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By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By J. T. Norton, N. J. Grant, A. R. Chaudhuri

MOST of the recent work to establish the mech-anism of creep in metals at high temperatures has utilized aluminum as the experimental material. It was thought desirable to initiate an investigation of a hexagonal close-packed metal, because of the relatively simple slip system, and compare the observed deformation characteristics with those that have been observed for the face-centerd cubic metals. High-purity magnesium was chosen for this purpose, first, because its strength and other mechanical properties are similar to those of aluminum in the same temperature range, and second, because the existing equipment was ideally suited to observe magnesium during creep. It is proposed in this paper to present a pictorial and qualitative account of the changes that high-purity magnesium undergoes during creep at 500°F. The characteristics of deformation of aluminum described below have been observed by various workers and accounts of these may be obtained from the papers of Chang and Grant.'- These characteristics are: slip, subgrain formation, grain boundary sliding and migration, fold formation, deformation bands, and kink bands. It is well known that in a flat magnesium specimen, slip on the basal plane (0001) in the [1120] direction results in the formation of straight bands on the surface of the specimen. Schmid and co-workers' have shown that this system is operative in the temperature range of -185" to 300°C (-300° to 572°F). They have also shown that a second system, slip on the pyramidal planes {1071} or {1012} in the [1120] direction, is operative at temperatures higher than 225°C (437°F). Between 225° and 300°C (437" to 572°F), therefore, deformation by both these systems is expected. Bakarian and Mathewson5 confirmed the occurrence of pyramidal slip on the {1011} plane and found that it resulted in irregular markings on the surfaces of their specimens. Burke and Hibbard6 obtained evidence of pyramidal slip in single crystals of magnesium deformed at room temperature. Bakarian and Mathewson5 suggested that the irregular appearance of these bands was due to slip on both of the pyramidal planes occurring simultaneously but in the same direction, the close angular relationship between the planes making this process possible. Furthermore, since neither of these planes is close enough to the basal plane, slip on the latter does not exhibit the irregular appearance of slip bands resulting from pyramidal slip. Experimental Procedure High-purity magnesium, supplied by the Dow Chemical Co., was used in these experiments. The analysis was as follows: Al, 0.0002 pct; Mn, 0.0018; Fe, 0.0024; Cu, 0.0002; Sn, 0.001; Ca, 0.01; Ni, 0.0003; Zn, 0.01; Pb, 0.0005; Si, 0.001; and Mg, 99.972. The magnesium was supplied in the form of 1/2 in. diam rods. The specimens had an overall length of 21/4 in., the round ends being threaded to fit the specimen holders. The previously round 3/16 in. diam gage section of the specimen had two parallel flats machined on opposite sides for microscopic observation, yielding a test zone having the dimensions of lx3/16x7/64 in. The specimens were electrolytically polished (without prior mechanical polishing of the machined flats), in a solution composed of 375 ml of ortho-phosphoric acid and 625 ml of ethyl alcohol.' The cathode was a stainless steel sheet bent so that the specimen was completely surrounded. The voltage for successful polishing was 1.5 v at 100 to 300 milli-amp current. Electropolishing for about 45 min sufficed to obtain a good metallographic surface on the specimens after they had been machined. The creep tests were performed under constant load, and two types of equipment were used. In the first, designed by Servi and Grant,V he specimens were beam-loaded, and a furnace could be lowered to surround the specimen. As the microstructural changes could not be observed during the course of the test, the tests had to be interrupted periodically by removing the specimen for microscopic examination. The second unit was a high temperature microscopy furnace designed by Chang and Grant.' The furnace was fitted with an optically flat quartz window having area dimensions 1.25x0.5 in., so that the whole test portion could be viewed through it at magnifications up to x240. The metallurgical microscope had three mutually perpendicular axes of motion, and, in addition, it was possible to measure angular displacements by rotation of the eyepiece. It was thus possible to make precise observations of the specimen during creep, and micrographs could be taken by attaching a camera to the eyepiece of the microscope. The average grain size of the specimens that were tested was about 1 to 3 mm. This grain size could

