Low metalloid containing amorphous metal alloys
DESCRIPTION 
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to iron, nickel, cobalt and/or chromium rich amorphous alloys that contain refractory metals and low boron content. 
     2. Description of the Prior Art 
     Chen et al. in U.S. Pat. No. 3,856,513, issued Dec. 24, 1974, have disclosed glassy alloys consisting essentially of about 60 to 90 atom percent of at least one element of iron, nickel, cobalt, vanadium and chromium, about 10 to 30 atom percent of at least one element of phosphorus, boron and carbon and about 0.1 to 15 atom percent of at least one element of aluminum, silicon, tin, germanium, indium, antimony and beryllium. Up to about one-fourth of the metal may be replaced by elements which commonly alloy with iron and nickel, such as molybdenum, titanium, manganese, tungsten, zirconium, hafnium and copper. Chen et al. also discloses wires of glassy alloys having the general formula T i  X j , where T is a transition metal and X is an element selected from the group consisting of phosphorus, boron, carbon, aluminum, silicon, tin, germanium, indium, beryllium and antimony, and where &#34;i&#34; ranges from about 70 to 87 atom percent and &#34;j&#34; ranges from about 13 to 30 atom percent. 
     More recently, Masumoto et al. have disclosed iron-chromium glassy alloys consisting essentially of about 1 to 40 atom percent chromium, 7 to 35 atom percent of at least one of carbon, boron and phosphorus and the balance iron. Up to about 40 atom percent of at least one of nickel and cobalt, up to 20 atom percent of at least one of molybdenum, zirconium, titanium and manganese and up to about 10 atom percent of at least one of vanadium, niobium, tungsten, tantalum and copper may also be employed. Elements useful for improving mechanical properties include molybdenum, zirconium, titanium, vanadium, niobium, tantalum, tungsten, copper and manganese, while elements effective for improving the heat resistance include molybdenum, zirconium, titanium, vanadium, niobium, tantalum and tungsten. 
     Efforts to develop new compositions which are easily formed in the glassy state with superior mechanical properties and which at the same time retain high thermal stability are continuing. Substantial amounts of metalloid elements (typically 15 to 25 atom percent) are usually found most suitable for producing the glassy state under reasonable quenching conditions of at least about 10 5  ° C./sec, consistent with forming a ductile product. However, such high metalloid content combined with a high refractory metal content also may result in increasing brittleness of the glassy alloy in the asquenched state. 
     SUMMARY OF THE INVENTION 
     The present invention provides substantially glassy iron, nickel, cobalt rich alloys that contain at least one of the refractory metals molybdenum, tungsten, titanium, chromium and vanadium with low boron content. The glassy alloys of the invention are defined essentially by the formula T a  R b  B c , where T is at least one metal selected from the group consisting of iron, nickel, cobalt and manganese, R is at least one refractory metal selected from the group consisting of molybdenum, tungsten, titanium, chromium and vanadium, and B is boron; &#34;a&#34;, &#34;b&#34; and &#34;c&#34; are in atomic percent and are about 72-86, 3-25 and 4-10, respectively, and &#34;a&#34; plus &#34;b&#34; plus &#34;c&#34; equals 100. The alloys of the invention evidence hardness values of at least about 530 Kg/mm 2 , yield strengths of at least about 220 Kpsi and crystallization temperatures of at least about 400° C. 
     DETAILED DESCRIPTION OF THE INVENTION 
     The glassy alloys of the present invention consist essentially of the composition T a  R b  B c , where T is at least one metal selected from the group consisting of iron, nickel, cobalt and manganese, R is at least one refractory metal selected from the group consisting of molybdenum, tungsten, titanium, chromium and vanadium, and B is boron; &#34;a&#34;, &#34;b&#34; and &#34;c&#34; are in atomic percent and are about 72-86, 3-25 and 4-10, respectively, and &#34;a&#34; plus &#34;b&#34; plus &#34;c&#34; equals 100. Examples of glassy alloys of the invention include those set forth below in Table I. 
