Process of forming titanium aluminides containing chromium, niobium, and boron

The present invention relates closely to commonly owned applications:
Ser. No. 07/546,962, filed Jul. 2, 1990 now U.S. Pat. No. 5,098,653;
Ser. No. 07/546,973, filed Jul. 2, 1990 now U.S. Pat. No. 5,080,860; and
Ser. No. 07/631,988, filed Dec. 21, 1990, now U.S. Pat. No. 5,131,959.
The text of the related applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
The present invention relates generally to the processing of gamma titanium aluminide (TiAl) alloys having improved castability in the sense of improved grain structure. More particularly, it relates to thermomechanical processing of castings of gamma titanium aluminide containing chromium, boron, and niobium dopants which achieve fine grain microstructure and a set of improved properties with the aid of the combination of chromium, niobium, and boron additives together with thermomechanical processing.
In forming a casting, it is generally desirable to have highly fluid properties in the molten metal to be cast. Such fluidity permits the molten metal to flow more freely in a mold and to occupy portions of the mold which have thin dimensions and also to enter into intricate portions of the mold without premature freezing. In this regard, it is generally desirable that the liquid metal have a low viscosity so that it can enter portions of the mold having sharp corners and so that the cast product will match very closely the shape of the mold in which it was cast. I have now found that once cast, the ingot itself may be improved pursuant to the present invention by combining thermomechanical processing with such casting.
Another desirable feature of cast structures is that they have a fine microstructure, that is a fine grain size, so that the segregation of different ingredients of an alloy is minimized. This is important in avoiding metal shrinking in a mold in a manner which results in hot tearing. The occurrence of some shrinkage in a casting as the cast metal solidifies and cools is quite common and quite normal. However, where significant segregation of alloy components occurs, there is a danger that tears will appear in portions of the cast article which are weakened because of such segregation and which are subjected to strain as a result of the solidification and cooling of the metal and of the shrinkage which accompanies such cooling. In other words, it is desirable to have the liquid metal sufficiently fluid so that it completely fills the mold and enters all of the fine cavities within the mold, but it is also desirable that the metal once solidified be sound and not be characterized by weak portions developed because of excessive segregation or internal hot tearing. In the case of cast ingots, the fine grain size generally ensures a higher degree of deformability at high temperatures where the thermomechanical processing is carried out. A large grained or columnar structure would tend to crack at grain boundaries during thermomejchanical processing, leading to internal fissures or surface bursting.
A copending application, Ser. No. 07/546,973, filed Jul. 2, 1990, describes a composition containing niobium and chromium in combination with boron additive which has superior fine grain cast structures and good properties. I have now discovered that it is possible to greatly improve these properties in a composition containing the niobium, chromium, and boron additives, and particularly ductility properties by thermomechanical processing.
With regard to the titanium aluminide itself, it is known that as aluminum is added to titanium metal in greater and greater proportions, the crystal form of the resultant titanium aluminum composition changes. Small percentages of aluminum go into solid solution in titanium and the crystal form remains that of alpha titanium. At higher concentrations of aluminum (including about 25 to 30 atomic percent) and intermetallic compound Ti.sub.3 Al forms and it has an ordered hexagonal crystal form called alpha-2. At still higher concentrations of aluminum (including the range of 50 to 60 atomic percent aluminum) another intermetallic compound, TiAl, is formed having an ordered tetragonal crystal form called gamma. The gamma titanium aluminides are of primary interest in the subject application.
The alloy of titanium and aluminum having a gamma crystal form and a stoichiometric ratio of approximately 1, is an intermetallic compound having a high modulus, low density, a high thermal conductivity, a favorable oxidation resistance, and good creep resistance. The relationship between the modulus and temperature for TiAl compounds to other alloys of titanium and in relation to nickle base superalloys is shown in FIG. 1. As is evident from the Figure, the gamma TiAl has the best modulus of any of the titanium alloys. Not only is the gamma TiAl modulus higher at higher temperature, but the rate of decrease of the modulus with temperature increase is lower for gamma TiAl than for the other titanium alloys. Moreover, the gamma TiAl retains a useful modulus at temperatures above those at which the other titanium alloys become useless. Alloys which are based on the TiAl intermetallic compound are attractive, light-weight materials for use where high modulus is required at high temperatures and where good environmental protection is also required.
One of the characteristics of gamma TiAl which limits its actual application is a relatively low fluidity of the molten composition. This low fluidity limits the castability of the alloy particularly where the casting involves thin wall sections and intricate structure having sharp angles and corners. Improvements of the gamma TiAl intermetallic compound to enhance fluidity of the melt as well as the attainment of fine microstructure in a cast product are very highly desirable in order to permit more extensive use of the cast compositions at the higher temperatures for which they are suitable. When reference is made herein to a fine microstructure in a cast TiAl product, the reference is to the microstructure of the product in the as-cast condition. I have found that for gamma TiAl compositions containing a combination of boron, chromium, and niobium have fine structure in ingots and that the presence of such fine structure helps the forgability of these compositions. I have also recognized that if the doped product containing carbon is forged or otherwise mechanically worked following the casting, the microstructure can be altered and may be improved to a surprising degree.