Jan 1, 1954

By R. H. Jamison

A relatively new haulage system is described. Employed by the Delmant Fuel Co.. the "Full Dimension" system provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. This system is said to provide a higher percentage of recovery as well as additional safety and production. Delmont Fuel Co. is employing a comparatively new system of transportation known as a Full Dimension system. Cne of these systems has been in operation for a year at the company's 10-B Mine as a part of a conventional section. A second was installed at the No. 10 mine in late 1960 to handle the production of a Colmol in a pillar section. SYSTEM COMPONENTS A Full Dimension system is a haulage system that provides an uninterrupted flow of coal from a loader or continuous miner at the face to the main line transportation system. The equipment required for this system consists of a series of interconnected chain conveyors that are mobile and articulated. They will retract or extend a sufficient distance for the development of a five-entry system; or, in the Colmol pillar section, it provides reach of 210 ft in all directions from the section belt. The components of this system are: l)One 160-ft chain line placed in tandem with the belt conveyor. It has a self-propelled drive, is 20 in. wide and 9 in. deep. Moving this conveyor requires the assistance of a loading machine or cutting machine. 2) One 40-ft piggyback that discharges along the entire length of the 160 ft chain conveyor. 3) A mobile bridge carrier, which is a self-propelled conveyor with four wheel steer and four wheel drive, twenty-eight feet long, it delivers coal to the receiving end of the piggyback. Axles steer individually making possible almost lateral movement. 4) Another 40-ft piggyback, duplicate of item 2 that delivers coal along the entire length of item 3 (mobile bridge carrier). 5) A second mobile bridge carrier, similar to the first, which deliver coal to the piggyback (item 4). 6) A third 40-ft piggyback, duplicate of items 2 and 4. This pig is attached to the loading machine and delivers its coal along the length of the second mobile bridge conveyor. Since the original preparation of this paper, the Delmot Fuel Co. has been able to eliminate the 160-ft chain conveyor. This was accomplished by connecting the outby piggyback directly to a loading machine with an extended boom. The loading machine loads directly onto the belt. This change has resulted in a substantial reduction in moving time and greatly increased flexability. A single trailing cable powers the entire string of equipment. It is attached to the side of the equipment in such a way as to keep it off the ground and afford maximum protection. The tramming rate of this equipment is 90 fpm. The conveyor capacity in a conventional section at Delmont's mines is 7.5 tpm and in the Colmol section is 5.5 tpm. This regulation is a simple function of conveyor speed. To visualize operation of this equipment, it would be well for me to touch briefly on local conditions in the Upper Freeport seam in which we mine. (Also, see the photographs of some of the equipment in use.) DELMONT'S TOPOGRAPHY The Delmont Fuel Co. operates two mines in this seam in Westmoreland County, Pa. The No. 10 mine, which was opened in about 1912, is now almost worked out. Depending on economics in the industry, it has a life of two to four years on a declining production basis. A year ago a new drift mine was opened which is called No. 10-B. It is about two miles from the cleaning plant and is connected thereto by an overland belt conveyor. The new mine is being developed at a rate calculated to take up the slack as the old mine plays out. The Upper Freeport seam averages 4.2 ft in thickness in the area of the Delmont mines. It carries 4 in. of boney coal at the top of the seam and a middle man of from 2 to 4 in. We mine just above a 1-in. slate parting which has 4 to 6 in. of highly laminated coal beneath it. This material normally makes a very firm bottom. The roof varies from dark shale to sand rock and 36-in. bolts are placed on 4-ft centers for roof support. All working places are driven 20 ft wide on development and 25 ft wide on retreat. Selection of mobile chain conveyor equipment when it became available, was a very natural move for Delmont Fuel to make, because chain conveyors and piggybacks had been in use at the company's mines for about 12 years. Grades in the new mine