     
                       TABLE I                                                     
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Alloy Composition (Atom %)                                                
Ni  Co     Cr     Fe   Mo    B    Ti   Mn    V    W                       
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45  24     10      7   4     10   --   --    --   --                      
11  10     5      60   4     10   --   --    --   --                      
7   7      --     70   8     8    --   --    --   --                      
7   7      --     72   8     6    --   --    --   --                      
8   --     6      66   12    8    --   --    --   --                      
5   --     10     62   15    8    --   --    --   --                      
8   --     6      64   12    10   --   --    --   --                      
5   --     10     60   15    10   --   --    --   --                      
8   --     6      62   12    8    4    --    --   --                      
--  --     --     72   20    8    --   --    --   --                      
10  10     7      49   10    6    1.5  3     3    .5                      
10  10     10     50   10    6    --   2     2    --                      
--  --     10     72   10    8    --   --    --   --                      
5   5      6      64   10    10   --   --    --   --                      
10  10     5      66   3     6    --   --    --   --                      
45  20     15      5   7     8    --   --    --   --                      
40  25     15      8   6     6    --   --    --   --                      
10  5      10     65   6     4    --   --    --   --                      
10  5      10     63   6     6    --   --    --   --                      
10  5      10     62   6     7    --   --    --   --                      
10  5      10     60   6     9    --   --    --   --                      
10  7      10     60   6     7    --   --    --   --                      
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     The low boron content and the refractory metal content are interdependent. When the boron content is less than about 4 atom percent and the refractory metal content lies within the limits specified, rapidly quenched ribbons are not substantially glassy. Rather, the rapidly quenched ribbons contain crystalline phases, which may comprise a substantial fraction (e.g., more than 50 percent) of the material, depending on specific composition. The rapidly quenched ribbons containing crystalline phases or mixtures of both glassy and crystalline phases have inferior mechanical properties, i.e., low tensile strength, and are brittle. Typically, such ribbons, having thicknesses up to 0.0015 inch, will fracture if bent to a radius of curvature less than 100 times the thickness. 
     When the boron content is greater than about 10 atom percent and the refractory metal content lies within the limits specified, rapidly quenched ribbons, while remaining substantially glassy are, nevertheless, more brittle than ribbons having compositions within the scope of the invention. Typically, such ribbons fracture when bent to a radius of curvature less than about 100 times the thickness. 
     Similarly, for refractory metal concentrations less than or greater than those listed above, compositions containing such low metalloid content do not form glassy alloys at the usual quench rates. While ductile glassy alloys have heretofore been obtained with refractory metal-boron combinations, such alloys have had a higher boron concentration (typically 15 to 25 atom percent) and higher refractory metal concentrations (typically more than about 20 atom percent). 
     In contrast, when the boron content ranges from about 4 to 10 atom percent, together with about 3  to 25 atom percent of at least one member selected from the group consisting of molybdenum, tungsten, titanium, vanadium and chromium, and about 72 to 86 atom percent of at least one member selected from the group consisting of iron, nickel, cobalt and manganese, rapidly quenched ribbons are substantially glassy and possess superior mechanical properties, i.e., high tensile strength, thermal stability and ductility. For example, glassy ribbons of the invention can be bent without fracture to a radius of curvature about 10 times the thickness. 
     Use of refractory metal elements other than miolybdenum, tungsten, titanium, vanadium and chromium, and use of metalloids other than boron in the amounts given do not form ductile glassy alloys at the usual quench rates. For example, replacing boron by carbon or silicon results in the formation of crystalline, rather than glossy, phases. 
     The purity of all elements is that found in normal commercial practice. However, it is contemplated that minor additions (up to a few atom percent) of other alloying elements may be made without an unacceptable reduction of the desired properties. Such additions may be made, for example, to aid the glass-forming behavior. Such alloying elements include the transition metal elements (Groups IB to VIIB and VIII, Rows 4, 5 and 6 of the Periodic Table, other than the elements mentioned above) and metalloid elements (carbon, silicon, aluminum, and phosphorus). 
