Preparation of zirconium alloys
CROSS-REFERENCE TO RELATED APPLICATION 
     This application is a continuation-in-part of U.S. Ser. No. 465,654, filed Apr. 30, 1974, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     This invention relates to the preparation of high strength zirconium alloys containing 7.0-10-0 wt% aluminum. 
     Structural materials for use in thermal nuclear reactors are required to satisfy a number of requirements, including: 
     1. Low absorption cross section for thermal neutrons. 
     2. High corrosion resistance to the gaseous or liquid reactor collant. 
     3. Good mechanical strength and ductility. 
     4. Resistance to creep deformation at elevated temperatures. 
     5. Resistance to wear and erosion. 
     Zirconium alloys have been found to satisfy many of these requirements. Commonly employed has been the alloy known under the trade name of Zircaloy-2, and a Zr-2.5%Nb alloy. 
     Since the earliest days of zirconium technology it has been recognised that alloys based on the αZr solid solution phase of the Zr-Al system, are superior to any other known group of Zr alloys in respect of their mechanical strength (see A. D. Schwope and N. Chubb Journal of Metals Vol. 4, 1942 page 1138,). However, additions of Al of sufficient magnitude to improve the mechanical properties also have the disadvantage that they greatly reduce the corrosion resistance of the alloys, resulting in catastrophic oxidation in steam or water (see R. L. Carpenter, M. D. Carver and E. T. Hayes, U.S. Bureau of Mines Report USBM-U-40 (1955) and M. D. Carver and E. T. Hayes, USBM-U-122 (1956). Because of this difficulty the Zr-Al alloys have been disregarded as possible construction materials for use in thermal nuclear reactors. 
     The alloys of zirconium in current use, and many others which have been invented are based on a matrix of zirconium which contains in solution one or more other elements, and in which matrix there may or may not be precipitates of compounds of zirconium and/or other elements. 
     The Zr-Al phase diagram was extensively studied by McPherson and Hansen and published in the Transactions of the American Society for Metals, Vol. 46, page 354, 1954. It was found that an intermediate phase, located close to 13% Al, and designated Zr 2  Al exists between about 1200° and 1300° C. It is formed by the peritectoid reaction: βZr + Zr 5  Al 3  ⃡ Zr 2  Al. Another peritectoid reaction was found to occur between 950° C and 1,000° C involving the phases: βZr + Zr 2  Al ⃡ Zr 3  Al (8.97%Al). 
     In the course of their work McPherson and Hansen prepared, from high-purity material, 25 gram buttons of Zr-alloys containing 7.0, 7.8, 9.4 and 9.7 wt% aluminum and subjected them to annealing treatments up to about 400 hours at less than approximately 950° C. They determined that the microstructure of the 7.8 wt% Al alloys annealed at these temperatures was substantially that of isolated crystals of Zr 3  Al dispersed in a matrix of transformed βZr containing Al in solution, implying that the alloys containing 7.0 wt% Al had a similar structure; the microstructure of the 9.4 and 9.7 wt% Al alloys was a mixture of Zr 3  Al and Zr 2  Al. Subsequently Keeler and Mallery (Transactions of American Inst. of Mining &amp; Metallurgical Engineers, Feb. 1955, Page 394) reported the crystal structure and confirmed the earlier McPherson and Hansen report on the plastic properties of Zr 3  Al. These workers did not, however, appreciate that Zr-Al alloys having a continuous or substantially continuous matrix of Zr 3  Al have significantly different characteristics than Zr-Al alloys having a matrix of α or β zirconium. Indeed, from the McPherson and Hansen observation (FIG. 9, p. 360) of crystals of Zr 3  Al in a Zr matrix, the knowledgeable metallurgist would have suspected that such alloys would have very low corrosion resistance. No corrosion, tensile or creep properties of the 7.0-9.7 wt% Al alloys were determined due, it is believed, at least in part to the poor corrosion experience previously reported which taught away from the practical use of any Zr-Al alloy with a zirconium matrix. It was not in fact known whether an alloy could be formed having a continuous or substantially continuous matrix of Zr 3  Al, or if possible, how such an alloy could be formed on a commercial scale. 
     Considering the McPherson and Hansen paper, page 360, FIGS. 8 and 9 (and captions therefor) and page 361, lines 5-8, it appears that the authors annealed their 7.8 wt% Al alloy to obtain &#34;Predominant phase is Zr 2  Al in a matrix of transformed beta&#34;. Thus the Zr 2  Al would seem to be largely isolated coarse particles of Zr 2  Al (see FIG. 8 and its caption). To obtain FIG. 9, the &#34;same alloy&#34; as in FIG. 8 was apparently annealed at 950° C for 45 hours to give &#34;Crystals of Zr 3  Al in a matrix of transformed beta&#34;. 
     From experimentation it has been found that annealing of alloys having coarse particles of Zr 2  Al in a β Zr matrix, for time periods up to about 160 hours at a temperature of about 950° C, results in transformation of Zr 2  Al to Zr 3  Al only at the interface surrounding the initial Zr 2  Al particles. 
     The layer of Zr 3  Al surrounding the Zr 2  Al phase apparently greatly slows the diffusion of Zr and the transformation to Zr 3  Al and tends to isolate the Zr 3  Al and prevent its forming the continuous matrix phase. It thus becomes clear that casting and initial annealing techniques should be controlled to avoid forming Zr 2  Al phase as coarse dispersed particles. In small ingots, coarse Zr 2  Al particles were found to inhibit the matrix phase Zr 3  Al transformation, and in much larger ingots one could assume still coarser Zr 2  Al particles would form and be even more of a problem. 
     Indeed it might well have been thought that in an ingot of sufficient size to be of practical value, the Zr 2  Al particles would be so large that transformation to give a Zr 3  Al matrix would be virtually impossible. However, we have shown that by control of ingot diameter and other casting parameters, ingots of 500 pounds can be subsequently transformed to a Zr 3  Al matrix in reasonable times. This could certainly not be deduced from the work of McPherson et al, who used very small ingots and high purity material, and had no disclosure of avoiding Zr 2  Al coarse particles which prevent obtaining a Zr 3  Al matrix phase. 
     SUMMARY OF THE INVENTION 
     An object of the present invention is to prepare high strength, corrosion resistant zirconium alloys, containing 7.0-10.0 wt% aluminum, which are suitable for thermal nuclear reactor applications. Ternary, quaternary or more additions may be introduced in order to enhance specific properties, within the broad 7.0-10.0 wt% aluminum range. Preferably binary Zr-Al alloys of the present invention will contain 7.5-9.5 wt%Al, and more preferably 7.6-9.0 wt%Al. The alloys prepared by the present invention may also find application in such fields as prosthetic devices and chemical engineering applications. 
