Metal strip manufacturing method and nozzle therefor
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a method of continuously manufacturing amorphous metal strip or crystalline metal strip by quench-solidification on the surface of a moving chill body of molten metal. 
     2. Description of the Prior Art 
     Various means have been disclosed relating to methods of continuously manufacturing strip from molten metal (continuous melt quenching method). In each case the molten alloy is ejected under a specific pressure from a nozzle having an orifice of a specific shape, and strikes a moving chill body that faces the nozzle orifice to be thereby solidified into continuous strip. 
     The important manufacturing factors at this time are the shape of the nozzle orifice, the relative positional arrangement of the nozzle and the chill body, the pressure at which the molten alloy is ejected from the nozzle, and advancing the chill surface at a predetermined speed. With respect to these manufacturing factors, in general, conditions tend to become narrower and more stringent as the width of the strip increases. 
     Japanese Patent Laid Open No. 53 (1978)-53525, &#34;Method and apparatus for continuous casting of metal a strip&#34;, is a representative example of means that have been disclosed for manufacturing wide strip, and in outline comprised a slotted nozzle positioned generally perpendicular to the direction of movement of a chill surface and located in close proximity to the chill surface to provided a gap of from about 0.03 to about 1 mm between the nozzle and the chill surface, molten alloy was ejected from the nozzle onto the chill surface at a velocity of 100 to 2,000 meters per minute for forming continuous strip by means of thermal-contact rapid-cooling solidification. 
     In the above-mentioned conventional method, in principle there is no limitation on the width of the strip. That is, if the length of the rectangular orifice (the length of the orifice measured in a direction that is at right-angles to the direction of movement of the chill surface) was increased, the width of the strip could be increased. 
     However, in practice, as the length of the rectangular orifice was increased it became difficult to maintain the parallelism of the orifice during the casting. Specifically, as shown in FIGS. 3a and 3b, convex or concave deformation of the nozzle portion caused by thermal expansion, deformation resulting from non-uniformity of the temperature and the like made it difficult to maintain the parallelism of the orifice. When the parallelism of the rectangular nozzle is thus lost, the thickness of the formed strip, especially in the direction of the width, becomes non-uniform. Accordingly, conventionally, the wider the strip became the more difficult it has been to produce strip having uniform thickness across its width. Also, strip that is of non-uniform thickness is undesirable because when such strip is laminated or coiled, for example, the space factor deteriorates. At present it is possible to keep thickness deviation in 25-mm-wide strip down to 5 to 10 per cent, but in the case of strip 150 mm in width it difficult to keep the deviation to 10 per cent or less. Thus, with conventional methods the width of the strip was subject to a technical limitation. As far as the present inventors know, at present the width of the widest rapid-cooled strip is around 300 mm. However, strip of this width is being produced only on an experimental basis, and it is difficult to consider that production stability is such as to permit commercial mass-production. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to remove constraints on width in the continuous manufacturing of metal strip from molten alloy by reducing non-uniformity of strip that with conventional methods often resulted from deformation of the nozzle portion during the manufacture of wide strip, and increasing the strength of the nozzle portion. 
     The present invention attains the above object on the basis of new knowledge that, in contrast to the conventional method of manufacturing wide strip using a nozzle having a slot-shaped rectangular orifice, wide strip possessing the same flatness as strip produced according to the conventional method can be manufactured using a nozzle that has an orifice that is discontinuous in the width direction of the strip. The method according to the present invention does not have the drawbacks associated with conventional methods, and enables the width of the strip to be increased without limit. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIGS. 1 and 2 are explanatory drawings showing the shape and arrangement of the nozzle orifices used in the method according to the present invention; 
     FIG. 3 is an explanatory drawing showing deformation of a slot-shaped nozzle caused by thermal expansion; 
     FIG. 4 illustrates a profile of a free surface in the width direction of strip produced according to a first embodiment of the present invention; 
     FIG. 5 illustrates a profile of a free surface in the width direction of strip produced according to a third embodiment of the present invention; 
     FIG. 6 illustrates a profile of a free surface in the width direction of strip produced according to a fourth embodiment of present invention; 
     FIG. 7 illustrates a profile of a free surface in the width direction of strip produced according to a conventional method (slot method); and 
     FIG. 8 is an explanatory drawing showing the shape and arrangement of nozzle orifices that may be used according to the method of the present invention. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The nozzle used in the method of the present invention is for example the kind of multiple-orifice nozzle 1 illustrated in FIG. 1. Orifices 2 are each a slender parallelogram in shape with the sides inclined in the direction of movement of a cooling surface 3 (indicated by the phantom line (single-dot chain line)). The orifices 2 are arrayed in a mutually parallel arrangement at right angles to the direction of movement. 