Jan 1, 1961

By R. I. Jaffee, F. C. Holden, H. R. Ogden

ECENT papers dealing with the properties of unalloyed iodide titanium have been directed primarily at the determination of base-line properties for alloy investigations. Early work was limited to a few tests because of the limited availability of iodide titanium at the time. In the results of papers by Campbell et al.,1 Gonser and Litton,2 Jaffee and Campbell,3 inlay and Snyder,4 and Jaffee, Ogden, and Maykuth, data on mechanical properties are presented for unalloyed iodide titanium in the annealed and cold-worked conditions. Data are presented in this paper which show the effects of heat treatment on the structure and mechanical properties of commercially produced iodide titanium. Correlation is made between microstruc-tural variables and the mechanical properties. Experimental Procedures Melting Stock: The melting stock used was as-deposited iodide titanium, produced by New Jersey Zinc Co. The furnished analysis showed the following range of impurities: N, 0.004 to 0.008 pct; Mn, 0.005 to 0.013; Fe, 0.0035 to 0.025; Al, 0.013 to 0.015; Mo, 0.0015; Pb, 0.0045 to 0.0065; Cu, 0.0015 to 0.002; Sn, 0.001 to 0.01; Mg, 0.0015 to 0.002; and Ni, 0.003. Hydrogen content as determined by vacuum-fusion analysis was 0.0091 wt pct (0.44 atomic pct) after arc melting and fabrication. Nitrogen analysis on the arc-melted and fabricated titanium showed a content of less than 0.002 pct N. The average hardness of the furnished stock was Rf 70, or approximately 85 VHN. Melting Procedure: The as-deposited rods were rolled, sheared, and degreased in preparation for arc melting. The charge was arc-melted with a tungsten electrode in a water-cooled copper crucible under a positive pressure of high purity (99.96 pct) argon. The final ingot was approximately 2 in. in diameter and showed no increase in hardness over that of the initial stock. Fabrication: Heating for fabrication was done in air. It was begun by forging the ingot into a 3/4 in. diam rod, at an initial temperature of 1600°F. Scale was removed by sandblasting. The rod was then swaged to 1/4 in. diam at room temperature through a series of 20 dies, with approximately 10 pct reduction in area between each die. An anneal of 1 hr at 850 °C in air was given after the 1/2 in. die, such that the final cold reduction was 75 pct. Sections cut from this rod were used for test and microstructure specimens. Heat Treatment: Heat treatments were carried out in resistance tube furnaces with stainless-steel linings, under an atmosphere of gettered argon. As further protection against contamination, the specimens were packed in titanium turnings in a titanium sleeve. Control experiments have shown negligible hardness increases with this method, indicating that contamination from oxygen and nitrogen is slight. Three cooling rates were employed in this work; these have been designated as water quenching, argon cooling (to simulate air cooling under a controlled atmosphere), and furnace cooling. The cooling rate for an argon cool is 100°C per min for the first minute, with an average cooling rate of 35°C per min over a 15-min period. A furnace cool requires about 10 hr, with an average cooling rate of 3.6oC per min during the first hour, and an average cooling rate of 1.2°C per min over the 10-hr period. Microimpact Test: The specimen adopted was based on the cylindrical Izod Type Y specimen (ASTM, E23-41T). All dimensions were reduced to half scale, including the notch radius. Specifications are shown in Fig. 1. The specimen is held vertically in an adapter and broken as a cantilever beam. Impact tests were run on a constant-velocity (11.34 ft per sec) Tinius Olsen impact testing machine with a total available energy of 100 in.-lb. Tests were made to determine the correlation between this microimpact and the standard V-notch Charpy impact test. Curves showing impact energy as a function of temperature for both impact tests are plotted in Fig. 2. Transition temperatures, when they occur, are about the same for both impact tests. All three titanium-rich materials have the same conversion factor, 10. Tensile Testing: Tensile tests were conducted on Baldwin-Southwark testing machines using the 600, 2400, or 3000 1b range. Specifications for the test specimen were taken from the 1948 edition of the ASM Metals Handbook, and are shown in Fig. 1. Strain measurements were made using an SR-4 resistance gage (Type A-7) cemented to the reduced section in conjunction with a lever-type extenso-meter. Readings on the SR-4 strain indicator were

Jan 1, 1954

By A. J. Shaler

The subject of the mechanism of sintering has received much attention in the past few years, particularly since the beginning of the series of AIME seminars in powder metallurgy of which this paper introduces the fourth. In the first of these, F. N. Rhines1 brought together and discussed the available experimental data on the sintering of pure metallic powder, and succeeded in bringing to a sharp focus the attention of workers in this field on the established observations which a satisfactory theory must explain. Several other authors3,5,6 have, in the last few years, studied the phenomena that occur when cold metallic powders, loose or in the form of compacts, are first brought to elevated temperatures. Some workers' in the field of friction have recently studied the adhesion of solid metal surfaces when they are brought into close contact. These researches have indicated that several separate mechanisms operate simultaneously, at least during the first part of the sintering process. Some of them have been called transient mechanisms4 because they are in general not absolutely necessary to sintering. Powders may be so prepared and so treated that these transient phenomena do not take place during subsequent sintering. This does not mean, of course, that their industrial and scientific importance is any less than that of the steady-state phenomena. The latter are changes that go on during sintering no matter how the powders are made or treated; they cannot be divorced from sintering. One way to analyze the process of sintering into its component parts is perhaps to distinguish between these transient and steady-state phenomena. Some of the transient phenomena have been studied in the past few years. Huttig3 has shown that, when the temperature of metallic powder is slowly raised, the following events generally occur in order: (1) physically adsorbed gases are desorbed; (2) there is an atomic rearrangement of the surface, a sort of two-dimensional "surface-reciystallization"; (3) there is a breakdown of chemically adsorbed surface compounds; (4) there is a recrystalliza-tion in the volume of the metal. All these changes are shown by Huttig and his coworkers to be completed fairly rapidly at lower temperatures than those generally used in sintering and are therefore not a part of the mechanism whereby the density of a mass of powder continues to change after long heating at an elevated temperature. But the first and third of these changes release gases in quantities which may or may not help to control the steady-state mechanisms, depending on when the voids become isolated from the outside of the compact. Among the phenomena studied by Steinberg and Wulff,8 there is the effect on sintering of residual stresses arising from the pressing operation. They found that the lateral surfaces of a green compact of iron are under a longitudinal residual tension-stress of the order of magnitude of half the yield-point for solid iron. If the outside surface is in tension, the core must be under longitudinal compression. When the compact is heated, the surface residual stress is thermally relieved first, and the compact therefore initially expands in the direction of its axis. This is a transient phenomenon, if for no other reason than the possibility of sintering unpressed powders, as demonstrated by Delisle,9 Libsch, Volterra and Wulff10 and others.1 The subject of recrystallization is dealt with further in a separate section, in view of its prominent place in sintering literature. It, too. is one of these transient phenomena. Among the steady-state parts there may be distinguished the attraction between particles and its consequences, the spheroidization of voids in the compacts, and the densification or swelling of the compact. There is considerable evidence4,7 showing that cold metallic surfaces, when brought to within a few interatomic distances of one another, are attracted to each other by forces of the order of many thousands of pounds per square inch. A calculation, discussed in greater detail in another section, shows that this force changes but slightly when the temperature of the surfaces approaches the melting point. Actual measurements of forces of adhesion of this magnitude have been made by Bradley12 on some nonmetals, but none has yet been made on cold or hot metals. This force is of sufficient magnitude to cause some plastic deformation in powder compacts, as will be shown below. A second force of steady-state nature is due to the surface tension, which probably has the same origin as the force of attraction between surfaces.164 A paper by Udin, Shaler, and Wulff1,3 gives the results of precise direct measurements of its value for solid copper. The demonstration of the tendency for the surface tension to shrink a pore was long ago given by Gibbs.17 He showed that its effect on a curved surface between two phases is equivalent to a pressure perpendicular to that