     The invention involves annealing a cast, or possibly a powder metallurgically produced, zirconium alloy containing 7.0-10.0 wt%, preferably 7.5-9.5 wt% aluminum, and more preferably 7.6-9.0 wt% aluminum, at a temperature below 992° C for a sufficient time such that the microstructure of the alloy is transformed to a substantially continuous matrix of the ordered intermetallic phase Zr 3  Al. To effect homogenization of alloys containing less than 9 wt% Al it is possible to heat soak in the βZr phase field at temperatures between about 1250° and about 1350° C for times up to a maximum of a few hours, depending on sample size, before transforming to Zr 3  Al at temperatures below about 992° C. The intermetallic compound Zr 3  Al has an ordered face-centered cubic crystal structure of the Cu 3  Au type. Therefore alloys in which the matrix is composed of this compound are fundamentally different from other zirconium alloys which have one or both of the close-packed hexagonal and body centered cubic crystal structures of zirconium as their primary phase. 
     Zr 3  Al is considered to be the primary phase in these alloys when it is present in quantities usually greater than about 50% by volume, forming a continuous or semi-continuous network throughout the alloys. The composition of a single phase Zr 3  Al alloy is approximately 8.97% by weight aluminum and in the simple example of a binary zirconium-aluminum alloy, the above criteria can be satisfied by alloys containing approximately 6.5 to 10 wt% aluminum. 
     In one aspect the invention provides a method of producing a high tensile strength, creep and corrosion resistant zirconium alloy containing 7.0-10.0 wt% Al, 0-3 wt% in total of one or more elements selected from the group consisting of magnesium, tin, chromium, iron, carbon, silicon, yttrium, niobium, molybdenum and beryllium, balance zirconium and incidental impurities, comprising annealing said alloy at a temperature below the decomposition temperature of Zr 3  Al for a period of time sufficient to produce a substantially continuous matrix of the intermetallic compound Zr 3  Al in said alloy. 
     The invention also contemplates a preliminary step, prior to annealing, of heat soaking the alloy in the βZr-Zr 2  Al two phase region and then working at a temperature between about 1000° C and the melting point of the alloy. Working can be by rolling or by extrusion, for example, the extrusion of tubes. The subsequent annealing is carried out at temperature below about 992° C. 
     Alloys prepared according to the present invention have higher corrosion resistance than dilute Zr-Al alloys while possessing superior mechanical properties to the usual Zr-based alloys, such as Zircaloy-2, currently used in nuclear reactor applications. The alloys prepared by the present invention also exhibit thermal neutron absorption cross section characteristics of the order of 0.0096 cm 2  /cm 3 , which is well within the designed limits for use in thermal nuclear reactors. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     The invention will be described in more detail with reference to the following examples and the drawings in which: 
     FIG. 1 is a sketch of part of the Zr-Al phase diagram; 
     FIGS. 2a-2h are photomicrographs of Zr 3  Al alloys containing (a) 6.5 wt% Al; (b) 7.0 wt% Al; (c) 8.0 wt% Al; (d) 8.8 wt% Al; (e) 9.0 wt% Al; (f) 9.3 wt% Al; (g) 9.4 wt% Al; (g) 9.4 wt% Al; (h) 9.5 wt% Al; balance Zr respectively; 
     FIG. 3 is a graph showing transition temperature of brittle-ductile fracture of zirconium alloys containing 9.3 to 9.5 wt% Al; 
     FIG. 4 is a graph, on a log-log scale, showing the relationship between creep rate and tensile stress for selected zirconium alloys in the hot worked and fully annealed conditions; 
     FIG. 5 is a graph showing the effect of temperature on the yield stress (at 0.2% strain offset) of zirconium allows and is located on the sheet containing FIG. 3; 
     FIG. 6 is a graph showing the effect of Al content on the yield stress for zirconium alloys between 20° C and 600° C; and 
     FIG. 7 is a graph showing the effect of temperature of the ultimate tensile stress of zirconium alloys. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Unless otherwise stated, all alloy compositions throughout this specification are defined in percentages by weight. From the phase diagram in FIG. 1 it will be observed that a peritectoid reaction occurs at approximately 975°-992° C and we have found that cast Zr alloys containing approximately 9 wt% Al will, if held at below about 975° C for a sufficiently long period of time, eventually undergo a peritectoid transformation and the βZr phase (or αZr depending on temperature) will react with the Zr 2  Al and/or Zr 5  Al 3  phases resulting in a substantially complete transformation to Zr 3  Al. Composition on either side of 9 wt% Al will, of course, show varying amounts of αZr or Zr 2  Al depending upon which side of 9 wt% Al they lie. For reasons which will be discussed in more detail hereinafter, the αZr must be either absent or, if present, distributed in the form of small isolated pools within a Zr 3  Al matrix if good corrosion resistance is to be maintained. In order for the Zr 3  Al matrix structure to be achieved, we have found it important to control the particle size of the Zr 2  Al phase before transformation to avoid coarse dispersed particles of Zr 2  Al. After transformation the αZr content must be below 15-20 vol. %, otherwise the corrosion kinetics of the alloy will be determined by the rapidly corroding αZr phase containing Al in solid solution and not by the slowly corroding Zr 3  Al phase. For good corrosion resistance, the binary Zr alloys of this invention should contain at least 7.5 wt% of aluminum. Similarly, but for reasons related to the ductility of the alloys described hereinafter, the Zr 2  Al content must be controlled and the binary Zr-Al alloys of the present invention should contain less than about 9.5 wt% aluminum. 
     EXAMPLE 1 
     Preparation and Examination of Cast Structures of Alloys of the Present Invention 
     A series of binary Zr- alloys containing from 6.5 wt% Al to about 9.5 wt% Al were prepared by melting together reactor grade zirconium sponge and Al wire (99.6 purity) in vacuum (10 -5  torr) on a water cooled copper block using an arc melting technique with a non-consumable thoriated tungsten electrode. The alloys were remelted three times and then cast sample buttons weighing approximately 150 grams each were produced. 
     The cast structures were examined by metallographic, X-ray and electron microprobe techniques, and revealed two phases (a) a transformed β-zirconium phase containing Al in solid solution and (b) an intermetallic compound Zr 2  Al. Another intermetallic phase Zr 5  Al 3  was also present in the form of a core structure within some of the large Zr 2  Al regions. In some castings the main phases were distributed as in a eutectic mixture and in others as Zr 2  Al regions within a matrix of Zr-Al solid solution. Often both microstructures were present in a single sample. Large ingots (up to 500 lbs.) containing 7.5, 8.6 and 9.0 wt% Al were also produced by arc melting. The structure was similar to that of the small castings: the main difference was the larger &#34;diameter&#34; of the Zr 2  Al particles, see Table 1. 
     
