               
               
                 (Comparative 
                   
                   
                   
                 Without 
                 unified by 
                 coarse α-Fe phase 
               
               
                 Example 4) 
                   
                   
                   
                 B 
                 high-frequency 
                 and the third phase 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                 Sample 5 
                 7.1 
                 80.8 
                 11.8 
                 0.3 
                 After alloyed and 
                 Fine 1-13 phase. 
                 34 
               
               
                 (Comparative 
                   
                   
                   
                 B small 
                 unified by 
                 α-Fe phase and the 
               
               
                 Example 5) 
                   
                   
                   
                   
                 high-frequency 
                 third phase of 25 to 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
                 50 μm 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                 Sample 6 
                 7.1 
                 80.8 
                 11.1 
                 1.0 
                 After alloyed and 
                 Fine 1-13 phase. 
                 65 
               
               
                 (Example 1) 
                   
                   
                   
                   
                 unified by 
                 α-Fe phase and the 
               
               
                   
                   
                   
                   
                   
                 high-frequency 
                 third phase are not 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
                 more than 5 μm 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                 Sample 7 
                 7.1 
                 80.8 
                 9.3 
                 2.8 
                 After alloyed and 
                 Fine 1-13 phase, 
                 24 
               
               
                 (Comparative 
                   
                   
                   
                 B large 
                 unified by 
                 coarse α-Fe phase 
               
               
                 Example 6) 
                   
                   
                   
                   
                 high-frequency 
                 and the third phase 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                 Sample 8 
                 7.1 
                 80.8 
                 8.4 
                 3.7 
                 After alloyed and 
                 Fine 1-13 phase, 
                 19 
               
               
                 (Comparative 
                   
                   
                   
                 B large 
                 unified by 
                 coarse α-Fe phase 
               
               
                 Example 7) 
                   
                   
                   
                   
                 high-frequency 
                 and the third phase 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                   
               
            
           
         
       