Jan 1, 1950

By H. V. Welch

In this paper, as prepared for delivery at the Southern California regional meeting on Oct. 14, 1948, it was thought best to interpret the term "economics" in a rather broad manner and to include, in addition to the material losses and recoveries and associated monetary values (Part I), a limited discussion of the increased difficulties or the particular problem and the special requirements, as the particle sizes of the suspended particles range down from the relatively coarse to 100, to 10, to 1 micron or even to a fraction of one micron (Part II). Further, it is not quite in order to overlook entirely the community and individual health problems, although space requires the economics of this to be considered only very incompletely. Therefore, Part III, covering this phase of the subject, is very limited. This paper, then, is divided into 5 parts or headings as follows: I Losses and/or values in suspended solids. II Particle size. III Dust and fumes in community and individual living. IV Means and Procedures for dust and fume collection. V Description or examples of specific equipment in service and of the several types used for dust and fume collection. Because of the wide extent and wealth of subject material available and the space and time limitation imposed, presentation and discussion are less than originally planned. I—Losses and/or Values in Suspended Solids The weight involved in moving streams of industrial plant gases is commonly not appreciated, neither is their carrying power in the weight of solids maintained in suspension and moved with the gas stream from a point of origin or pick-up to a point of dissipation or settlement. These, however, are major weight figures; for example, in a modern iron blast furnace there may be five tons of gas for every ton of iron produced and by the time this blast furnace gas has been burned in stoves or under boilers the weight of gas discharged to atmosphere is on the order of eight times the weight of iron produced. Similarly for nonferrous metallurgy there may readily be from 10 to 20 times the weight of gases discharged to atmosphere as there is metal produced. A cement kiln in operation or a kiln in service to produce metallurgical lime may have on the order of 5 to 6 times the weight of stack gases as of clinker or lime produced, and at least the cement kiln, because of the very fine nature of its feed, is a very heavy dust producer. It may be noted that there have been two developments in progress for nearly three decades. Both are extraordinary in the industrial economics effected and in their ready availability to ever larger units of operation and their ever widening importance in industry, and both are productive of great quantities of finely divided material in furnacing. The first of these is the flotation process for ores, especially the metallics such as copper, lead, and zinc; and the second, powdered fuel combustion for power plant, industrial plants and metallurgical operations. Today, new developments, for example, flotation for the nonmetallics such as higher grade limestone for cement manufacture which requires still finer grinding and the powdered-coal-fired boilers with production ratings of over 1,000,000 lb of steam per hr, bring still more concentrated and hugely increased quantities of stack emission. Perhaps the honors for the greatest interest in the quantities and values escaping in waste furnace and equipment gases belong to the nonferrous metallurgical operations. Their record of achievement in the installation of dust and fume collection equipment, largely baghouses or Cottrell electrical precipitators, is exceeded by no other industry. Something of the magnitude and variety of equipment utilized in such recovery systems was covered by the writer in two papers presented to the Institute some 10 years ago.1,2 It is not intended to repeat the material of those articles, but it is thought that they complement this offering and should be noted. COPPER ROASTERS As the copper roasters are the first of the series of furnaces handling the copper-bearing concentrates in the usual copper smelter of today, it is in order to make them the first consideration. Multiple hearth sulphide roasters, not hard driven, often maintain their dust loss through exit gases at 3 pet or below of feed to furnace; in hard-driven or maximum-driven furnaces, exit gas losses often approximate 7 pet of charge with a ±2 pet variation for special conditions prevailing at some plants. A 5 pet loss of feed in a roaster gas exit, unless reclaimed, often makes the difference between a profit and loss operation, and in many cases substantial recovery is the very basis of dividend payments. As there is available very practical and successful equipment for the collection of the