                       Table 1                                                     
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                       Zr.sub.2 Al width                                  
                       seen on                                            
                       Metallurgical                                      
                                   Zr.sub.2 Al                            
Ingot size  Composition                                                   
                       Sections    Content                                
Dia. (cm)                                                                 
       Wt. (kg) (wt.% Al)  (μm)   (vol.%)                              
______________________________________                                    
1.3    0.15     8.6 ± 0.1                                              
                           1-1.5     55                                   
15     50       8.6 ± 0.1                                              
                           3-4       55                                   
23     225      8.6 ± 0.1                                              
                           8-10      55                                   
______________________________________                                    
 Effect of ingot size on the size of Zr.sub.2 Al particles in Zr 8.6 wt.% 
 Al ingots prepared by arc-melting reactor grade sponges zirconium and    
 commercial purity aluminum.                                              
 
    
     EXAMPLE 2 
     Heat Treatment to Effect Transformation; Effect of Condition of Zr 2  Al phase on Transformation 
     150 gram samples of cast alloys produced in Example 1 were annealed under vacuum at 1200° C in the β+Zr 2  Al region for 12 hours and then annealed at 950° C under vacuum for times up to 160 hours. The samples were then examined by X-ray, electron microprobe and metallographic techniques and it was found the transformed structures consisted mainly of coarse particles of Zr 2  Al within a matrix of Zr-Al solid solution; a small amount of Zr 3  Al was present in the form of a narrow rim around the Zr 2  Al particles, thus confirming the peritectoid formation of Zr 3  Al. The corrosion resistance (e.g. in moist air at 300° C) of these samples was poor, illustrating the desirability of producing a continuous Zr 3  Al phase in the alloys. However, when alloys are first heat treated in the βZr solid solution region at temperatures well above 1200° C, depending on composition, and are then heat treated below 975° C, the required Zr 3  Al matrix structure is produced quickly and these alloys have good corrosion properties. This example also serves to show that the heat treatment technique to be employed is critical and cannot be merely deduced from the phase diagram of the system. 
     EXAMPLE 3 
     Transformation to Zr 3  Al Matrix Structure. 
     Samples of cast alloys produced as in Example 1 were annealed at temperatures in the range 700° - 975° C, preferably at about 900° C for times up to 380 hours, usually about 100 hours or less being satisfactory. The required annealing time depended upon the temperature, the coarseness of the as-cast structure and the desired grain size of the final product. All annealing was effected in vacuum to avoid disintegration of the castings due to rapid oxidation at temperatures above 700° C. Subsequent examination by X-ray, electron microprobe and metallographic techniques revealed that the transformed structures of the alloys consisted essentially of a Zr 3  Al matrix plus very small amounts of residual Zr 5  Al 3  ; αZr and Zr 2  Al were also present, the amounts depending on the exact composition of the alloy. FIGS. 2a-2h illustrate the microstructures of transformed alloys, at a magnification of X500, assaying: 
     
         ______________________________________                                    
a) 6.5 wt % Al  b) 7.0 wt % Al                                            
c) 8.0 wt % Al  d) 8.8 wt % Al                                            
e) 9.0 wt % Al  f) 9.3 wt % Al                                            
g) 9.4 wt % Al  h) 9.5 wt % Al balance Zr                                 
______________________________________                                    
 
    
     respectively. The alloys of FIGS. 2a-2d were transformed at 900° C for 50 hours. hot worked at about 1050° C and then annealed at 900° C for about 1 to 2 hours; the alloys of FIGS. 2e-2h were transformed at 900° C for 168 hours, hot worked at about 1050° C and then annealed at 900° C for about 2 hours. 
     Table 2 below summarizes the alloy composition and phase content of these particular alloys. The amount of each phase present in any composition is determined, to some extent, by the time and temperature of heat treatment. For example some 8.8 wt% Al alloys have been prepared which contains as little as 10% Zr 2  Al, and some 8.95 wt% Al alloys have recently been prepared which contain less than 1% αZr and no Zr 2  Al. 
     
                       TABLE 2                                                     
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Alloy Composition and Phase Content                                       
Alloys Composition                                                        
             Phase Content (%)                                            
(wt. % Al)   Zr.sub.3 Al                                                  
                      α(Zr)                                         
                               Zr.sub.2 Al                                
                                      Zr.sub.5 Al.sub.3                   
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6.5          65       35       --     --                                  
7.0          80       20       --     --                                  
8.0          80       10       10     --                                  
8.8          65       12       23     --                                  
9.0          65        8       27     --                                  
9.3          55       16       29     --                                  
9.4          45       10       44     0.4                                 
9.5          45       10       45     --                                  
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     In FIG. 2a, illustrating an alloy containing 6.5 wt% Al, αZr is present as an interconnected network within the Zr 3  Al matrix, whereas in FIGS. 2b-2h illustrative of alloys with higher Al contents, αZr is only present in the form of small, isolated pools within the Zr 3  Al matrix. Metallographic examination of oxidized alloys containing 6.5 wt% Al revealed network corrosion of the αZr phase. For good corrosion resistance, therefore, it is clear that the αZr content must be kept below 15-20 vol. % so that the αZr regions are isolated. This effectively limits the Al content to be greater than about 7.5 wt %. 
     Samples of Zr alloys containing 8.8 wt% Al were heat soaked at 1285° C for 21 hours so as to produce a microstructure containing βZr and Zr 5  Al 3 , two of the phases present in the cast alloys. These samples were then transformed into Zr 3  Al at temperatures between 825° C and 925° C. The results of these experiments showed that a large fraction of the matrix transformed to Zr 3  Al in times less than 10 hours; also the results indicated that the rate of transformation at 875° C was higher than that at 925° C and at 825° C. 
     EXAMPLE 4 
     Optimization of the Transformation to Zr 3  Al 
     Using the alloys listed in Table 1, detailed studies have been made of the peritectoid transformation kinetics as a function of transformation temperature, particle size and impurity content. The results revealed the following: 
     (i) In ingots containing small Zr 2  Al particles, i.e. particles of diameter below ≃ 4 μm, the transformation velocity reached a maximum at about 887° C. This occurred because the transformation velocity becomes nucleation controlled the finer are the Zr 2  Al particles. In ingots containing large Zr 2  Al particles, i.e. particles exceeding 8 to 10μm in diameter, the velocity increased with increasing temperature, so that the transformation at 925° C was faster than that at about 887° C. This occurred because with larger particles the transformation velocity is controlled by long range atomic diffusion. 
     (ii) In 50 kg ingots containing ˜4 μm diameter Zr 2  Al particles (i.e. ingots of a size suitable for commercial pressuretube fabrication for thermal-nuclear power reactors of the CANDU-type), the transformation velocity was retarded and the amount of Zr 3  Al produced in an alloy of given aluminum content was reduced through the additions of Nitrogen. For instance, 1600 ppM N (by weight) in a Zr-8.6 wt% Al alloy lowered the equilibrium peritectoid temperature to the extent that the initial transformation velocity at 875° C was reduced by a factor of 4 and the equilibrium amount of Zr 3  Al was reduced from about 90% to about 60%. These observations show that nitrogen levels must be kept small to allow the transformation to proceed to completion in reasonable times. 
     (iii) Annealing longer than necessary to effect the transformation is to be avoided because this has been observed to result in larger Zr 3  Al grains and, hence, lower yield strength. For an alloy containing 4 μm diameter Zr 2  Al particles, 8 to 16 hours at about 800° - 900° C preferably 887° C is the optimum time and temperature. 
     EXAMPLE 5 
     Working of Alloys by Rolling 
     Cast alloys produced in Example 1 were hot rolled at temperatures up to about 900° C. Cracks formed even after only small reductions in thickness. 
     Alloys, produced as in Example 1 and heat treated as in Example 3 were heat soaked at 600° C to 975° C for a few minutes and were then rolled at temperatures in the range 600° - 975° C. It was found that cracking may occur in irregularly shaped specimens and if the initial reduction per pass is too large. To prevent cracking on rolling, therefore, it is preferred to use rectangular shape and to keep the initial reductions below about 1-2%. 
     EXAMPLE 6 
     Measurement of Tensile Strength of Alloys of the Invention. 
     Alloys produced as described in Example 1 and transformed as described in Example 3 were hot worked as described in Example 5 but at higher temperatures i.e. above 1000° C. A final transformation anneal in vacuum at 900° C for 45 minutes, was carried out to give the desired structure. The microstructures are shown in FIGS. 2a-2h. 
     Transmission electron microscopy revealed that in this condition the Zr 3  Al phase was well ordered and the grain size was rather small (1-2 μm in diameter). Samples were then tensile tested at temperatures from 20° C to 600° C. The results are summarized in Table 3a overleaf. 
     Other alloys were also transformed as in Example 3 but for 120 hours at 900° C and then tensile tested at temperatures from 20° C to 700° C, without intermediate hot working. The tensile properties of these alloys are shown in Table 3b overleaf. The yield points of alloys with compositions between 8.5 and 9.5 wt% Al are somewhat lower than those of alloys which have been hot worked because their grain size was larger due to the longer transformation anneal. 
     These results indicate that the mechanical properties of the material can be controlled within certain limits by control of the temperature and time of the transformation heat treatment. The transformation heat treatment should be performed in the range about 500°-975° C. 
     