Another of the characteristics of gamma TiAl which limits its actual application to such uses is a brittleness which is found to occur at room temperature. Also, the strength of the intermetallic compound at room temperature needs improvement before the gamma TiAl intermetallic compound can be exploited in structural component applications. Improvements of the gamma TiAl intermetallic compound to enhance ductility and/or strength at room temperature are very highly desirable in order to permit use of the compositions at the higher temperatures for which they are suitable. It is such improvement for particular gamma TiAl compositions which is made possible by the present invention.
With potential benefits of use at light weight and at high temperatures, what is most desired in the gamma TiAl compositions which are to be used is a combination of strength and ductility at room temperature. A minimum ductility of the order of one percent is acceptable for some applications of the metal composition but higher ductilities are much more desirable. A minimum strength for a composition to be useful is about 50 ksi or about 350 MPa. However, materials having this level of strength are of marginal utility and higher strengths are often preferred for some applications.
The stoichiometric ratio of gamma TiAl compounds can vary over a range without altering the crystal structure. The aluminum content can vary from about 50 to about 60 atom percent. However, the properties of gamma TiAl compositions are subject to very significant changes as a result of relatively small changes of 1% or more in the stoichiometric ratio of the titanium and aluminum ingredients. Also, the properties are similarly affected by the addition of relatively small amounts of ternary, quaternary, and additional elements as additives or as doping agents.
PRIOR ART
There is extensive literature on the compositions of titanium aluminum including the TiAl.sub.3 intermetallic compound, the gamma TiAl intermetallic compounds and the Ti.sub.3 Al intermetallic compound. A patent, U.S. Pat. No. 4,294,615, entitled "Titanium Alloys of the TiAl Type" contains an intensive discussion of the titanium aluminide type alloys including the gamma TiAl intermetallic compound. As is pointed out in the patent in column 1, starting at line 50, in discussing the advantages and disadvantages of gamma TiAl relative to Ti.sub.3 Al:
"It should be evident that the TiAl gamma alloy system has the potential for being lighter inasmuch as it contains more aluminum. Laboratory work in the 1950's indicated that titanium aluminide alloys high temperature strength, they had little or no ductility at room and moderate temperatures, i.e., from 20.degree. to 550.degree. C. Materials which are too brittle cannot be readily fabricated, nor can they withstand infrequent but inevitable minor service damage without cracking and subsequent failure. They are not useful engineering materials to replace other base alloys."
It is known that the gamma alloy system TiAl is substantially different from Ti.sub.3 Al (as well as from solid solution alloys of Ti) although both TiAl and Ti.sub.3 Al are basically ordered titanium aluminum intermetallic compounds. As the '615 patent points out at the bottom of column 1:
"Those well skilled recognize that there is a substantial difference between the two ordered phases. Alloying and transformational behavior of Ti3Al resembles that of titanium, as the hexagonal crystal structures are very similar. However, the compound TiAl has a tetragonal arrangement of atoms and thus rather different alloying characteristics. Such a distinction is often not recognized in the earlier literature."
A number of technical publications dealing with the titanium aluminum compounds as well as with characteristics of these compounds are as follows:
1. E. S. Bumps, H. D. Kessler, and M. Hansen, "Titanium-Aluminum System", Journal of Metals, June, 1952, pp. 609-614, TRANSACTIONS AIME, Vol. 194.
2. H. R. Ogden, D. J. Maykuth, W. L. Finlay, and R. I. Jaffee, "Mechanical Properties of High Purity Ti-Al Alloys", Journal of Metals, February, 1953, pp. 267-272, TRANSACTIONS AIME, Vol. 197.
3. Joseph B. McAndrew and H. D. Kessler, "Ti-36 Pct Al as a Base for High Temperature Alloys", Journal of Metals, October, 1956, pp. 1345-1353, TRANSACTIONS AIME, Vol. 206.
4. S. M. Barinov, T. T. Nartova, Yu L. Krasulin and T. V. Mogutova, "Temperature Dependence of the Strength and Fracture Toughness of Titanium Aluminum", Izv. Akad. Nauk SSSR, Met., Vol. 5, 1983, p. 170.
In reference 4, Table I, a composition of titanium-36 aluminum -0.01 boron is reported and this composition is reported to have an improved ductility. This composition corresponds in atomic percent to Ti.sub.50 Al.sub.49.97 B.sub.0.03.