Jan 1, 1950

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By Wilbur T. Stuart

TO assist the mining industry in attacking problems of water control, the U. S. Geological Survey has begun a program of research in mining hydrology. In certain fundamental respects water control is similar to development of water supplies from wells or to the drainage of agricultural lands, as many of the tools developed in recent years for quantitative ground-water problems are applicable, with modification, to mine-water problems. In 1952 a 30-day pumping test conducted jointly by the Eureka Corp. Ltd. and the Defense Minerals Exploration Agency provided an opportunity to gain knowledge concerning water movements around a flooded mine shaft. The methods of analyzing the data may be used as a guide for the evaluation of similar problems elsewhere. The Fad shaft of the Eureka Corp. is on Ruby Hill, 1 1/2 miles west of Eureka, Nev. The shaft was completed at a depth of 2465 ft in November 1947 at a site adjacent to the downfaulted block in which the ore was found. As the drift on the 2250 level progressed toward the ore zone, a large flow of water was encountered after the Martin fault was intersected. This flow exceeded the installed pump capacity, and an unsuccessful attempt to recover the shaft and the 2250 level was made in 1948.1, 2 Geology and Hydrology: The complex structure of Ruby Hill is that of an anticline broken first by thrust faulting and later by normal faults. The present orebody comprises several mineralized zones within a block of the Eldorado limestone of middle Cambrian age which was downfaulted 1400 to 1600 ft, and it may be related to a similar body mined at a higher level south of the Ruby Hill fault. At the depth of the largest zone of ore the block is roughly rectangular in shape, about 1000 ft wide and 1500 ft long, and dips about 30" NE, see Fig. 1. It is apparently bounded on the south by the Ruby Hill fault, on the east by the Jackson fault, on the north by the Martin fault, and the west by the Bowman fault. Within the block, but between the Ruby Hill and the Martin faults, are the Office and Adams Hills faults; west of the block and the Bowman fault are the Albion and Spring Valley faults. There are many conflicting reports concerning the water-yielding characteristics of the Eldorado limestone and the condition of the fault zones, that is, whether they are open or tight. However, the diamond-drill records indicate that open spaces as much as 2 or 3 ft across were encountered, and considerable cementing and lining of holes was necessary to maintain circulation of drilling fluid. There is also evidence that the Eldorado limestone was cavernous where it was mined in the early days south of the Ruby Hill fault. At the site of the Fad shaft the formations encountered from the surface down included the Pogonip limestone, Dunderberg shale, Hamburg limestone, and Secret Canyon shale. These formations did not yield large quantities of water to the shaft. The Pogonip limestone, which appears to be permeable and might yield water elsewhere, is above the water table in the vicinity of the shaft. The Secret Canyon shale, immediately overlying the Eldorado in some places but in most places separated from it by the Geddes limestone,3 is apparently tight and does not transmit water. During the 30-day test period the shale briefly confined the water in the underlying formations so that artesian conditions were observed in drillholes E and F, which are cased into the Eldorado limestone, whereas unconfined conditions were observed in drillholes B, C, and D, which were open to the shale. The Geddes limestone, which normally lies between the Secret Canyon shale and the Eldorado limestone, was not encountered in the Fad shaft. The Geddes, a flaggy, fractured limestone, is reported capable of yielding large volumes of water. Water stored in the interstices of this thin-bedded limestone within the Ruby Hill fault zone on the 1200 level of the Locan shaft drowned the pumps in 1923 when the Richmond-Eureka Mining Co. attempted to explore the area along the fault. Eldorado limestone was not encountered in the Fad shaft. In the ore-block area the Eldorado limestone was not entirely offset from other water-yielding formations by movement along the Bowman fault; therefore it may be hydraulically connected with the other formations. Adjacent to the Ruby Hill, Jackson, and Martin faults, the Eldorado lies in contact with other possible water-yielding formations. One of these, the Prospect Mountain quartzite, is separated from the Eldorado by thin, sheared, and broken beds of the Geddes within the Ruby Hill fault zone. A limited examination by the author of the Prospect Mountain quartzite in the Richmond mine at a higher level and south of the Ruby Hill fault indicates that the quartzite is poorly permeable. The monzonite mass south of the quartzite would be a further barrier to the flow of water. The poor permeability of this area is substantiated by records of levels at which water was encountered south of the Ruby Hill fault. In view of the normally low rate of ground-water recharge, if this desert area had been permeable, water levels could not have been maintained at altitudes of many hundred feet above the present water table west and north of Ruby Hill. Thus the ore-bearing block of Eldorado limestone is in contact with possible water-yielding rocks on at least two sides, and if the fault zones are possible conduits for water circulation the geologic and hydrologic conditions are suitable for the infinite-aquifer type of analysis as used and modified here. History of Pumping: During sinking of the Fad shaft a maximum pumping rate of 1500 gpm kept the shaft dewatered sufficiently, but in March 1948, after the 2250 level drift passed through the Martin fault into the Eldorado limestone, the pumps and shaft were flooded. Subsequently additional pump-