     The thermal stability of a glassy alloy is an important property in certain applications. Thermal stability is characterized by the time-temperature behavior of an alloy, and may be determined in part by differential thermal analysis (DTA). Glassy alloys with similar crystallization behavior as observed by DTA may exhibit different embrittlement behavior upon exposure to the same heat treatment cycle. By DTA measurement, crystallization temperatures T c  can be accurately determined by heating a glassy alloy (at about 20° to 50° C./min) and noting whether excess heat is evolved over a limited temperature range (crystallization temperature) or whether excess heat is absorbed over a particular temperature range (glass transition temperature). In general, the glass transition temperature is near the lowest, or first, crystallization temperature T cl  and, as is conventional, is the temperature at which the viscosity ranges from about 10 13  to 10 14  poise. 
     The glassy alloys of the invention are formed by quenching an alloy melt of the appropriate composition at a rate of at least about 10 5  ° C./sec. A variety of techniques are available, as is well-known in the art, for fabricating rapidly-quenching continuous filament in ribbon and sheet form. Typically, a particular composition is selected, powders of the requisite elements (or of materials that decompose to form the elements) in the desired proportions are melted and homogenized, and the molten alloy is rapidly quenched on a chill surface, such as a rapidly rotating cylinder. 
     The alloys of the invention are substantially totally glassy, as determined by X-ray diffraction. The term &#34;glassy,&#34; as used herein, means a state of matter in which the component atoms are arranged in a disorderly array; that is, there is no long range order. Such a glassy alloy material gives rise to broad, diffuse diffraction peaks when subjected to electromagnetic radiation in the X-ray region (about 0.01 to 50 A wavelength). This is in contrast to crystalline material, in which the component atoms are arranged in an orderly array, giving rise to sharp diffraction peaks. 
     The glassy alloys of the invention evidence hardness values of at least about 530 Kg/mm 2 , yield strengths of at least about 220 Kpsi and crystallization temperatures of at least about 400° C. In alloys having iron and molybdenum as principle components, decreasing the iron content and increasing the molybdenum content results in an increase in hardness to values approaching 750 Kg/mm 2 . Compositions with boron content of about 8 to 10 atom percent are especially ductile. Accordingly, such compositions, which consist essentially of about 8 to 10 atom percent boron, about 8 to 12 atom percent molybdenum, about 66-70 atom percent iron and about 3-14 atom percent of combined content of nickel, cobalt and chromium plus incidental impurities are preferred. These alloys also evidence excellent fabricability and, in ribbon form, excellent ductility. Examples of such preferred alloys include Fe 70  Ni 7  Co 7  Mo 8  B 8  and Fe 66  Ni 8  Cr 6  Mo 12  B 8 . 
     Especially preferred compositions include those with about 8 to 10 atom percent boron, about 8 to 15 atom percent molybdenum, about 60-66 atom percent iron, about 5-10 atom percent nickel, about 6-10 chromium and/or cobalt, plus incidental impurities. These alloys possess excellent ribbon fabricability and ductility. Examples include Fe 62  Ni 5  Mo 15  Cr 10  B 8  and Fe 64  Ni 8  Mo 12  Cr 6  B 10 . 
     The high mechanical strength and high thermal stability of the glassy alloys of the invention renders them suitable for use as high strength fibers and as reinforcement in composites for high temperature applications. Ribbon and sheet composed of the glassy alloys of the invention make useful cutting implements such as razor blades, knives and the like. 
    
    
     EXAMPLE I 
     Alloys of the compositions Fe 60  Ni 11  Co 10  Cr 5  Mo 4  B 10  and Fe 60  Ni 10  Co 5  Cr 10  Mo 6  B 9  were prepared from constituent elements of high purity (≧99.9%). The elements with a total weight of 20 g were melted by induction heater in a quartz crucible under vacuum of 10 -3  Torr. The molten alloy was held at 150° to 200° C. above the liquidus temperature for 10 min. and allowed to become completely homogenized before it was slowly cooled to solid state at room temperature. The alloy was fractured and examined for complete homogeneity. 
     About 10 g of the alloys was remelted to 150° C. above liquidus temperatures in a quartz crucible provided with a helium atmosphere having an orifice of about 0.010 inch diameter in the bottom. The chill substrate used in the present work was copper having moderately high strength and high thermal conductivity. The substrate was rotated at a surface speed of 4000 ft/min. 