     The parameters defining the structure of the multiple-orifice nozzle 1 employed in the method of this invention as illustrated in FIG. 1 are side d of the orifice 2 parallelogram; spaces b, c, by which adjacent orifices are separated; angle of inclination α of each parallelogram relative to the direction of travel of the cooling plate 3; and the height a of the parallelograms. In general, a is larger than d and the shape is long and slender. With respect to the range of parameter dimensions, the orifice angle of inclination α is 10-80 degrees, the length of the lower side d is 0.1-2.0 mm, the height a is 0.5-8.0 mm, and as the separation between adjacent orifices, preferably a distance b in the direction of the orifice array is within the range 0.2-3.0 mm and the distance c in the direction of travel of the cooling plate 3 is within the range 0.2-4.0 mm. 
     Of the shape parameters, the distance c in the direction of movement of the chill surface 3 is important. It was found that if the said distance c exceeded 4.0 mm, strip having a good shape would not be formed. This is of special importance when it is amorphous alloy strip that is to be manufactured, wherein if 4.0 mm is exceeded the strip thus produced is often crystallized. Other shape parameters shown are the preferred ranges for embodiments in practicing of the present invention. For example, height a is a parameter related to the strip thickness and is preferably within the range 0.5-8.0 mm; the lower limit is set at a value that eliminates difficulties in the manufacture of the nozzle. 
     The major fear in the method according to the present invention is whether there will appear in the formed strip longitudinal strand-shaped hollows or open portions, or protrusions. Such strip is regarded as a product of low commercial value, tending as it does to produce a lowering of the space factor when it is utilized as a core material. 
     Unexpectedly, however, tests confirmed that selection of correct combinations within the parameter ranges proposed for the method of the present invention enabled strip to be obtained which substantially was free of the aforementioned strand-shaped hollows or protrusions, and therefore there was almost no lowering of the space factor. 
     The method according to the present invention goes beyond the conventional state of knowledge of the art as recited in columns 2 to 3 of the Official Gazette entry for Japanese Laid Open Publication No. 53 (1978)-53525 in the point that the thickness of strip formed by the ejection of the molten alloy from a nozzle having a plurality of orifices in the width direction of the strip is substantially uniform. 
     In addition, it was found that as, if the method of the present invention is adopted, there are none of the drawbacks associated with the conventional method, constraints on the width of the strip are removed and the strip can be made wider. 
     The method used according to the present invention, as already described, is what is referred to as the single-roll rapid-cooling method, a variation of the melt rapid-cooling method, wherein molten metal is forced onto the chill surface 3 under the pressure by means of nozzle 1 for thermal-contact rapid-cooling solidification. It goes without saying that this also includes centrifugal cooling type methods in which the inner wall of a drum is utilized, as well as improvements thereto such as, for example, methods using auxiliary rolls or attachments such as a roll-surface-temperature control means, or casting under reduced pressure or in a vacuum, or in an inert gas. 
     Casting conditions employed with the method of the present invention will now be described. The distance between the nozzle tip and the chill surface is in the range of about 0.05-about 3.0 mm. The molten metal ejection pressure is 0.01-2.0 kg/cm 2  and the travel speed of the chill surface is 5-50 m/sec. The optimum value the above mentioned distance and travel speed within this range will be selected according to the structure of the nozzle. 
     With respect to the shape of the nozzle orifices, there are a number of possible variations within the range of the basic concept that has been described. For example, an orifice may be trapezoidal in shape, as shown in FIG. 2. In this case, the angle of inclination α of the orifice with respect to the direction of movement of the chill surface is 10-80 degrees, the lengths d1 and d2 of the upper and lower legs are each 0.1-6.0 mm and as the separation between adjacent orifices, preferably distances b1 and b2 in the direction of the orifice array are within the range 0.2-6.0 mm and the distance c in the direction of travel of the chill surface 3 is within the range 0.2-7.0 mm, and the height a within the range 0.5-8.0 mm. 
     Here, the angle of inclination α of the orifice with respect to the direction of movement of the chill surface, as shown in FIG. 2, is the angle formed between a line joining the respective midpoints of the upper and lower sides of the trapezoidal orifices and the direction of movement of the chill surface 3. In FIG. 2, with regard to the d1 and d2 of the upper and lower sides of the trapezoidal orifice, d1 is shown as smaller than d2, but if it is within the aforementioned range, d1 may be larger than d2. 