Jan 1, 1956

By M. J. Richards, A. Szirmae, G. R. Speich

The formation of austenite from ferrite, ferrite plus retastable carbide, spheroidite, and pearlite has been studied in a series of irons, Fe-C alloys, and plain-carbon steels using fast heating techniques. In the absence of carbide, austenite nucleates at ferrite/ferrite grain boundaries; nucleation is followed by the rapid growth characteristic of a massive transfornation. The trarnsformation occurs at 950°C at heating rates of 106º C per sec and cannot be suppressed. Metastable carbide dissolves before austenite forms and does not influence the transformation kinetics. For spheroidite structures, austenite nucleates preferentially at the jinction between carbides and ferrite grain boundaries. Growth from these centers proceeds until the carbide is completely enveloped; subsequent growth occurs by carbon diffusion through the austenite envelope. For pearlite structures, austenite nucleates preferentially at pearlite colony intersections. Carbide la)?zellae dissolve at the advancing austenite interface but complete solution of carbide does not occur; the residtial carbide is eventually dissolvled or spheroid-ized depending on the carbon cuntent. The magnitude and temperature dependence of the austenite growth rate into Fe-C pearlite when incomplete carbide dissolution is assumed are satisfactorily explained by an approximate colume diffusion model. The impurities present in plain-carbon steel reduce the growth rate of austenite in comparison to that jound in an Fe-C alloy. The formation of austenite has been studied in much less detail than the decomposition of austenite. This is primarily a result of the importance of harden-ability in determining the mechanical properties of steel. Recently, more interest in the kinetics of austenite formation has resulted from the discovery by Grange1 that rapid heating techniques strengthen steel by refining the austenite grain size. Although the strengthening effect is not large, it is accompanied by no loss in ductility. In addition, interest continues in rapid heat treatment of low-carbon steel sheet for tin plate applications.2,3 Among the few systematic studies of austenite formation are the early work of Roberts and Mehl4 on formation of austenite from pearlite and recent work of Molinder5 and of Judd and paxton6 on formation of austenite from spheroidite. Also, Boedtker and Duwez7 and Haworth and paar8 have recently studied the formation of austenite from ferrite in relatively pure iron, Kidin et al.9,10 have studied the formation of austenite in 8 pct Cr steels, and Paxton has recently discussed various aspects of austenite formation in steels." The present work was undertaken to determine the kinetics of austenite formation for a variety of starting structures including ferrite, ferrite plus metastable carbide, ferrite plus spheroidal cementite, and ferrite plus pearlitic cementite. Emphasis was placed on determining the active sites for austenite nucleation, determining the temperature and time range of austenite formation, and in the case of pearlite a careful study of the growth rate of austenite was made in the absence and presence of impurities. By using a variety of heating techniques including laser-pulse heating, it has been possible to study austenite formation in an isothermal fashion over a wide range of temperatures. EXPERIMENTAL PROCEDURE The alloys studied in the present work are a zone-refined iron with 4 pprn C, an Fe-C alloy with 130 pprn C, 2 Fe-C alloys with 0.77 and 0.96 wt pct C, and a plain carbon steel with 0.96 wt pct C. The zone-refined iron and Fe-C alloys contained 60 pprn and 200 pprn total substitutional impurities, respectively. The plain carbon steel contained 2400 pprn Si, 2000 pprn Mn, and 900 pprn Cr. Various heat treatments were given to these alloys to produce different starting structures of equiaxed ferrite, ferrite plus metastable carbide, fine pearlite, and spheroidite. These heat treatments are given in Table I. A wide range of heating rates were employed in this work because many of the reactions occur so quickly at temperatures in the austenite range that they are completed during the initial heating cycle unless very fast heating rates are used. Essentially the same heating techniques employed by Speich et a1.12 and Speich and Fisher13 were used in this work. For time intervals of 2 sec to 20 hr, simple hand immersion of 0.010-in. thick specimens in a Pb-Bi bath was employed. These specimens were quenched in a 10 pct NaC1, 2 pct NaOH aqueous bath. For time intervals of 100 m-sec to 2 sec, an automatic dunking and quenching device was employed with 0.002-in. thick specimens. Again, liquid Pb-Bi baths were used for a heating medium but now helium gas quenching was employed. For time intervals of 2 to 100 m-sec a laser heating device was employed with 0.002-in. thick specimens; a helium plus fine water-droplet spray was now used for quenching. Additional information on heating times shorter than 2 m-sec was obtained by study of the zones around the centrally heated laser spot. Here diffusion of heat from the centrally heated zone raises the temperature of the specimen locally to all temperatures between ambient and the peak temperature, but for times of the order of microseconds. All the heat-treated specimens were examined by

Jan 1, 1970

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.' The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8'10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By C. Feng, W. E. Krul