     
     Optical microscope photographs for cross sections of the samples 1, 2 and 3 are shown in  FIGS. 2 ,  3  and  4 , respectively. 
     As seen in  FIG. 2 , yield of the NaZn 13  type crystal structure phase was not found in the sample 1, but two phases of the α-Fe phase and the third phase were seen. The size of the α-Fe phase region was 25 to 50 μm. Yield of the LaFe 13  type crystal structure phase was not found also in the X-ray diffraction pattern. 
     Yield of the NaZn 13  type crystal structure phase was not found also in the sample 2 as shown in  FIG. 3 , and the result was substantially the same as the sample 1. Similar to the case for sample 1, the two phases of the α-Fe phase and the third phase were seen for the sample 2, and the third phase was found to contain B. In the X-ray diffraction pattern, yield of the LaFe 13  type crystal structure phase was not found. 
     Yield of the NaZn 13  type crystal structure phase was not seen also in the sample 3, as shown in  FIG. 4 . The result was similar to the case for the sample 1 and 2. The α-Fe phase and the third phase were seen in this figure similar to the case for the sample 2. Yield of the LaFe 13  type crystal structure phase was not seen in the X-ray diffraction pattern of this sample, similar to the case for the sample 1 and 2 
     As described above, yield of the NaZn 13  type crystal structure phase was not found but the α-Fe phase and the third phase were seen for all these alloys obtained by melting the alloys of the above described respective compositions and solidifying at slow cooling speed below the speed of forced cooling. 
     In the alloy compositions of the sample 2 and 3, the composition of the third phase regions were replaced by mainly La, Si and B from La and Si of the sample 1 as a result of comprising B at quantities described above. For yielding the NaZn 13  type crystal structure phase, however, no remarkable improvement was seen. 
     The main points of structure observation results for the samples 1 to 3 using the optical microscope were summarized in Table 1 (In the table and the figures, the NaZn 13  type crystal structure phase is expressed simply by 1-13 phase). The heat treatment time of 250 hours or more was needed to yield the NaZn 13  type crystal structure phase by heat-treating these alloys. 
     The samples 4 to 8 shown in Table 1 were obtained as follows. Each unified alloy of the compositions shown in Table 1 for samples 4 to 8 was obtained using high-frequency melting method. Subsequently, each unified alloy was melted into molten alloy and cooled artificially at the cooling speed of about 3×10 5 ° C./second in vacuum using a single roll rapid cooling apparatus. Then, the samples 4 to 8 were obtained. The sample 6 is an example according to an embodiment of the present invention (Example 1), and the samples 4, 5, 7 and 8 are comparative examples to the example of the invention (Comparative Examples 4 to 7). The cross section microstructure of each sample was examined by optical microscope observation in detail. In the composition of these samples, La and Fe were fixed at 7.1 atomic percent and 80.8 atomic percent, respectively, total content of Si and B was set at 12. 1 atomic percent, and the atomic percentage of B was varied. 
       FIG. 5  shows an optical microscope photograph of sample 4 without containing B prepared as a comparative example (Comparative Example 4). As seen in  FIG. 5 , yield of extremely small NaZn 13  type crystal structure phase regions of 5 μm or less was found in the sample 4 solidified using the forced cooling process. However, the coarse third phase regions and α-Fe phase regions of 50 to 100 μm size were formed accompanied with the NaZn 13  type crystal structure phase regions. X-ray diffraction pattern of the sample confirmed formation of the third phase, the α-Fe phase and the LaFe 13  type crystal structure phase. The main reflection line intensity ratio of the LaFe 13  type crystal structure phase was 26 percent. Yield of the NaZn 13  type crystal structure phase was attained as an extremely small microstructure obtained by the forced cooling. However, long heat treatment time over 150 hours was still needed to yield the NaZn 13  type crystal structure phase sufficiently since the coarse third phase and the α-Fe phase were seen in the sample 4 alloy. 
       FIG. 6  shows an optical microscope photograph of sample 5 prepared by forced cooling of the alloy comprising 0.3 atomic percent of B. In the sample 5 prepared by the forced cooling of the molten metal comprising 0.3 atomic percent of B, yield of extremely small NaZn 13  type crystal structure phase regions was found as seen in  FIG. 6 . The third phase and the α-Fe phase were also formed in the alloy, and the diameters of these phase regions were found to be smaller sizes of about 25 to 50 μm. In this way, the alloy comprising very small NaZn 13  type crystal structure phase regions accompanied with the relatively small third phase and α-Fe phase regions was obtained when the molten metal contained 0.3 atomic percent of B, and the molten metal was rapidly cooled and solidified artificially. The X-ray diffraction pattern confirmed formation of the third phase, the α-Fe phase and the LaFe 13  type phase. The main reflection line intensity ratio of the LaFe 13  type crystal structure phase was 34 percent. The heat-treating time for yielding the NaZn 13  type crystal structure phase was reduced from this result, however, further improvement was needed. 
       FIG. 7  shows an optical microscope photograph of the sample 6 manufactured as an example of the present invention (Example 1). This sample was obtained by forced cooling of molten alloy comprising 1.0 atomic percent of B. As seen in  FIG. 7 , the alloy prepared by the forced cooling of the molten metal comprising 1.0 atomic percent of B was constructed mostly by small NaZn 13  type crystal structure phase regions accompanied with the small size third phase regions and α-Fe phase regions of not more than 5 μm. The X-ray diffraction pattern confirmed formation of the NaZn 13  type crystal structure phase, the third phase and the α-Fe phase. The main reflection line intensity ratio of the NaZn 13  type crystal structure phase was 65 percent. This alloy comprises the NaZn 13  type crystal structure phase as the main phase and exhibits a large magnetic entropy change. Therefore, this alloy is suitable as magnetic refrigeration material. Heat treating the alloy for a short time, yield of the NaZn 13  type crystal structure phase was further increased, and LaFe 13  type magnetic material providing a larger magnetic entropy change was obtained. 
       FIG. 8  shows an optical microscope photograph of sample 7 prepared as Comparative Example 6. Containing an increased B content of 2.8 atomic percent, the alloy prepared by forced cooling molten metal exhibited yield of the fine NaZn 13  type crystal structure phase, while formation of the coarse third phase and the α-Fe phase were also observed as shown in  FIG. 8 . The X-ray diffraction pattern confirmed formation of the third phase, the α-Fe phase and the LaFe 13  type phase, and the main reflection line intensity ratio of the LaFe 13  type crystal structure phase was 24 percent. 
       FIG. 9  shows an optical microscope photograph of the sample 8 prepared as Comparative Example 7. In the sample 8 prepared by solidifying the molten metal containing an enhanced B content of 3.7 atomic percent using the forced cooling process, formation of the coarse third phase and the α-Fe phase was observed, although the yield of the fine NaZn 13  type crystal structure phase was observed similar to the case for the sample 7 as shown in  FIG. 9 . The X-ray diffraction pattern confirmed formation of the third phase, the α-Fe phase and the LaFe 13  type crystal structure phase. The main reflection line intensity ratio of the LaFe 13  type crystal structure phase was 19 percent. Heat treatment time over 150 hours was needed for heat-treating the sample 7 and the sample 8. 
     The main points of the microstructure observation results obtained using the optical microscope for each alloy of samples 4 to 8 were summarized in Table 1 together with each composition and the preparation condition. 
     As a result of forced cooling and solidifying the molten metal comprising 0.5 atomic percent to 1.5 atomic percent of B in the alloy composition forming the LaFe 13  type crystal structure phase, the microstructure of the metal alloy was made small, suppressing formation of the third phase and making the size of the α-Fe phase regions extremely small from these results. These results shows that the yield of the NaZn 13  type crystal structure phase by atomic diffusion advances efficiently, and LaFe 13  type magnetic materials having more uniform structure and providing excellent in magnetic refrigeration characteristics superior to the prior art are manufactured with higher productivity. 
     EXAMPLES 2 TO 5 
     Samples 8 to 11 were manufactured choosing compositions neighboring to the composition of Example 1 exhibiting good results from the range including the Example and the Comparative Examples described above using the same manufacturing process conditions for Example 1 and Comparative Examples 4-5. Microstructure observation by an optical microscope and crystal structure analysis by the powder X-ray diffraction method were performed for these samples 8 to 11. The structure observation results and the main intensity ratios of the LaFe 13  type phases in the X-ray diffraction with the compositions and the process conditions are shown in Table 2. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 2 
               