     The nozzle orifices may also be ellipsoidal in shape as shown in FIG. 8. In this case, preferably the angle of inclination α of the orifices relative to the direction of movement of the chill surface 3 is 10-80 degrees, the length of the short diameter is 0.1-3.0 mm, the length of the long diameter is 0.5-10.0 mm and the narrowest distance between adjacent orifices is in the order of 0.2 mm. Here, α refers to the angle between the long diameter and the direction of movement of the chill surface. Moreover, orifices may be polygonal in shape, such as hexagonal. 
     The provision at the edge portions of additional small triangular/parallelogram/trapezoid orifices such as are shown in FIGS. 1A and 2A is an effective way of ensuring strip does not become thinner at the edge portions. The shapes and dimensions of these small orifices will be selected according to the shapes and positioning of adjacent orifices. The height will be in the range 0.5-7.0 mm. The length of the lower side thereof will be about the same as the length of the lower side of adjacent orifices. However if the angle α should exceed 60 degrees, making the length of the lower side longer than the length of the lower side of the adjacent orifice, or adding a plurality of small orifices, is effective. 
     The various conditions described in the foregoing are mutually interrelated, not independent. Accordingly, what constitutes an optimum combination is determined by experiment. Desirable parameter combinations are shown below in the form of examples. 
     The advantages are particularly marked when the method of this invention is applied to alloys which readily become amorphous and to metals which are difficult to roll or otherwise process, but the method is not limited to such applications. 
     
                                           TABLE 1                                 
__________________________________________________________________________
                                        Casting conditions                
Slot-shape                                    Roll                        
Orifice                  No. of         Ejection                          
                                              surface                     
                                                    Strip shape           
    shape a   b   d   α                                             
                         orfices                                          
                              Composition (at %)                          
                                        pressure                          
                                              velocity                    
                                                    Width                 
                                                        Thickness         
__________________________________________________________________________
Sample                                                                    
    Paral-                                                                
          2 mm                                                            
              0.7 mm                                                      
                  0.9 mm                                                  
                      45°                                          
                         14   Fe.sub.30.5 Si.sub.6.5 B.sub.12 C.sub.1     
                                        0.2 kg/cm.sup.2                   
                                              24 m/s                      
                                                    25 mm                 
                                                        36 km             
1   lelogram                                                              
Sample                                                                    
    Paral-                                                                
          4   &#34;   0.6 &#34;  16   Fe.sub.30.5 Si.sub.6.5 B.sub.12 C.sub.1     
                                        &#34;     &#34;     24.5                  
                                                        62                
2   lelogram                                                              
Sample                                                                    
    Paral-                                                                
          &#34;   &#34;   &#34;   &#34;  16   Fe.sub.30.5 Si.sub.6.5 B.sub.12 C.sub.1     
                                        &#34;     &#34;     25  64                
3   lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Trapezoid                                                             
          2   b.sub.1 1                                                   
                  d.sub.1 1                                               
                      48 12   Fe.sub.30.5 Si.sub.6.5 B.sub.12 C.sub.1     
                                        &#34;     &#34;     &#34;   45                
4             b.sub.2 0.5                                                 
                  d.sub.2  1.5                                            
                         Small                                            
                         orifices: 2                                      
Sample                                                                    
    Trapezoid                                                             
          4   &#34;   &#34;   &#34;  &#34;    Fe.sub.79 Si.sub.5 B.sub.13                 
                                        &#34;     12    &#34;   92                
Sample                                                                    
    Paral-                                                                
          2   0.7 1   26 42   Fe.sub.79 Si.sub.5 B.sub.13                 
                                        &#34;     24    74  42                
6   lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Paral-                                                                
          1   &#34;   &#34;   &#34;  &#34;    Fe.sub.75 Ni.sub.5 Mo.sub.4 B.sub.12        
                              C.sub.4   &#34;     &#34;     &#34;   32                
7   lelogram                                                              
Sample                                                                    
    Paral-                                                                
          1.5 &#34;   &#34;   37 &#34;    Co.sub.69 Fe.sub.4 Mo.sub.2 Si.sub.16       
                              B.sub.9   &#34;     &#34;     74.5                  
                                                        38                
8   lelogram                                                              
Sample                                                                    
    Paral-                                                                
          &#34;   &#34;   &#34;   30 88   Fe.sub.72 Co.sub.10 Mo.sub.2 B.sub.12       
                              C.sub.4   &#34;     28    151 35                
9   lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Paral-                                                                
          &#34;   &#34;   &#34;   &#34;  130  Fe.sub.72 Co.sub.10 Mo.sub.2 B.sub.12       
                              C.sub.4   &#34;     24    221 43                
10  lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Paral-                                                                
          2   &#34;   &#34;   37 42   Fe.sub.60 Ni.sub.20 Cr.sub.4 B.sub.12       
                              C.sub.4   &#34;     &#34;     74.5                  
                                                        48                
11  lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Paral-                                                                
          1.5 &#34;   &#34;   30 130  Fe.sub.54 Ni.sub.20 Cr.sub.10 B.sub.12      
                              C.sub.4   &#34;     &#34;     222 40                
12  lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Trapezoid                                                             
          2   &#34;   &#34;   37 14   Cu.sub.66 Ti.sub.34                         
                                        &#34;     &#34;     25.5                  
                                                        54                
13                       Small                                            
                         orifices: 2                                      
Sample                                                                    
    Paral-                                                                
          4   &#34;   0.6 45 16   Fe.sub.91.4 Si.sub.8.6                      
                                        0.3   11    25  82                