5. S. M. L. Sastry, and H. A. Lispitt, "Plastic Deformation of TiAl and Ti.sub.3 Al", Titanium 80 (Published by American Society for Metals, Warrendale, Pa.), Vol. 2 (1980) page 1231.
6. Patrick L. Martin, Madan G. Mendiratta, and Harry A. Lispitt, "Creep Deformation of TiAl and TiAl+W Alloys", Metallurgical Transactions A, Vol. 14A (October 1983) pp. 2171-2174.
7. Tokuzo Tsujimoto, "Research, Development, and Prospects of TiAl Intermetallic Compound Alloys", Titanium and Zirconium, Vol. 33, No. 3, 159 (July 1985) pp. 1-13.
8. H. A. Lispitt, "Titanium Aluminides -- An Overview", Mat. Res. Soc. Symposium Proc., Materials Research Society, Vol. 39 (1985) pp. 351-364.
9. S. H. Whang et al., "Effect of Rapid Solidification in Ll.sub.o TiAl Compound Alloys", ASM Symposium Proceedings on Enhanced Properties in Struc. Metals Via Rapid Solidification, Materials Week (October 1986) pp. 1-7.
10. Izvestiya Akademii Nauk SSR, Metally. No. 3 (1984) pp. 164-168.
11. P. L. Martin, H. A. Lispitt, N. T. Nuhfer and J. C. Williams, "The Effects of Alloying on the Microstructure and Properties of Ti.sub.3 Al and TiAl", Titanium 80 (published by the American Society of Metals, Warrendale, Pa.), Vol. 2 (1980) pp. 1245-1254.
12. D. E. Larsen, M. L. Adams, S. L. Kampe, L. Christodoulou, and J. D. Bryant, "Influence of Matrix Phase Morphology on Fracture Toughness in a Discontinuously Reinforced XD.TM. Titanium Aluminide Composite", Scripta Metallurgica et Materialia, Vol. 24, (1990) pp. 851-856.
13. J. D. Bryant, L. Christodon, and J. R. Maisano, "Effect of TiB.sub.2 Additions on the Colony Size of Near Gamma Titanium Aluminides", Scripta Metallurgica et Materialia, Vol. 24 (1990) pp. 33-38.
A number of other patents also deal with TiAl compositions as follows:
U.S. Pat. No. 3,203,794 to Jaffee discloses various TiAl compositions.
Canadian Pat. No. 621884 to Jaffee similarly discloses various compositions of TiAl.
U.S. Pat. No. 4,661,316 (Hashimoto) teaches titanium aluminide compositions which contain various additives.
U.S. Pat. No. 4,842,820, assigned to the same assignee as the subject application, teaches the incorporation of boron to form a tertiary TiAl composition and to improve ductility and strength.
U.S. Pat. No. 4,639,281 to Sastry teaches inclusion of fibrous dispersoids of boron, carbon, nitrogen, and mixtures thereof or mixtures thereof with silicon in a titanium base alloy including Ti-Al.
European patent application no. 0275391 to Nishiejama teaches TiAl compositions containing up to 0.3 weight percent boron and 0.3 weight percent boron when nickel and silicon are present. No chromium or niobium is taught to be present in a combination with boron.
U.S. Pat. No. 4,774,052 to Nagle concerns a method of incorporating a ceramic, including boride, in a matrix by means of an exothermic reaction to impart a second phase material to a matrix material including titanium aluminides.
BRIEF DESCRIPTION OF THE INVENTION
It is, accordingly, one object of the present invention to provide a method of improving the properties of cast gamma TiAl intermetallic compound bodies which have a fine grain structure.
Another object is to provide a method which permits gamma TiAl castings to be modified to a desirable combination of properties.
Another object is to provide a method for modifying cast gamma TiAl into structures having reproducible fine grain structure and an excellent combination of properties.
Other objects and advantages of the present invention will be in part apparent and in part pointed out in the description which follows.
In one of its broader aspects, the objects of the present invention can be achieved by providing a melt of a gamma TiAl containing between 43 and 48 atom percent aluminum between 1.0 and 5.0 atom percent niobium, between 0 and 3.0 atom percent chromium, between 0 and 0.2 atom percent carbon, adding boron as an inoculating agent at concentrations of between 0.5 and 2.0 atom percent, casting the melt, and thermomechanically working the casting. Compositions containng between 0.05 and 0.2 atom percent carbon are preferred.

BRIEF DESCRIPTION OF THE DRAWINGS
The description which follows will be understood with greater clarity if reference is made to the accompanying drawings in which:
FIG. 1 is a graph illustrating the relationship between modulus and temperature for an assortment of alloys.
FIG. 2 is a macrograph of a casting of Ti-46.5Al-2Cr-4Nb-1B-0.1C (Example 18).