                       TABLE 3a                                                    
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 Flow Parameters at 20° C, at ˜300° C, at             
˜450° C and at                                               
˜600° C for Several Zr.sub.3 Al-Based Ordered Alloys         
Transformed 45 Minutes at 900° C                                   
(strain rates - 4.5 × 10.sup.-4 /sec)                               
               Yield Stress                                               
                           Ultimate                                       
       Test    0.2% at     Tensile Total                                  
Alloy  Temp.   Strain Offset                                              
                           Stress  Elongation                             
(wt.% Al                                                                  
       (° C)                                                       
               (psi)       (psi)   (%)                                    
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6.5     20     112,000     148,000 26.7                                   
6.5     &#34;      114,000     --      --                                     
8.8     &#34;      116,000     132,000 4.0                                    
9.0     &#34;      109,000     111,000 &lt; .3                                   
9.3     &#34;      135,000     133,000 1.2                                    
9.4     &#34;      122,000     125,000 &lt; .3                                   
9.5     &#34;      126,000     131,000 &lt; .3                                   
6.5    350     100,000     124,000 30.6                                   
7.0    300      86,000     150,000 29.2                                   
7.0    300      88,000     149,000 29.2                                   
8.0    300     106,000     160,000 29.2                                   
8.0    300     110,000     165,000 26.2                                   
8.8    310     108,000     145,000 19.4                                   
9.0    320     103,000     133,000 10.0                                   
9.3    335     116,000     127,000 9.1                                    
9.5    305     114,000     132,000 10.4                                   
6.5    465      84.000     112,000 26.0                                   
8.8    465     106,000     118,000 14.7                                   
9.3    460     105,000     113,000 9.2                                    
9.4    455     103,000     117,000 8.5                                    
9.5    450     117,000     132,000 10.0                                   
6.5    600      48,000      70,000 8.0                                    
8.8    605      90,000      94,000 21.7                                   
9.0    600      85.000      93,000 13.3                                   
9.3    625      81,000      89,000 5.0                                    
9.4    605      87,000     100,000 9.0                                    
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                       TABLE 3b                                                    
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 Flow Parameters between 20° C and 700° C for Several       
Zr.sub.3 Al                                                               
Based Ordered Alloys Transformed 120 Hours at 900° C               
(Strain Rate = 1.7×10.sup.-4 /sec.)                                 
               Yield Stress                                               
                           Ultimate                                       
       Test    0.2% at     Tensile Total                                  
Alloy  Temp.   Strain Offset                                              
                           Stress  Elongation                             
(wt. %Al                                                                  
       (° C)                                                       
               (psi)       (psi)   (%)                                    
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6.9     20     105,000     149,000 10                                     
&#34;      180     97,000      150,000 25                                     
&#34;      300     88,000      132,000 29                                     
&#34;      400     89,000      127,000 31                                     
&#34;      500     73,000      102,000 34                                     
&#34;      600     65,000      --      &gt;100                                   
&#34;      700     31,000       39,000 28                                     
7.8     20     92,000      124,000 5                                      
&#34;      110     92,000      130,900 9                                      
&#34;      200     90,000      171,000 33                                     
&#34;      300     96,000      162,000 38                                     
&#34;      400     93,000      144,000 40                                     
&#34;      500     88,000      118,000 50                                     
&#34;      600     72,000      75,000  31                                     
&#34;      700     48,000      --      &gt;100                                   
8.5    400     60,000      112,000 25                                     
&#34;      600     63,000       86,000 50                                     
9.0    400     63,000      148,000 23                                     
&#34;      600     63,000       89,000 42                                     
9.5    400     66,000        99,000                                       
                                   13                                     
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     Compared with conventional solution and precipation strengthened Zr alloys used commercially, as shown in Table 4, the Zr 3  Al based alloys of the present invention generally show higher ultimate tensile strengths. 
     