A study was made of the development of texture and the anisotropy in plastic flow of Ti-8Al-1Mo-1V alloy. Based on Pole figure determinations, the shifting of texture induced by rolling at approximately 400°C was found to be due primarily to slip rotation for the major Portion of the material. Grain boundary shear is believed to be an important factor. The anisotropy of the textured alloy was examined in terms of the variations of yield stress under tension and the ratio of bi -axial strain increments µp, in the temperature range 25" to 290°C. The results were related to Hill&apos;s theory on plastic anisotropy. The Schmid factors of (1100)[1120], (1101)[1120/, and (1101)[1120] slip systems were analyzed and found to be compatible with the observed anisotropy. Cross-slip between these planes was proposed as a possible deformation mode. In a number of published articles, considerable interest has been directed to the possible achievement of texture hardening in hcp metals. Following Backofen, Hosford, and Burke,&apos; this phenomenon was related to the yield criteria of the material and was expressed in terms of the biaxial strain ratio, r = d?w/d?l. The higher the value of r, the greater is the expected potential for texture hardening under certain loading conditions. For a given material, r varies with direction. Such variation can be traced to the anisotropy in plastic flow and can be explained within the framework of the various modes of deformation. Hatch2 found that a high r value coincides with a texture whereby the (0001) pole is closely aligned with the surface normal for sheet materials, Based on the analysis of the slip on the {1010}, {1011}, and (0001) planes, Lee and Backofen3 and Avery, Hosford, and Backofen4 concluded that the resistance to thinning is reduced by the operation of the (0001) <1120> slip system; with this reasoning they were able to explain the low r values (i.e., r « 1) observed in magnesium alloy sheets in the rolling direction and in commercially pure titanium in the transverse direction. The general equation, dealing with plastic flow in a polycrystalline aggregate has been used to correlate the plastic anisotropy and texture. In this expression, T and s are shear and normal stresses, and dri and d? are shear and normal strain increments, respectively. Assuming that five slip systems are operative within each grain and applying the principle of maximum work,5,6 one can determine the m value among the available systems. On this basis, Hosford7 and Chin, Nesbitt, and Williams&apos; were able to correlate m with yield stress under plane-strain compression, and Svensson9 was able to predict the variation of yield stress in textured aluminum. These workers made their analyses from materials in which slip operation is known to be associated with plastic flow. Questions remain regarding the derivation of Hill&apos;s theory on plastic anisotropy,10,11 since it was formulated on von Mises&apos; yield criterion.&apos;&apos; Its ability to deal with other forms of deformation has been in doubt.13 Others have discussed the validity of Hill&apos;s quadratic equation relating strain and yield stress.14&apos;15 For hcp titanium, deformation by various modes of slip and twinning operations has been reported.16-20 If all possible modes of deformation operate and contribute substantially to the plastic flow, it is difficult to imagine how the quadratic expression can suitably describe the anisotropic plastic flow of titanium alloys. Backofen and Hosford15 considered that Hill&apos;s is a macroscopic theory and implied that the major mode of deformation by slip mechanism will adequately describe anisotropy of the material. In the present investigation, slip operation will be shown to play the major role in the development of sheet texture induced by rolling of a commercial titanium alloy. Although twinning and other modes of deformation may also operate, their operation is believed to be secondary. The anisotropic properties of the sheet, which can be expressed in terms of directional variation of r, µp = -d?w/d?l and the yield stress will be shown to be governed primarily by slip operation. MATERIALS AND EXPERIMENTAL TECHNIQUES The titanium alloy chosen for the present investigation had a nominal composition of 8 wt pct Al, 1 wt pct Mo, 1 wt pct V, and 0.1 wt pct interstitial impurities. Sheets varying between 0.1 and 0.15 in. thickness were used. The alloy was received in a condition which was prepared by rolling at 900°C and annealing at 700°C. Subsequently, the sheets were subjected to further reduction in thickness by rolling at 400°C. A total reduction in thickness of 65 to 70 pct was obtained by a series of quick passes in a rolling mill with intermediate reheating. Further reduction in thickness was not possible due to cracking developed at the edges of the sheets. X-ray measurements were conducted in a Siemens and a Norelco unit to determine the texture of the sheets. Reflection techniques were used exclusively with CuK, radiation and a nickel filter. The loss of X-ray intensity due to geometric defocusing was calibrated with a technique described previously." The (0001), (1010), and (1071) pole figures were plotted from 0 to 80 deg, and to present the texture elements quantitatively, inverse pole figures were constructed following the technique described by Jetter, McHargue, and Williams.22 Tensile experiments were carried out at 25", 175",

Jan 1, 1970

By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.&apos; reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By B. A. Wilcox, A. H. Clauer