FIG. 3 is a bar graph illustrating the property differences between the alloy with and without thermomechanical processing of FIG. 2.

DETAILED DESCRIPTION OF THE INVENTION
It is well known, as is extensively discussed above, that except for its brittleness the intermetallic compound gamma TiAl would have many uses in industry because of its light weight, high strength at high temperatures and relatively low cost. The composition would have many industrial uses today if it were not for this basic property defect of the material which has kept it from such uses for many years.
Further, it has been recognized that cast gamma TiAl suffers from a number of deficiencies some of which have also been discussed above. These deficiencies include the absence of a fine microstructure; the absence of a low viscosity adequate for casting in thin sections; the brittleness of the castings which are formed; the relatively poor strength of the castings which are formed; and a low fluidity in the molten state adequate to permit castings of fine detail and sharp angles and corners in a cast product. Those deficiencies also prevent cast gamma products from being thermomechanically processed to improve their properties.
The inventor has now found that substantial improvements in the ductility of cast gamma TiAl with a fine structure containing a combination of boron, niobium, carbon, and chromium additives, and substantial improvements in the cast products can be achieved by thermomechanical modifications of processing the cast product as now herein discussed.
To better understand the improvements in the properties of gamma TiAl, a number of examples are presented and discussed here before the examples which deal with the novel processing practice of this invention.
EXAMPLES 1-3
Three individual melts were prepared to contain titanium and aluminum in various binary stoichiometric ratios approximating that of TiAl. Each of the three compositions was separately cast in order to observe the microstructure. The samples were cut into bars and the bars were separately HIPed (hot isostatic pressed) at 1050.degree. C. for three hours under a pressure of 45 ksi. The bars were then individually subjected to different heat treatment temperatures ranging from 1200.degree. to 1375.degree. C. Conventional test bars were prepared from the heat treated samples and yield strength, fracture strength and plastic elongation measurements were made. The observations regarding solidification structure, the heat treatment temperatures and the values obtained from the tests are included in Table I.
TABLE I__________________________________________________________________________Example Alloy Compo- Solidifica- Heat Treat Yield Fracture PlasticNumber sition (at %) tion Structure Temperature (.degree.C.) Strength (ksi) Strength (ksi) Elongation__________________________________________________________________________ (%)1 Ti-46Al large equiaxed 1200 49 58 0.9 1225 * 55 0.1 1250 * 56 0.1 1275 58 73 1.82 Ti-48Al columnar 1250 54 72 2.0 1275 51 66 1.5 1300 56 68 1.3 1325 53 72 2.13 Ti-50Al columnar-equiaxed 1250 33 42 1.1 1325 34 45 1.3 1350 33 39 0.7 1375 34 42 0.9__________________________________________________________________________ * specimens failed elastically
As is evident from Table I, the three different compositions contain three different concentrations of aluminum and specifically 46 atomic percent aluminum; 48 atomic percent aluminum; and 50 atomic percent aluminum The solidification structure for these three separate melts are also listed in Table I, and as is evident from the table, three different structures were formed on solidification of the melt. These differences in crystal form of the castings confirm in part the sharp differences in crystal form and properties which result from small differences in stoichiometric ratio of the gamma TiAl compositions. The Ti-46Al was found to have the best crystal form among the three castings but small equiaxed form is preferred.
Regarding the preparation of the melt and the solidification, each separate ingot was electroarc melted in an argon atmosphere. A water cooled hearth was used as the container for the melt in order to avoid undesirable melt-container reactions. Care was used to avoid exposure of the hot metal to oxygen because of the strong affinity of titanium for oxygen.
Bars were cut from the separate cast structures. These bars were HIPed and were individually heat treated at the temperatures listed in the Table I.
The heat treatment was carried out at the temperature indicated in the Table I for two hours.
From the test data included in Table I, it is evident that the alloys containing 46 and 48 atomic percent aluminum had generally superior strength and generally superior plastic elongation as compared to the alloy composition prepared with 50 atomic percent aluminum. The alloy having the best overall ductility was that containing 48 atom percent aluminum.
However, the crystal form of the alloy with 48 atom percent aluminum in the as cast condition did not have a desirable cast structure inasmuch as it is generally desirable to have fine equiaxed grains in a cast structure in order to obtain the best castability in the sense of having the ability to cast in thin sections and also to cast with fine details such as sharp angles and corners.
EXAMPLES 4-6
The present inventor found that the gamma TiAl compound could be substantially ductilized by the addition of a small amount of chromium. This finding is the subject of a U.S. Pat. No. 4,842,819.
A series of alloy compositions were prepared as melts to contain various concentrations of aluminum together with a small concentration of chromium. The alloy compositions cast in these experiments are listed in Table II immediately below. The method of preparation is essentially that described with reference to Examples 1-3 above.