                       TABLE 4                                                     
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(From P.A. Ross-Ross &amp; C.E.L. Hunt                                        
Journal of Nuclear Materials 26                                           
1968, 2-17)                                                               
                    Yield                                                 
        Stress                                                            
                    at 0.2%  Ultimate                                     
                    Strain   Tensile Total                                
                    Offset   Stress  Elonga-                              
                    (psi)    (psi)   tion (%)                             
Alloy   Condition   at 300° C                                      
                             at 300° C                             
                                     at 300° C                     
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Zircaloy 2                                                                
        Cold                                                              
        Worked (18%)                                                      
                    45,000   52,000  26                                   
Zr-2.5Nb                                                                  
        Worked (22%)                                                      
                    53,000   76,000  15                                   
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     For instance the highest ultimate tensile stress (U.T.S.) at 300° C for Zr 3  Al based alloys is &gt;160,000 psi, while the highest U.T.S. at 300° C for commercial Zr alloys is &gt;150,000 psi. Furthermore the Zr 3  Al based alloys retain their strength to higher temperatures. 
     EXAMPLE 7 
     Ductility of Zr 3  Al Based Alloys. 
     Generally, the Zr 3  Al based alloys produced and transformed as described above in Examples 1, 3 and 5 show significant ductility. However, the hyperstoichiometric 9.0-9.5 wt% Al alloys of the structures described here and tested at a strain rate of 4.5 × 10 -4  per sec, become ductile only above about 250° C ± 50° C, and even then tend to show strain to fracture less than that of the hypostoichiometric alloys. FIG. 3 shows the brittle to ductile transition in these hyperstoichiometric alloys. It is believed this transition is due to the presence of a second intermetallic phase Zr 2  Al, distributed throughout the Zr 3  Al matrix. As the amount of Zr 2  Al increases, for instance from about 23 vol. % in the 8.8 wt% Al alloy to about 45 vol. % in the 9.5 wt% Al alloy, the room temperature ductility decreases from about 4% to 0.3%. Thus the presence of Zr 2  Al limits the Al content in the alloys of the present invention to less than about 9.5 wt% for good ductility. It can be seen by the comparison of the ductility data in Tables 3a and 3b that the alloys with longer transformation times in general display greater elongations to failure than similar alloys which have been subjected to only a short heat treatment. 
     EXAMPLE 8 
     Creep strength at Elevated Temperatures of Alloys of the Present Invention 
     In-laboratory tensile creep experiments on a 9.5 wt% Al alloy (prepared as described in Examples 3 and 5) were performed over a range of temperatures from 300° C to 500° C and under a range of tensile stresses from 20,000 psi to 75,000 psi. After a period of primary creep, the percent elongation versus time relationship became reasonably linear. The creep rates were then computed from the slopes of the linear segments of the strain-elongation curves. Table 5a summarizes the results. 
     Creep tests have also been performed on other alloys, transformed as in Example 3 by a single stage heat treatment at 900° C for 120 hrs. The results are reported in Table 5b. Of particular interest are the data determined on the 8.5 wt% alloy at 60,000 to 40,000 psi and 400° C. These data are compared with the 400° C results for the 9.5 wt% Al alloy in FIG. 4. It can be seen that below 43,000 psi the alloy with the longer heat treatment has superior creep properties, while above this stress the merits of the alloys are reversed. This again indicates the importance of the degree of annealing of the alloys in determining their mechanical properties, although as the alloys do have different compositions this could also be a contributing factor. 
     At 300° C, the creep rate at a given stress for the Zr 3  Al-based alloy is lower by a factor of 2 or 3 than that for a Zr-2.5 wt% Nb alloy and for Zircaloy-2, two materials currently used for structural components in &#34;CANDU&#34; thermal nuclear reactors. At higher temperatures (i.e., 400° C to 500° C), the results indicate that the creep rate at a given stress for the Zr 3  Al-based alloys is lower by a factor of 10 or more. 
     
                       Table 5a                                                    
______________________________________                                    
Tensile Creep Rates for a Hot                                             
Worked Zr-9.5 wt.% Al Alloy                                               
Test Temp.  Tensile Stress Creep Rate                                     
(° C)                                                              
            (psi)          (hour.sup.-1)                                  
______________________________________                                    
300         30,000         1.0 × 10.sup.-7                          
            60,000         1.0 × 10.sup.-6                          
400         30,000         7.7 × 10.sup.-7                          
            45,000         1.1 × 10.sup.-6                          
            60,000         3.3 × 10.sup.-6                          
            75,000         1.3 × 10.sup.-5                          
500         30,000         8.5 × 10.sup.-6                          
            45,000         4.2 × 10.sup.-5                          
            60,000         6.0 × 10.sup.-5                          
            30,000         4.3 × 10.sup.-6                          
            20,000         2.1 × 10.sup.-6                          
______________________________________                                    
 
    
     
                       Table 5b                                                    
______________________________________                                    
Tensile Creep Rates for Fully                                             
Annealed Zr.sub.3 Al-Based Alloys                                         
Composition,                                                              
           Stress,   Temperature,                                         
                                 Creep Rate                               
wt.% Al    psi       ° C  hr.sup.-1                                
______________________________________                                    
Zr-6.8% Al 10,000    650         1.6 × 10.sup.-3                    
Zr-6.8% Al 10,000    600         1.2 × 10.sup.-4                    
Zr-7.8% Al 10,000    650         5.9 × 10.sup.-4                    
Zr-7.8% Al 10,000    600         1.2 × 10.sup.-4                    
Zr-7.8% Al 10,000    550         1.4 × 10.sup.-5                    
Zr-7.8% Al 15,000    500         4.0 × 10.sup.-6                    
Zr-8.5% Al 60,000    400         1.8 × 10.sup.-4                    
Zr-8.5% Al 50,000    400         4.8 × 10.sup.-6                    
Zr-8.5% Al 40,000    400         5.8 × 10.sup.-7                    
Zr-8.8% Al 10,000    640         9.3 × 10.sup.-6                    
Zr-9.1% Al 10,000    640         1.0 × 10.sup.-5                    
Zr-9.3% Al 10,000    640         1.4 × 10.sup.-5                    
Zr-2.5% Nb 20,000    450           5 × 10.sup.-5                    
Zircaloy-2 20,000    450           8 × 10.sup.-5                    
______________________________________                                    
 
    
     EXAMPLE 9 
     Creep Strength in an Irradiation Field. 
     To obtain a relative measure of the creep strength of Zr 3  Al-based alloys in a field of fast neutrons, four specimens of the 9.5 wt% Al alloy, prepared as in Examples 3 and 5, were subjected to a bent-beam type stress-relaxation test in a thermal nuclear reactor. The test period was 1543 hours; the test conditions were 295° C ± 5° C water environment, ≃ 33,500 psi maximum stress, and a fast flux (E &gt; 1 Mev) of 1.6 × 10 13  neutrons/cm 2  /sec. The unrelaxed stress ratios σ/σ o , were found to be 0.814 and 0.503 for annealed and for hot-worked specimens, respectively, and the reproducibility was very good. This again indicates the importance of the degree of annealing in controlling the properties of the alloys. 
     To obtain some very short-term data, experiments under similar conditions of temperature and stress were performed out-reactor in an autoclave. As is the case for conventional zirconium-based alloys, it is assumed that very short-term auto-clave experiments give a reasonable indication of the early stages of the in-reactor stress relaxation behaviour of the Zr 3  Al-based alloys. From these experiments, the ratios σ/σ o  were found to be 0.945, 0.972 and 0.905 after test periods of 30 hours, 130 hours, and 500 hours, respectively. 
     In keeping with common practice of analyzing stress-relaxation data, the results from the in-reactor and from the out-reactor experiments were plotted in terms of the logarithm of the unrelaxed stress ratio, ln σ/σ o , versus the relaxation time. From the slope of this plot, the stress-relaxation parameter A·E (where A is a &#34;material constant&#34; which takes into account the conditions under which the experiments were performed, and E is Young&#39;s modulus which was found to be ˜18.3 × 10 6  psi (example 10 overleaf)) was found to be less than 1.0 × 10 -4  per hour for the annealed material. 
     Table 6 compares this result with that from experiments by D. E. Fraser, P. A. Ross-Ross and A. R. Causey (J. Nuclear Materials, Vol. 46 1973 in press) on Zr-2.5 wt.% Nb and on Zircaloy-2, two alloys presently used for structural components in `CANDU` thermal nuclear reactors. (An adjustment is made for the 25% higher flux in the Zr-2.5 wt.% Nb and in the Zircaloy-2 alloys.) Clearly, the &#34;material constant&#34; A for the present alloy in the annealed condition is lower than that for the other alloys. This result indicates that the in-reactor creep rate for the Zr 3  Al-based alloy is lower than that for the Zr-2.5 wt.% Nb and the Zircaloy-2 alloys. 
     