14  lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Paral-                                                                
          2   &#34;   1   &#34;  14   Fe.sub.87.9 Si.sub.121                      
                                        &#34;     &#34;     &#34;   68                
15  lelogram             Small                                            
                         orifices: 2                                      
Sample                                                                    
    Paral-                                                                
          &#34;   &#34;   &#34;   &#34;  &#34;    Fe.sub.73.3 Cr.sub.19.2 Ni.sub.7.5          
                                        &#34;     &#34;     &#34;   72                
16  lelogram                                                              
Sample                                                                    
    Paral-                                                                
          &#34;   &#34;   &#34;   &#34;  &#34;    Fe.sub.70.2 Cr.sub.20.1 Al.sub.9.7          
                                        &#34;     &#34;     &#34;   71                
    lelogram                                                              
Sample                                                                    
    Paral-                                                                
          &#34;   &#34;   &#34;   &#34;  &#34;    Fe.sub.59.4 Mn.sub.28.5 Si.sub.121          
                                        &#34;     14    &#34;   56                
18  lelogram                                                              
__________________________________________________________________________
Strip shape                    180° Bending                        
Thickness Magnetic properties  Free surface/                              
                                          Corrosion-                      
                                                Amorphous/                
    ratio W 13/50                                                         
                W 1/10K                                                   
                     μ  B   Roll surface                               
                                      T.S.                                
                                          resistance                      
                                                crystalline               
                                                       Remarks            
__________________________________________________________________________
Sample                                                                    
    94.6% 0.102 w/kg                                                      
                --   --    B.sub.1                                        
                               O/O    kg/ton                              
                                          --    Amorphous                 
                                                       Edge sharpness     
1                          1.52       L 252                               
Sample                                                                    
    --    --    --   --    --  O/Δ                                  
                                      --  --    Amorphous                 
                                                       Edge sharpness     
Sample                                                                    
    96.5  0.110 --   --    B.sub.1                                        
                               O/Δ                                  
                                      --  --    Amorphous                 
3                          1.54                                           
Sample                                                                    
    95.9  0.096 --   --    B.sub.1                                        
                               O/O    --  --    Amorphous                 
4                          1.54                                           
Sample                                                                    
    96.8  0.120 --   --    B.sub.1                                        
                               O/O    L 320                               
                                          --    Amorphous                 
5                          1.56                                           
Sample                                                                    
    96.8  0.095 --   --    B.sub.1                                        
                               O/O    --  --    Amorphous                 
6                          1.53                                           
Sample                                                                    
    95.6  0.096 W/kg μ.sub.s                                           
                           B.sub.s                                        
                               O/O    --  --    Amorphous                 
7               1.0  6,000 1.3                                            
Sample                                                                    
    94.8  --    --   μ.sub.i                                           
                           B.sub.s                                        
                               O/O    --  --    Amorphous                 
8                    55,000                                               
                           0.7                                            
Sample                                                                    
    95.8  0.130 --   μ.sub.50                                          
                           B.sub.s                                        
                               O/O    L 210                               
                                          --    Amorphous                 
                     180,000                                              
                           1.5        C 187                               
Sample                                                                    
    95.4  0.128 --   μ.sub.50                                          
                           B.sub.s                                        
                               O/O    L 203                               
                                          --    Amorphous                 
10                   180,000                                              
                           1.5        C 179                               
Sample                                                                    
    96.2  --    --   --    --  O/O    --  30%   Amorphous                 
11                                                                        
Sample                                                                    
    95.4  --    --   --    --  O/O    --        Amorphous                 
12                                                                        
Sample                                                                    
    93.2  --    --   --    --  O/O    --  --    Amorphous                 
13                                                                        
Sample                                                                    
    90.4  0.71  --   --    B.sub.1                                        
                               O/O    --  --    Crystalline               
14                         1.12                                           
Sample                                                                    
    91.5  0.73  --   --    B.sub.1                                        
                               X/X    --  --    Crystalline               
15                         1.10                                           
Sample                                                                    
    92.4  --    --   --    --  O/O    L 60                                
                                          --    Crystalline               
16                                                                        
Sample                                                                    
    92.1  --    --   --    --  O/O    L 62                                
                                          --    Crystalline               
17                                    C 55                                
Sample                                                                    
    93.1  --    --   --    --  O/O    --  --    Crystalline               
18                                                                        
__________________________________________________________________________
 *In the TS column, L is tensile strength in the strip longitudinal       
 direction, and C in the width direction.                                 