TABLE II__________________________________________________________________________Example Alloy Compo- Solidifica- Heat Treat Yield Fracture PlasticNumber sition (at %) tion Structure Temperature (.degree.C.) Strength (ksi) Strength (ksi) Elongation__________________________________________________________________________ (%)4 Ti-46Al-2Cr large equiaxed 1225 56 64 0.5 1250 44 53 1.0 1275 50 59 0.75 Ti-48Al-2Cr columnar 1250 45 60 2.2 1275 47 63 2.1 1300 47 62 2.0 1325 53 68 1.96 Ti-50Al-2Cr columnar-equiaxed 1275 50 60 1.1 1325 50 63 1.4 1350 51 64 1.3 1375 50 58 0.7__________________________________________________________________________
The crystal form of the solidified structure was observed and, as is evident from Table II the addition of chromium did not improve the mode of solidification of the structure of the materials cast and listed in Table I. In particular, the composition containing 46 atomic percent of aluminum and 2 atomic percent of chromium had large equiaxed grain structure. By way of comparison, the composition of Example 1 also had 46 atomic percent of aluminum and also had large equiaxed crystal structure. Similarly for Examples 5 and 6, the addition of 2 atomic percent chromium to the composition as listed in Examples 2 and 3 of Table I showed that there was no improvement in the solidification structure.
Bars cut from the separate cast structures were HIPed and were individually heat treated at temperatures as listed in Table II. Test bars were prepared from the separately heat treated samples and yield strength, fracture strength and plastic elongation measurements were made. In general, the material containing 46 atomic percent aluminum was found to be somewhat less ductile than the materials containing 48 and 50 atomic percent aluminum but otherwise the properties of the three sets of materials were essentially equivalent with respect to tensile strength.
EXAMPLES 7-9
Melts of three additional compositions of gamma TiAl were prepared with compositions as listed in Table III immediately below. The preparation was in accordance with the procedures described above with reference to Examples 1-3. Elemental boron was mixed into the charge to be melted to make up the boron concentration of each boron containing alloy. For convenience of reference, the composition and test data of Example 2 is copied into Table III.
TABLE III__________________________________________________________________________Example Alloy Compo- Solidifica- Heat Treat Yield Fracture PlasticNumber sition (at %) tion Structure Temperature (.degree.C.) Strength (ksi) Strength (ksi) Elongation__________________________________________________________________________ (%)2 Ti-48Al columnar 1250 54 72 2.0 1275 51 66 1.5 1300 56 68 1.3 1325 53 72 2.17 Ti-48Al-0.1B columnar 1275 53 68 1.5 1300 54 71 1.9 1325 55 69 1.7 1350 51 65 1.28 Ti-48Al-2Cr-4Nb-0.1B columnar 1275 54 72 2.1 1300 56 73 1.9 1325 59 77 1.9 1350 64 78 1.59 Ti-48Al-2Cr-4Nb-0.2B columnar 1275 52 69 2.0 1300 55 71 1.6 1325 58 72 1.4__________________________________________________________________________
Each of the melts were cast and the crystal form of the castings was observed. Bars were cut from the casting and these bars were HIPed and were then given individual heat treatments at the temperatures listed in the Table III. Tests of yield strength, fracture strength and plastic elongation were made and the results of these tests are included in the Table III as well.
As is evident from the Table III, relatively low concentrations of boron of the order of one tenth or two tenths of an atom percent were employed. As is also evident from the table, this level of boron additive was not effective in altering the crystalline form of the casting.
The table includes as well a listing of the ingredients of Example 2 for convenience of reference with respect to the new Examples 7, 8, and 9 inasmuch as each of the boron containing compositions of the examples contained 48 atomic percent of the aluminum constituent.
It is important to observe that the additions of the low concentrations of boron did not result in any significant reduction of the values of the tensile and ductility properties.
EXAMPLES 10-13
Melts of four additional compositions of gamma TiAl were prepared with compositions as listed in Table IV immediately below. The preparation was according to the procedures described above with reference to Examples 1-3. In Examples 12 and 13, as in Examples 7-9, the boron concentrations were added in the form of elemental boron into the melting stock.