             
            
               
                   
                   
               
               
                   
                 Composition 
                   
                 Structure 
                 1-13 phase X-ray 
               
               
                   
                 (atomic percent) 
                   
                 observation 
                 diffraction 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 La 
                 Fe 
                 Si 
                 B 
                 Treatment 
                 result 
                 intensity (percent) 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Sample 8 
                 7.1 
                 80.8 
                 11.6 
                 0.5 
                 After alloyed and 
                 Fine 1-13 phase, and 
                 52 
               
               
                 (Example 2) 
                   
                   
                   
                   
                 unified by 
                 α-Fe phase and the 
               
               
                   
                   
                   
                   
                   
                 high-frequency 
                 third phase of 10 to 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
                 20 μm 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                 Sample 9 
                 7.1 
                 80.8 
                 11.3 
                 0.8 
                 After alloyed and 
                 Fine 1-13 phase, and 
                 62 
               
               
                 (Example 3) 
                   
                   
                   
                   
                 unified by 
                 α-Fe phase and the 
               
               
                   
                   
                   
                   
                   
                 high-frequency 
                 third phase of not 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
                 more than 10 μm 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                 Sample 10 
                 7.1 
                 80.8 
                 10.9 
                 1.2 
                 After alloyed and 
                 Fine 1-13 phase, and 
                 66 
               
               
                 (Example 4) 
                   
                   
                   
                   
                 unified by 
                 α-Fe phase and the 
               
               
                   
                   
                   
                   
                   
                 high-frequency 
                 third phase of not 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
                 more than 10 μm 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                 Sample 11 
                 7.1 
                 80.8 
                 10.6 
                 1.5 
                 After alloyed and 
                 Fine 1-13 phase, and 
                 55 
               
               
                 (Example 5) 
                   
                   
                   
                   
                 unified by 
                 α-Fe phase and the 
               
               
                   
                   
                   