     The melt was spun as a molten jet by applying argon pressure of 5-10 psi over the melt. The molten jet impinged at an angle of about 20° off verticle onto the external surface of the rotating substrate. The ribbon was displaced from the substrate naturally at a position along the circumference away from the point of jet impingement. The substrate surface was polished with 320 grit emery paper and cleaned and dried with acetone prior to the start of the casting operation. The as-cast ribbons were found to have good edges and surfaces. The ribbons had the following dimensions: 0.001 to 0.002 inch thickness and 0.015 to 0.020 inch width. 
     The degree of glassiness was determined by X-ray diffraction. A cooling rate of at least about 10 5  ° C./sec was attained by the quenching process. 
     Hardness (H) was measured by the diamond pyramid technique using a Vickers-type indenter, consisting of a diamond in the form of a square-base pyramid with an included angle of 136° between opposite faces. Loads of 50 g were applied. Crystallization temperature was measured by differential thermal analysis at a scan rate of about 20° C./min. Yield strength (Y) was estimated as per the following equation H÷Y=3.2, developed by L. A. Davis, Scripta Metallurgica, Vol. 9, pp. 431-436 (1975). 
     The following values of hardness in Kg/mm 2 , yield strength in Kpsi and crystallization temperature in °C., listed below in Table II, were measured for these compositions. 
     
                       TABLE II                                                    
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Mechanical and Thermal Properties of Fe-Mo-B                              
and Fe-W-B Glassy Alloys of the Invention                                 
                                 Crystal-                                 
                        Yield    lization                                 
Composition   Hardness, Strength,                                         
                                 Temperature,                             
(Atom Percent)                                                            
              Kg/mm.sup.2                                                 
                        Kpsi     °C.                               
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Fe.sub.60 Ni.sub.10 Co.sub.5 Cr.sub.10 Mo.sub.6 B.sub.9                   
              532       237      601° C.                           
Fe.sub.60 Ni.sub.11 Co.sub.10 Cr.sub.5 Mo.sub.4 B.sub.10                  
              750       334      405° C.                           
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     EXAMPLE II 
     Three alloys having lower boron content (e.g., Fe 66  Ni 8  Cr 6  Mo 12  B 8 , Fe 5  Ni 45  Co 20  Cr 15  Mo 7  B 8  and Fe 8  Ni 40  Co 25  Cr 15  Mo 6  B 6 ) were prepared according to the procedure set forth in Example I. 
     About 10 g of the alloys was remelted to 150° C. above liquidus temperatures under vacuum of 10 -3  Torr in a quartz crucible having an orfice of about 0.010 inch diameter in the bottom. The chill substrate used in the present work was heat treated beryllium-copper alloy having moderately high strength and high thermal conductivity. The substrate material contained 0.4 to 0.7 wt% beryllium, 2.4 to 2.7 wt% cobalt and copper as balance. The subtrate was rotated at a surface speed of 4000 ft/min. The substrate and the crucible were contained inside a vacuum chamber evacuated to 10 -3  Torr. 
     The melt was spun at a molten jet by applying argon pressure of 5-10 psi over the melt. The molten jet impinged at an angle of about 20° off verticle onto the internal surface of the rotating substrate. The chill-cast ribbon was maintained in good contact with the substrate by the centrifugal force acting on the ribbon against the surface. The ribbon was displaced from the substrate by nitrogen gas at 30 psi at a position two-thirds of the circumferential length away from the point of jet impingement. During the metallic glass ribbon casting operation, the vacuum chamber was maintained under a dynamic vaccum of 20 Torr. The substrate surface was polished with 320 grit emery paper and cleaned and dried with acetone prior to the start of the casting operation. The as-cast ribbons were found to have good edges and surfaces. The ribbons had the following dimensions: 0.001 to 0.002 inch thickness and 0.015 to 0.020 inch width. 
     The degree of glassiness was determined by X-ray diffraction. A cooling rate of at least about 10 5  ° C./sec was attained by the quenching process. Hardness, crystallization temperature and yield strength were measured as in Example I. The alloys were amorphous, ductile, strong, hard and thermally stable up to 472° C. 
     Having thus described the invention in rather full detail it will be understood that these details need not be strictly adhered to but that various changes and modifications may suggest themselves to one skilled in the art, all falling within the scope of the invention as defined by the subjoined claims.