TABLE IV__________________________________________________________________________Example Alloy Compo- Solidifica- Heat Treat Yield Fracture PlasticNumber sition (at %) tion Structure Temperature (.degree.C.) Strength (ksi) Strength (ksi) Elongation__________________________________________________________________________ (%) 4 Ti-46Al-2Cr large equiaxed 1225 56 64 0.5 1250 44 53 1.0 1275 50 59 0.710 Ti-46Al-2Cr-0.5C columnar 1250 97 97 0.2 1300 86 86 0.2 1350 69 73 0.3 1400 96 100 0.311 Ti-46.5Al-2Cr-0.5N fine, equiaxed 1250 + 77 0.1 1300 73 75 0.2 1350 + 60 0.1 1400 + 80 0.112 Ti-45.5Al-2Cr-1B fine, equiaxed 1250 77 85 0.5 1275 76 85 0.7 1300 75 89 1.0 1325 71 80 0.5 1350 78 85 0.413 Ti-45.25Al-2Cr-1.5B fine, equiaxed 1250 81 88 0.5 1300 79 85 0.4 1350 83 94 0.7__________________________________________________________________________ + specimens failed elastically
Again, following the formation of each of the melts of the four examples, observation of the solidification structure was made and the structure description is recorded in Table IV. The data for Example 4 is copied into Table IV to make comparison of data with the Ti-46Al-2Cr composition more convenient. In addition, bars were prepared from the solidified sample, the bars were HIPed, and given individual heat treatments at temperatures ranging from 1250.degree. to 1400.degree. C. Tests of yield strength, fracture strength and plastic elongation are also made and these test results are included in Table IV for each of the specimens tested under each Example.
It will be noted that the compositions of the specimens of the Examples 10-13 corresponded closely to the composition of the sample of Example 4 in that each contained approximately 46 atomic percent of aluminum and 2 atomic percent of chromium. Additionally, a quaternary additive was included in each of the examples. For Example 10, the quaternary additive was carbon and as is evident from Table IV the additive did not significantly benefit the solidification structure inasmuch as a columnar structure was observed rather than the large equiaxed structure of Example 4. In addition, while there was an appreciable gain in strength for the specimens of Example 10, the plastic elongation was reduced to a sufficiently low level that the samples were essentially useless.
Considering next the results of Example 11, it is evident that the addition of 0.5 nitrogen as the quaternary additive resulted in substantial improvement in the solidification structure in that it was observed to be fine equiaxed structure. However, the loss of plastic elongation meant that the use of nitrogen was unacceptable because of the deterioration of tensile properties which it produced.
Considering next Examples 12 and 13, here again the quaternary additive, which in both cases was boron, resulted in a fine equiaxed solidification structure thus improving the composition with reference to its castability. In addition, a significant gain in strength resulted from the boron addition based on a comparison of the values of strength found for the samples of Example 4 as stated above. Also very significantly, the plastic elongation of the samples containing the boron quaternary additive were not decreased to levels which rendered the compositions essentially useless. Accordingly, I have found that by adding boron to the titanium aluminide containing the chromium ternary additive I am able not only to substantially improve the solidification structure, but am also able to significantly improve tensile properties including both the yield strength and fracture strength without unacceptable loss of plastic elongation. I have discovered that beneficial results are obtainable from additions of higher concentrations of boron where the concentration levels of aluminum in the titanium aluminide are lower. Thus the gamma titanium aluminide composition containing chromium and boron additives are found to very significantly improve the castability of the titanium aluminide based composition particularly with respect to the solidification structure and with respect to the strength properties of the composition. The improvement in cast crystal form occurred for the alloy of Example 13 as well as of Example 12. However, the plastic elongation for the alloy of Example 13 were not as high as those for the alloy of Example 12.
EXAMPLE 14-15
A set of two additional alloy compositions were prepared having ingredient content as set forth in Table V immediately below. The method of preparation was essentially as described in Examples 1-3 above. As in the earlier examples, elemental boron was mixed into the charge to be melted to make up the boron concentration of each boron containing alloy.
TABLE V__________________________________________________________________________Example Alloy Compo- Solidifica- Heat Treat Yield Fracture PlasticNumber sition (at %) tion Structure Temperature (.degree.C.) Strength (ksi) Strength (ksi) Elongation__________________________________________________________________________ (%)14 Ti-45.5Al-2Cr-1B-4Nb fine, equiaxed 1250 82 83 0.2 1275 79 92 0.9 1300 80 91 0.7 1350 --* 83 0.1 1400 82 92 0.715 Ti-45.25Al-2Cr-1.5B-4Nb fine, equiaxed 1275 74 91 1.3 1300 73 92 1.4 1325 77 95 1.4__________________________________________________________________________ * specimens failed elastically
As is evident from Table V, the two compositions are essentially the compositions of Examples 12 and 13 to which 4 atomic percent of niobium have been added. A U.S. Pat. No. 4,879,092, assigned to the present assignee, teaches a novel composition of titanium aluminum alloys modified by chromium and niobium. Further, a copending application, Ser. No. 354,965, filed May 22, 1989, deals with a method of processing TiAl alloys modified with chromium and niobium.
Again, following the description given in Examples 1-3, the solidification structure was examined after the melt of this compositions had been cast. The solidification structure found was the fine equiaxed form which had also been observed for the samples of Examples 12 and 13.