                       Table 6                                                     
______________________________________                                    
Values of the Stress-Relaxation Parameters A·E and               
A for an Annealed Zr-9.5 wt.% Al Alloy and for                            
a Zr-2.5 wt.% Nb Alloy and for Zircaloy-2 at                              
295 ± 5° C and Under a Neutron Flux (E &gt; 1 Mev)                 
of 1.6 × 10.sup.13 n/cm.sup.2 /sec                                  
           Test Period                                                    
                     A·E × 10.sup.4                        
                                A × 10.sup.12                       
Material   (hours)   (hours.sup.-1)                                       
                                (psi.sup.-1 hour.sup.-1)                  
______________________________________                                    
Zr-9.5 wt.% Al                                                            
           1543      ≦1.0                                          
                                ≦6.6                               
Zr-2.5 wt.% Nb                                                            
           8200      1.3        12                                        
Zircaloy-2 8200      2.0        19                                        
______________________________________                                    
 
    
     EXAMPLE 10 
     Elastic Constants (Young&#39;s Modulus) 
     Specimens of 8.8, 9.0, 9.2 and 9.5 wt% Al alloys, prepared as in Examples 3 and 5, were compressed under a static load at room temperature. The corresponding reductions in specimen length (Δl) were monitored using calibrated strain gauges attached to the specimens. From a knowledge of the initial lengths of the specimens and Δl, the strains were computed; and from a knowledge of the static loads and the cross-sectioned areas of the specimens, the applied stresses were computed. Young&#39;s moduli were then computed by dividing the applied stresses by the measured strains, and were found to be ˜18.3 × 10 6  psi. No significant effect of composition was apparent. This compares with a value of ˜13 × 10 6  psi at 20° C for conventionally strengthened Zr alloys. 
     EXAMPLE 11 
     Corrosion Resistance. 
     Zr 3  Al-based alloys, cast, transformed in the single-stage process, as described in Example 3, and worked as in Example 5 were subsequently annealed in vacuum at 900° C for 45 min. Corrosion coupons were then prepared and tests were carried out in moist air. Zircaloy-2 specimens were included for comparison. 
     Table 7a summarizes the results after 30 days at 300° C in moist air. Clearly, the near-stoichiometric compositions (i.e. ˜8.0 - ˜9.5 wt.% Al) have considerably better corrosion resistance than alloys of lower Al content. Also, the results suggest that alloys closer to the stoichiometric composition should have corrosion resistance comparable to that for Zircaloy-2, at least in the present environment. 
     
                       Table 7a                                                    
______________________________________                                    
Oxidation Parameters at 300° C (Moist Air) for                     
Several Zr.sub.3 Al-Based Alloys                                          
                    Total wt. gain/                                       
         Vol. %     unit area   Rate of wt. gain/                         
Alloy    Zr-Al      after 30 days                                         
                                unit area                                 
(wt.% Al)                                                                 
         Solid Soln.                                                      
                    (mg/dm.sup.2)                                         
                                (mg/dm.sup.2 -day)                        
______________________________________                                    
6.5      35         510         20.4                                      
7.0      ˜10  19          0.34                                      
8.0      ˜9   5           &lt; 0.1                                     
9.5      ˜9   11          0.21                                      
Zircaloy-2                                                                
         --         8.5         0.13                                      
(Batch Bh)                                                                
______________________________________                                    
 
    
     Table 7b summarizes the results after 30 days at 400° C in 1 atm. steam, in comparison to a commercial Zircaloy-2 alloy and to a dilute Zr-Al alloy which is based on the α Zr phase. 
     
                       Table 7b                                                    
______________________________________                                    
                           Rate of wt. gain/                              
Alloy    wt. gain after 30 days                                           
                           unit area                                      
(wt.% Al)                                                                 
         (mg/dm.sup.2)     (mg/dm.sup.2 -day)                             
______________________________________                                    
Zr-8.0 Al                                                                 
         29.6              0.55                                           
Zircaloy-2                                                                
         30.0              0.55                                           
(Bh-Batch)                                                                
Zr-1.0 Al                                                                 
         - alloy disintegrated                                            
                           600                                            
         after two days                                                   
         exposure                                                         
______________________________________                                    
 
    
     EXAMPLE 12 
     Short Term Corrosion Resistance in Pressurized Water. 
     The alloys given in example 11 were also subjected to some short term corrosion tests in pressurized water (˜1300 psi) at 300° C. After 49 days, alloys near 8.0 wt.% Al continued to show interference colors indicating a very thin oxide film, while the Zircaloy-2 control specimens appeared black indicating a thicker oxide film. This again illustrates the considerable improvement to be realized in the corrosion-resistance of the Zr-Al system by designing alloys based on the Zr 3  Al compound. 
     EXAMPLE 13 
     Corrosion Resistance in an Irradiation Field. 
     A Zr alloy containing 9.5 wt.% Al was subjected to a bent-beam type stress-relaxation experiment in a thermal nuclear reactor (see Example 9). The test environment was pressurized water (˜1300 psi) at 295° ± 5° C and the test period was 1543 hours; the neutron flux (E &gt; 1 MeV) was 1.6 × 10 13  neutrons/cm 2  /sec. On completion of the test, it was found that the oxide films which formed during the exposure could not be loosened on vigorous scraping against metal tweezers, indicating considerable film adherence to the underlaying Zr 3  Al-based substrate. Subsequent metallographic examination revealed that the film thickness varied from ˜1 micron to ˜8 microns. 
     These observations again illustrate the improvement to be gained in the corrosion-resistance of Zr-Al alloys by designing alloys based on the Zr 3  Al intermetallic compound. 
     EXAMPLE 14 
     Resistance of Alloys of the Present Invention to Corrosion by Carbon Dioxide 
     Zr 8.7 wt% Al and Zr-9.4 wt% Al alloys of the present invention, prepared as in Example 3, were exposed to flowing commercial purity carbon dioxide for prolonged periods at a temperature of 400° C. Carbon dioxide is used as a coolant in some reactors and as the surrounding medium for the coolant channels in others. For these reasons resistance to corrosion by CO 2  is an important property of Zr alloys for nuclear reactor applications. 
     In addition to the Zr 3  Al-based alloys, samples of Zr-2.5 wt% Nb and zircaloy-2 were exposed in the same tests under identical conditions. The gain in weight for each alloy, which is a measure of the extent of corrosion, is recorded for various times of exposure in Table 8 below. 
     The data show that the alloys have a corrosion resistance considerably better than Zr-2.5 wt% Nb, and have corrosion rates comparable to Zircaloy-2. 
     