                   
                   
                 high-frequency 
                 third phase of 10 to 
               
               
                   
                   
                   
                   
                   
                 melting, forced 
                 20 μm 
               
               
                   
                   
                   
                   
                   
                 cooling treatment 
               
               
                   
               
            
           
         
       
     
     From these results, these alloys comprising B in the range of 0.5 to 1.5 atomic percent were composed mainly of the fine NaZn 13  type crystal structure phases accompanied with the third phase and the α-Fe phase both having very small region sizes, and these alloys formed LaFe 13  type magnetic materials providing a large magnetic entropy change. By heat-treating these alloys for a short time, the alloys further yield the NaZn 13  type crystal structure phase and LaFe 13  type magnetic materials providing larger magnetic entropy changes were obtained. 
     The above-described examples are for compositions setting La and Fe at 7.1 and 80.8 atomic percent, respectively, Si and B at 12.1 in total, and varying atomic percent of B. Similar to the case for these examples, microstructure composed mostly of the fine NaZn 13  type crystal structure phase was also obtained for the metal alloys comprising 5 to 10 atomic percent of La, 70 to 91 atomic percent of Fe, and 3.5 to 18.5 atomic percent of Si, and 0.5 atomic percent to 1.5 atomic percent of B manufactured using the forced cooling process. The phase regions of the third phase and the α-Fe phase were very small and further yield of the NaZn 13  type crystal structure phase was obtained by heat-treating for a short time. Similar result was also obtained for alloy compositions comprising 0.5 percent to 15 percent of Co. 
     Furthermore, the alloys having the fine NaZn 13  type crystal structure phase as the main phase accompanied with the very small third phase and very small α-Fe phase were obtained by using forced cooling process for each of molten alloy for the compositions comprising at least one element selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb in a total of 4 to 15 atomic percent, at least one element selected from the group consisting of Fe, Co, Ni, Mn and Cr in a total of 60 to 93 atomic percent, at least one element selected from the group consisting of Si, C, Ge, Al, Ga and In in a total of 2.5 to 23.5 atomic percent, and B of 0.5 atomic percent to 1.5 atomic percent. Furthermore, yield increase of the NaZn 13  type crystal structure phase in each alloy was obtained by a short time annealing. In this way, LaFe 13  type magnetic materials were obtained. 
     EXAMPLE 6 
     The sample 12 was fabricated by cooling at the forced cooling speed of 1×10 4 ° C./second which was lower than 3×10 5 ° C./second for Example 1. Optical microscope observation of the sample alloy cross section microstructure and powder X-ray diffraction crystal structure analysis were performed. The microstructure observation result and the main reflection line intensity ratio of the LaFe 13  type phase by X-ray analysis as well as the composition and treatment condition of the sample 12 are shown in Table 3. 
     
       
         
           
               
               
               
               
               
             
               
                   
                 TABLE 3 
               
             
            
               
                   
                   
               
               
                   
                 Composition 
                   
                 Structure 
                 1-13 phase X-ray 
               
               
                   
                 (atomic percent) 
                   
                 observation 
                 diffraction 
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                   
                 La 
                 Fe 
                 Si 
                 B 
                 Treatment 
                 result 
                 intensity (percent) 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
               
               
            
               
                 Sample 10 
                 7.1 
                 80.8 
                 11.1 
                 1.0 
                 After alloyed and 
                 Fine 1-13 phase, 
                 50 
               
               
                 (Example 6) 
                   
                   
                   
                   
                 unified, forced 
                 α-Fe phase and the 
               
               
                   
                   
                   
                   
                   
                 cooling at 1 × 
                 third phase are not 
               
               
                   
                   
                   
                   
                   
                 10 4 ° C./sec 
                 more than 20 μm 
               
               
                   
               
            
           
         
       
     
     As shown in Table 3, alloy microstructure of the fine NaZn 13  type crystal structure phase with controlled α-Fe phase regions and the third phase region sizes not more than 20 μm was obtained and the advantageous effect of an embodiment of the present invention was obtained even by the forced cooling treatment at the cooling speed of 1×10 4 ° C./second. 
     Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and representative embodiments shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.