 
    
     Table 1 shows data relating to shape, magnetic properties, 180-degree bend-testing, tensile strength testing, corrosion-resistance and other such properties of examples of strip of various alloys manufactured using the nozzle according to the present invention. 180° bending, free surface/roll surface refers to the situation where the strip is bent back 180° into fact-to-face contact with itself with the free surface on the outside. The free surface is the surface of the solidified strip which does not contact the shell surface upon solidification. The roll surface is the surface of the solidified strip which contacts the chell surface upon solidification. Strip thickness ratio is the ratio of the thickness calculated according to weight to the thickness measured using a micrometer. That is, thickness ration is the ratio of the computed sheet thickness based upon weight to the actual sheet thickness as measured by a micrometer. Magnetic properties data are figures obtained after annealing. For amorphous strip, annealing conditions were 60 minutes at 380° C. in an N2 atmosphere and a field strength of 40 Oe. Crystalline strip was annealed at 1,100°  C. for 60 minutes in a vacuum (down to 10 -4  torr). Ni is initial permeability, μ5 is the permeability at 5 mOe and μ50 at 50 mOe. The corrosion-resistance test was according to the method of JIS Z-23711 (Salt Water Exposure Method; equivalent to the U.S. Salt Spray Test). All strip was subjected to x-ray diffraction and differential scanning calorimetry to confirm amorphosity. 
     In Table 1, W1/10K stands for the core loss at a frequency of 10 KHz and a magnetic flux density of 1 Tesla. W13/50 stands for the core loss at a frequency of 50 Hz and a magnetic flux density of 1.3 Tesla. 
     Thickness ratios were high, all over 90%. Thickness ratios exceeding 90% are high and are on a par with those for strip manufactured according to the conventional method. 
     The surface (free surface) characteristics of strip obtained in Examples 1, 3 and 4 are shown in FIGS. 4, 5 and 6, respectively. These data are equivalent to those for the surface characteristics of strip produced by the conventional method shown in FIG. 7. 
     Thickness deviation in the width direction was examined with respect to strip obtained in the Examples 1, 6, 9, and 10. It was found that even when strip width was increased, there were virtually no differences in thickness deviation, in each case the figure not exceeding 10%. Also, while flume-shaped warping was often seen in the width direction of wide trip manufactured according to a conventional method, such flume-shaped warps were almost entirely absent in strip manufactured according to the method of the present invention. 
     Thus, as has been described in the above, adoption of the method of this invention enables metal strip of a desired large width to be manufactured, and substantially without any lowering of the space factor. 
     As the method according to this invention allows the production of, for example, wide Fe amorphous alloy strip, it can be applied to large wound or laminated core transformers. It is also well suited for use with magnetic shielding materials, decorative and other building materials and, if plated with copper or other such high-conductivity metal, as electro- magnetic-frequency shielding material, especially as a material for the blinds used in electromagnetic dark-rooms. 
     At present the widest amorphous alloy strip that can be obtained is around 10 cm wide. The method according to the present invention eliminates the conventional necessity to resort to brazing or the like in order to increase the width of the available strip. Also, the strip can be cut into thin slices to form composite reinforced material which can be copper-plated and made into spirals for use as coaxial cable shielding.