                       Table 8                                                     
______________________________________                                    
The Corrosion of Zr.sub.3 Al-Based Alloys in CO.sub.2 at 400° C    
Composition                                                               
         Weight Gain, mg/dm.sup.2, After                                  
wt%      5 days  10 Days  20 Days                                         
                                 40 Days                                  
                                        60 Days                           
______________________________________                                    
Zr-8.7% Al                                                                
          6      11       18     24     30                                
Zr-9.4% Al                                                                
          9      14       19     26     34                                
Zr-2.5% Nb                                                                
         18      32       52     77     95                                
Zircaloy-2                                                                
         11      17       23     27     33                                
______________________________________                                    
 
    
     The major impurities in the CO 2  are: O 2  = 100 to 170 ppm, H 2  O = 20 ppm, H 2  = &lt;20 to 30 ppm. 
     EXAMPLE 15 
     Hardness of Alloys of the Present Invention. 
     The damage to fuel cans and coolant channels by wear due to vibrations in nuclear reactors is of considerable concern. In general the resistance of a material to wear may be approximately related to the hardness of the material. Alloys which are based on Zr 3  Al have considerably higher hardness, and consequently expected resistance to wear, than the conventional zirconium alloys, Zr-2.5 wt% Nb and Zircaloy-2. The Diamond Pyramid Hardness of alloys of a range of compositions, prepared as in Example 3, has been measured at various temperatures in an atmosphere of purified argon. The measurements are recorded in Table 
     The same measurements were performed on samples of Zr-2.5 wt% Nb and Zircaloy-2, and are included for comparison. It is apparent that all of the alloys based on Zr 3  Al have considerably higher hardness values than two conventional alloys, and therefore are an improvement over existing alloys in this respect. 
     
                       Table 9                                                     
______________________________________                                    
The Hardness of Alloys Based on Zr.sub.3 Al                               
Composition          Diamond Pyramid Hardness Kg/mm.sup.2                 
wt %     Heat-Treatment                                                   
                     100° C                                        
                             300° C                                
                                   500° C                          
                                         700° C                    
______________________________________                                    
Zr-6.8%Al                                                                 
         380 hrs at 900° C                                         
                     260     191   132    64                              
Zr-7.8%Al                                                                 
         380 hrs at 900° C                                         
                     258     201   149   104                              
Zr-8.6%Al                                                                 
         380 hrs at 900° C                                         
                     307     232   170   113                              
Zr-8.7%Al                                                                 
         380 hrs at 900° C                                         
                     391     317   224   100                              
Zr-8.9%Al                                                                 
         380 hrs at 900° C                                         
                     380     310   215    72                              
Zr-9.1%Al                                                                 
         380 hrs at 900° C                                         
                     402     332   228   100                              
Zr-9.2%Al                                                                 
         380 hrs at 900° C                                         
                     428     323   210    65                              
Zr-9.5%Al                                                                 
         380 hrs at 900° C                                         
                     356     273   203   106                              
Zr-9.7%Al                                                                 
         380 hrs at 900° C                                         
                     292     201   150    84                              
Zr-2.5%Nb                                                                 
          1 hr at 500° C                                           
                     186      92    58   --                               
Zircaloy-2                                                                
          1 hr at 500° C                                           
                     160     100    55   --                               
______________________________________                                    
 
    
     Further miscellaneous properties will be discussed with reference to the drawings. 
     FIG. 5 shows the effects of temperature on yield stress (σ 0 .2%) of the hot worked and annealed alloys. Because of the proximity of the points separate curves were drawn only through the 6.5, the 9.5 and the collective 8.8 - 9.4 wt% Al points. For all compositions tested σ 0 .2% decreases with increasing temperature. Two regions, however, are apparent, a low temperature region from 20° C to ˜450° C in which the temperature effect is rather small, and a high temperature region from ˜450° C to 600° C in which the effect is more pronounced. For instance σ 0 .2% (6.5 wt% Al) decreases by ˜20% over the first region, and by a further 50% over the second. Similarly, σ 0 .2% (8.8 and 9.3 wt% Al) decreases by 10-20% over the first region, and by an equivalent amount over the second. However, the data in Table 3b shows that 8.5 and  9.0 wt% Al alloys in the fully annealed condition have similar values of σ 0 .2% at 400° and 600° C. 
     FIG. 6 shows the effects of composition on σ 0 .2% for the hot worked and annealed alloys. At all test temperatures σ 0 .2% of the hot worked alloys increases with increasing Al content. The effect, however, is rather small. For example, in the low temperature region σ 0 .2% increases by ˜20% over the composition range tested, and in the high temperature range, by ˜30%. However, at 400° C the fully annealed alloys was found to have a drop in σ 0 .2% at compositions between 8.5 and 9.5 wt% Al. 
     FIG. 7 shows the effects of temperature on σ UTS  for the hot worked alloys. Again two regions are apparent, analogous to the yield stress behaviour. The variation within each region, however, appears to differ for the hypostoichiometric and the hyperstoichiometric alloys. In the low temperature region (i.e. ≲ 450° C), σ UTS  (6.5 wt% Al) decreases with increasing temperature by ˜25%, and in the second region by a further ˜50%. For the hyperstoichiometric alloys on the other hand, σ UTS  appears to be relatively independent of temperature over the first region, but decreases by ˜30% over the second region. Also, σ UTS  for these alloys appears to be independent of Al content, being generally within the range 125 - 135,000 psi over the first region. 
     While the effect of temperatures on the 7.0 and 8.0 wt% Al alloys is not defined, the results at 300° C clearly indicate that σ UTS  is considerably higher in these cases than it is for both the 6.5 wt% Al alloy and the hyperstoichiometric alloys. 
     EXAMPLE 16 
     Hot Working of Alloys 
     Cast alloys produced in Example 1 were rolled at temperatures up to 1100° C. At 500° C, cracks formed after ˜5% reduction in thickness, but the alloys could be reduced in thickness by about 50% (10% per pass) at which point failure occurred suddenly. At 700° C, cracks again formed during the first few percent reduction. In this case, the alloys were reduced in thickness by more than 50% without disintegrating. Further reductions were not attempted. At temperatures above 1000° C, however, no cracks formed and the cast alloys rolled very easily. Reductions in area of at leat 25% per pass at strain rates of at least 40 sec -1  were achieved with no difficulty. Edge cracking was not detected. Following working, metallographic and X-ray examinations revealed that the structure still consisted of Zr(Al) and Zr 2  Al mainly. This transformed to Zr 3  Al by annealing at 875° C, for less than 24 hours. 
     In a second series of experiments, the cast alloys were transformed as in Example 3 to produce a Zr 3  Al matrix, and then rolled. It was observed that the transformed alloy cracked during rolling at temperatures below about 950° C. Above about 1000° C however, the alloys could be worked. Reductions in thickness of 10% per pass were easily achieved and strip material 0.080 inch thick was produced from slabs initially 0.5 inch thick; i.e. reductions of 85% were possible without reaching the malleability limit. 
     All working was carried out in a protective enviroment of argon to minimize metal loss due to oxidation. 
     In a further series of experiments, samples from cast zirconium aluminum alloy ingots weighing 50 kg containing 7.6 wt%, 8.6 wt% and 9.0 wt% Al, were rolled following heat soaking, in the BZr-Zr 2  Al two phase region at temperatures of approximately 502° C, 702° C, 902° C, 1002° C, 1052° C and 1102° C. The two phase β-Zr+Zr 2  Al ingots cracked after less than a few percent reduction in thickness when heated to about 502° C, 702° C and 902° C. However, when heat soaked at about 1000° C, 1050° C and 1100° C the material rolled easily. At about 1050° C, for example, thickness was reduced by more than 90%, without edge cracking, indicating that the limit of malleability had not been reached. Following rolling, the alloy samples which had been heat soaked at about 1000° C, 1050°  C and 1100° C were annealed at temperatures below about 992° C for a time sufficient to transform the alloys to the desired Zr 3  Al matrix. 
     EXAMPLE 17 
     Hot Working of Alloys by Extrusion 
     Zirconium-aluminum alloys, in the BZr-Zr 2  Al two phase region were extruded following heat soaking to form tubes. 
     Table 10 sets forth basic extrusion particulars, while Table 11 sets forth extrusion results. 
     