Following the steps set forth with reference to Examples 1-3, bars of the cast material were prepared, HIPed, and individually heat treated at the temperatures listed in Table V. The test bars were prepared and tested and the results of the tests are listed in Table V with respect to both strength properties and with respect to plastic elongation. As is evident from the data listed in Table V, significant improvements particularly in plastic elongation were found to be achievable employing the compositions as set forth in Examples 14 and 15 of Table V. The conclusions drawn from the findings of Examples 14 and 15 are that the boron additive greatly improves the castability of the composition of the issued patent referenced immediately above. I have found that lower concentrations of aluminum permit incorporation of higher concentrations of boron. For this reason, I reduced the aluminum concentration of Example 15, as compared to Example 14, to partially compensate for the increase in the boron concentration in Example 15.
Accordingly, it is apparent that not only does the cast material have the desirable fine equiaxed form, but the strength of the compositions of Examples 14 and 15 are greatly improved over the composition of Examples 1, 2, and 3 of Table I. Furthermore, the plastic elongation of the samples of Examples 14 and 15 are not reduced to unacceptable levels as employed in Example 10, or from the use of the nitrogen additive as employed in Example 11.
The improvements in the properties of the TiAl compositions containing chromium and niobium by the doping with boron is the subject of commonly owned copending application Ser. No. 07/546,973, filed Jul. 2, 1990 now U.S. Pat. No. 5,080,860.
EXAMPLES 16-18
Three additional melts were prepared according to method described with references to Examples 1-3. Compositions of the three additional melts are listed in Table VI immediately below. As in the earlier examples, elemental boron was mixed into the charge to be melted to make up the boron concentration of each boron containing alloy.
TABLE VI__________________________________________________________________________Example Alloy Compo- Solidifica- Heat Treat Yield Fracture PlasticNumber sition (at %) tion Structure Temperature (.degree.C.) Strength (ksi) Strength (ksi) Elongation__________________________________________________________________________ (%)16 Ti-44.5Al-2Cr-1B-4Nb-0.1C fine, equiaxed 1250 93 103 0.6 1275 97 105 0.5 1300 92 103 0.617 Ti-45.5Al-2Cr-1B-4Nb-0.1C fine, equiaxed 1250 85 96 0.8 1275 93 96 0.4 1300 87 90 0.318 T-46.5Al-2Cr-1B-4Nb-0.1C fine, equiaxed 1250 79 84 0.4 1275 73 83 0.7 1300 73 88 1.3 1325 77 85 0.7__________________________________________________________________________
The compositions of these three melts corresponded to the composition of the melt of Example 14 with two exceptions. One exception is that each of the three melts of Examples 16, 17, and 18 had a different aluminum concentration and specifically 44.5 atomic percent for Example 16; 45.5 atomic percent for Example 17; and 46.5 atomic percent for Example 18. Secondly, each of the melts had 0.1 atomic percent of carbon. These compositions were cast and the cast compositions were examined as to solidification structure. For each case, the structure was found to be fine equiaxed structure. The fine equiaxed structure was not attributed to the addition of carbon because the carbon addition of Example 10 produced columnar solidification structure.
Bars were prepared from the cast material, HIPed, and were subjected to separate heat treatments according to the schedule set forth in Table VI. Tests were performed on the individually heat treated samples and yield strength, fracture strength and plastic elongation data was obtained and is included in Table VI as well. A comparison of the data obtained from the samples of Example 17 with the data obtained from the samples of Example 14 reveals that there is appreciable strengthening which results from the addition of 0.1 carbon as the compositions are otherwise identical. In addition, the plastic elongation of the material of Example 18 containing 46.5 atomic percent aluminum was acceptably high for an as cast composition. In evaluating the results observed from these three Examples, 16-18, it is evident that as the concentration of aluminum is increased, the strength is decreased and the ductility is increased.
It is noted above that the titanium aluminum alloy modified by chromium and niobium is the subject matter of U.S. Pat. No. 4,879,092 and pending application Ser. No. 354,965 to the same assignee as the subject application.
It will be appreciated that my testing has shown that the patented alloy containing niobium and chromium additives is a highly desirable alloy because of the combination of properties and specifically the improvement of the properties of the TiAl which is attributed to the inclusion of the niobium and chromium additives. However, it is also evident from the above that the crystal form of an alloy containing the chromium and niobium is basically columnar and is not in the preferred finely equiaxial crystal form desired for casting applications. Accordingly, the base alloy containing the chromium and niobium additives has a desirable combination of properties which may be attributed to the presence of the chromium and niobium. In addition, because of the infusion of boron into the base alloy, the crystal form of the alloy, and its castability, is very drastically improved. But, at the same time, there is no significant loss of the unique set of properties which are imparted to the base TiAl alloy by the chromium and niobium additives. From the study of the influence of several additives such as carbon and nitrogen above, it is evident that it is the combination of additives which yields the unique set of desirable results. Numerous other combinations, including many containing nitrogen, for example, suffer significant loss of properties although gaining a beneficial crystal form.