                                           TABLE 10                                
__________________________________________________________________________
SUMMARY OF MATERIALS AND EXPERIMENTAL CONDITIONS FOR EXTRUSION OF Zr-Al   
TUBES                                                                     
         Metallurgical                                                    
        Condition                                                         
        Ingot Material:    Experimental Conditions                        
        (=50% Zr.sub.2 Al parti-                                          
                   Tube Size                                              
                           Thickness                 Average              
                                                          Soak            
Alloy   cles of 3 to 4 μm dia.                                         
                      Dimen-                                              
                           of               Materi-                       
                                                 Extru-                   
                                                     Strain               
                                                          Temp.           
Zr.7.6 wt.% Al                                                            
        in transformed β-Zr                                          
                      sions                                               
                           cladding                                       
                                 Lubricant                                
                                       Tool als**                         
                                                 sion                     
                                                     Rate*                
                                                          (° C)    
(Type A &amp; B)                                                              
        matrix     Type                                                   
                      (cm) (cm)  Base**                                   
                                       Die  Mandrel                       
                                                 Ratio                    
                                                     (sec.sup.-1)         
1hr-                                                                      
__________________________________________________________________________
Zr.9.0 wt.% Al                                                            
        Ingot material:                                                   
                   A  1.87 I.D.                                           
                           0.09  Cu and pb                                
                                       Atlas                              
                                            Atlas                         
                                                 4.8:1                    
                                                     7    1182 or         
(Type A)                                                                  
        (=60% Zr.sub.2 Al parti-                                          
                      4.24 O.D.        Seneca.sup.®                   
                                            Spar-         1152            
                                            tan 7.sup.®-              
                                                 cles of 3 to 4 μm     
                                                 dia.       Graphite Atlas
                                                          .sup.® Atlas
                                                          .sup.®      
        in transformed β-Zr                                          
                   B  3.50 I.D.                                           
                           0.64                                           
        matrix).      6.97 O.D.                                           
                           (outer)     Red  Red   16:1                    
                                                     1    1152            
                           0.32        Indian.sup.®                   
                                            Indian.sup.®              
                           (inner)                                        
__________________________________________________________________________
 *The average strain rate is defined as the total strain divided by the   
 time required for a unit volume of material to flow through the die.     
 Billets A were extruded through a die in which the semi-angle decreased  
 with distance so that the strain rate was approximately constant. The    
 semi-angle of the die used for billet B was 45° which gave an     
 increasing strain rate during extrusion.                                 
 **Tools and lubricants were chosen on the basis of availability. While   
 adequate, they do not necessarily represent the best choice for high     
 temperature extrusion.                                                   
 
    
     
                       TABLE 11                                                    
______________________________________                                    
SUMMARY OF EXTRUSION RESULTS FOR Zr-Al TUBES                              
Extruded in β-Zr.sub.2 Al TWO PHASE REGION                           
                                           Extru-                         
                            Break-         sion                           
                            through        Con-                           
                      Pre-  Pres-  Steady  stant*                         
                      Heat  sure   State   (MN/                           
                      Temp. p      Pressue m.sup.2)                       
Tube Alloys   Billet  (° C)                                        
                            (MN/m.sup.2)                                  
                                   (MN/m.sup.2)                           
                                           k                              
______________________________________                                    
1    Zr, 7.6  A       1102  624    575     500                            
     wt.% Al                                                              
2    Zr, 7.6  B       1152  793    --      286                            
     wt.% Al                                                              
3    Zr, 9.0  A       1152  505    452     322                            
     wt.% Al                                                              
______________________________________                                    
 *k was computed from the expression p=kln R where R is the extrusion     
 ratio. It was assumed that the steel cladding had the same flow stress as
 the alloy.                                                               
 
    
     In each case the tube extruded without difficulty, was straight and of reasonably uniform wall thickness. 
     The miscrostructures of tubes 1 and 2 of Table 11 were examined optically following surface preparation using the attack polishing/color etching technique (J. R. F. Ambler, E. M. Schulson and G. P. Kiely, J. Nucl. Mat., 50 (1974) 107). Transverse sections of tubes 1 and 2 revealed a relatively uniform Zr 2  Al particle size, of approximately 3-4 μm in average diameter. This feature was also evident from longitudinal sections, which also showed the Zr 2  Al particles reoriented in the direction of extrusion. Further, it appears that plastic flow during extrusion occurred mainly within the β Zr matrix, the Zr 2  Al phase acting as an obstacle to flow. Possibly dynamic recovery and recrystallization of β zr are important softening processes. 
     Transformation, subsequent to extrusion, from the β Zr-Zr 2  Al two phase region to the Zr 3  Al matrix was essentially complete in about 4 hours at an annealing temperature of about 877° C, in alloys containing Zr 2  Al particles averaging 3-4 μm in diameter. 
     An important conclusion to be drawn from the Examples is that temperature is an extremely important variable in determining the workability of the zirconium alloys. Temperatures above about 1000° C are recommended in order to avoid cracking. Another important conclusion is that the alloys need not be transformed to Zr 3  Al before working. They can be worked in the as-cast condition (at the temperatures mentioned above) and then subsequently transformed to Zr 3  Al by annealing at temperatures below 992° C, and more preferably below 975° C. 
     The principle difficulty experienced with working, in the case of either rolling or extruding, arises through excessive heat loss before or during working. Steps which can be taken to avoid undesirable alloy chilling include the provision of heat shields, heat soaking at somewhat higher temperatures than the subsequent working temperature - but of course below the alloy melting temperature, by preheating of working tools, and the like. 
     It will be appreciated that, while this specification is directed primarily to binary Zr-Al alloys, one or more other alloying elements may be introduced into the alloys provided always that the essential Zr 3  Al structure is maintained. For example, one or more of the elements, magnesium, tin, chromium, iron, carbon, silicon, yttrium, niobium, molybdenum and beryllium in amounts up to about 3 wt% would be expected to improve strength in creep and/or resistance to corrosion, and furthermore to enhance the rate of formation of Zr 3  Al. It will be further appreciated that such additional alloying elements may have some effect upon the amount of Al necessary in the alloy to provide the required Zr 3  Al structure, and for this reason the range of Al present may be above or below that preferred for the binary alloys.