EXAMPLES 15A-18A
Samples of the cast alloys as described with reference to Examples 15-18 were prepared by cutting disks from the as-cast ingots.
Each of the cut ingots is about 2" in diameter and about 1/2" thick in the approximate shape of a hockey puck. The ingot was enclosed within a steel annulus having a wall thickness of about 1/2" and having a vertical thickness which matched identically that of the hockey puck ingot. Before being enclosed within the retaining ring, the hockey pucked ingot was homogenized by being treated to 1250.degree. C. for two hours. The assembly of the hockey puck and retaining ring were heated to a temperature of about 975.degree. C. The heated sample and containing ring were forged to a thickness of approximately half that of the original thickness.
After the forged ingot was cooled, a number of pins were machined out of the ingot for a number of different heat treatments. The different pins were separately annealed at the different temperatures listed in Table VII below. Following the individual anneals, the pins were aged at 1000.degree. C. for two hours. After the anneal and aging, each pin was machined into a conventional tensile bar and conventional tensile tests were performed on the resulting bars. The results of the tensile tests are listed in Table VII below.
TABLE VII__________________________________________________________________________Example Alloy Compo- Heat Treat Yield Fracture PlasticNumber sition (at %) Temperature (.degree.C.) Strength (ksi) Strength (ksi) Elongation (%)__________________________________________________________________________15A Ti-45.25Al-2Cr-1.5B-4Nb 1275 76 93 1.9 1300 76 94 1.9 1325 77 94 1.516A Ti-44.5Al-2Cr-1B-4Nb-0.1C 1250 97 114 1.5 1275 99 120 1.5 1300 102 115 0.817A Ti-45.5Al-2Cr-1B-4Nb-0.1C 1250 88 100 1.4 1275 86 101 1.4 1300 -- 80 018A Ti-46.5Al-2Cr-1B-4Nb-0.1C 1275 81 95 1.9 1300 80 98 2.1__________________________________________________________________________
From the data listed in Table VII, and by comparison with the data listed in Table V, it is evident that a remarkable increase in properties of the alloy of Example 15 were accomplished by the thermal mechanical treatment which was accorded this alloy composition. Thus, with respect to the yield strength, there was a gain at the 1300.degree. heat treating temperature of yield strength of about 10% and a gain of fracture strength of about 11%. However, the really important gain for the subject alloy as a result of the thermal mechanical processing was a gain of over 60% in the ductility property. The properties at the other heat treatment temperature also improved.
Accordingly, it is evident from the data listed in Table VII that for the sample of Example 15 heat treated at 1300.degree. C., there was a slight increase in both the yield strength and the fracture strength but there was, in addition, a gain of over 60% in the ductility value. A gain of 60% in ductility for an alloy having the initial properties of the titanium aluminide is very significant and can, in fact, greatly extend the utility of such an alloy.
More uniquely, a comparison of the compositions containing the carbon additive in addition to chromium, niobium, and boron reveals an even more remarkable improvement in properties. Thus, for example, the alloy of Example 16 treated at 1275.degree. C. had a ductility value of 0.5. When this same material was subjected to thermomechanical processing the ductility increased to 1.5. This is a 200% increase. For the material treated at 1250.degree. C. the increase was from 0.6 to 1.5 -- an increase of 150%.
In addition, both the fracture strength of the wrought composition of Example 16A was significantly improved over that of material of Example 16 and there was essentially no loss of yield strength.
These improvements in properties of the carbon containing material were quite remarkable and unexpected.
By comparison of Tables V, VI, and VII, it becomes apparent that the properties of each alloy are generally improved after thermomechanical processing.

Number	Name	Date
3203794	Jaffee et al.	Aug 1965
4294615	Blackburn et al.	Oct 1981
4639281	Sastry et al.	Jan 1987
4661316	Hashimoto et al.	Apr 1987
4774052	Nagle et al.	Sep 1988
4842819	Huang et al.	Jun 1989
4842820	Huang et al.	Jun 1989
4879092	Huang	Nov 1989
4916028	Huang	Apr 1990
5076858	Huang	Dec 1991
5080860	Huang	Jan 1992
5082506	Huang	Jan 1992
5082624	Huang	Jan 1992
5098653	Huang	Mar 1992

Number	Date	Country
621884	Jun 1961	CAX
0275391	Dec 1987	EPX
1298127	Dec 1989	JPX

Process of forming titanium aluminides containing chromium, niobium, and boron

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