The steady-state creep of TD Nickel NL + 2 001 pct TltOz) has been studied orer the telirperatve range 325&apos; to 1100O and the stress range 15,000 to 36,000 psi. At high temperatures (aboue 0.5 T& gran-boundary slzding is the )nost znportant )node of creep deformation, and the steady-state creep rate, is, can be related to stress and temperature by: where Q = 190 kcal pev mole and n has an unusually high value of 40. A creep mechanism based on cross slip of dislocations around The O2 particles can satisfactovily explain the low-temperature (T < 0.5 T,) cveep behavior, and the follo wing relation is applicable: Q, (a) is found to decrease from 57 to 46 kcal per mole as the stress is increased from 32,000 to 36,000 psi. THERE have been a variety of theories proposed to explain the influence of dispersed second-phase particles on the yield strength and flow stress of metals, and these have been reviewed recently by Kelly and icholson.&apos; However, only several attempts2"4 have been made to develop mechanistic treatments which characterize the creep behavior of dispersion-strengthened metals, and to date these have not been fully evaluated experimentally. weertman2 and Ansell and weertman3 proposed a quantitative creep theory for coarse-grairzed dispersion-strengthened metals, based on the concept that the rate-controlling process for steady-state creep was the climb of dislocations over second-phase particles, as suggested by choeck. The theory predicted that the steady-state creep rate, <,, was proportional to the applied stress, a, for low stresses and that is a4 o for high stresses. The activation energy for creep, Q,, was equivalent to that for self-diffusion, Qs.d., in the matrix. Some limited experimental evidence in support of this theory was obtained on a recrystallized Al-Alz03 S.A.P.-type alloy by Ansell and Lenel.6 Ansell and weertman3 also developed a semiquanti-tative theory for high-temperature creep of lineg-rained dispersion-strengthened metals in order to explain their results on an extruded S:A.P.-type alloy, which had a fine-grained fibrous structure. They suggested that the rate of dislocation generation from grain boundaries was the rate-controlling process, and fitted their results to the equation: where Q, was found to be 150 kcal per mole, i.e., QC- 4Q,.d. in aluminum. Similar high activation energies for creep7-&apos;&apos; and tensile deformation" of dispersion-strengthened alloys have been observed by other investigators for S.A.P.,&apos;" indium-glass bead omosites, and Ni + A1203 alls.&apos; There is no general agreement regarding the mechanisms involved in the creep of dispersion-strengthened metals, and this is due in part to the lack of detailed studies relating the structures of crept specimens to the mechanical behavior. The present investigation on thoriated nickel was undertaken with the aim of studying the structural changes which occur during creep of a dispersion-strengthened alloy and rationalizing the observed mechanical behavior in terms of the creep structures. EXPERIMENTAL METHODS The material used in this investigation was 1/2-in.-diam TD Nickel bar, which contained 2.3 vol pct Tho,. Obtained from E. I. duPont de Nemours & Co., Inc. The final fabrication treatment by DuPont consisted of -95 pct reduction by swaging followed by a 1-hr anneal at 1000°C. Transmission and replica electron microscopy revealed that the material had a fine-grained fibered structure with an average transverse grain size of -1 p and a longitudinal grain size of 10 to 15 p. Selected-area diffraction indicated that the fiber axis was parallel to (OOl), in agreement with the results of Inman eta1." All creep specimens were vacuum-annealed at 1300°C for 3 hr prior to testing. Transmission electron microscopy showed that the only structural change due to annealing was a slight decrease in dislocation density, confirming the reported high degree of structural stability.13 Furthermore, recrys-tallization or grain growth during creep was never observed. The structure typical of uncrept material (after the 1300 C, 3-hr anneal) is shown in Fig. 1. The grain boundaries are predominantly high angle and. although some areas show a tangled cell structure, the grain interiors are relatively dislocation-free. Individual dislocations are strongly pinned by the Tho2 particles; i.e., very rarely did dislocations move within a thin foil. The grey "halos" around some of the larger particles which protrude out of the foil surface arise from contamination in the electron microscoge. The Tho, particle size ranged from -100 to IOOOA, and the distribution is shown in Fig. 2. The technique used to obtain the data in Fig. 2 consisted of dissolving the nickel matrix in acid, collecting the Tho2 particles on cellulose acetate, and measuring about 1000 particle diameters in the electron microscope. Similar results were obtained by measuring about 600 particles in thin foils, an; the average particle size was found to be 2r, = 370A. Using the data in Fig. 2 (annealed structure), the mean planar center-to-center particle

Jan 1, 1967

By W. F. Chiao

With the application of dislocation damping theory an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. A ductile steel was compared with a brittle stee1 by simultaneously measuring the ultrasonic attenuation and velocity during tensile test, and the density of free dislocations and their mean loop length were then calculated as a function of strain. The results showed that in the ductile steel there was always a large generation of dislocations and great extension of loop length occurring at some stage within the early plastic region. In contrast, the brittle steel showed very little or no such sudden changes in dislocation dynamic states after the onset of plastic deformation. Furthermore, a strong temperature dependence of dislocation dynamic states was also observed in the ductile steel and a hypothesis was suggested that a thermally activated process of dislocation rearrangement could occur at higher deformation temperatures. The activation energy of dislocation rearrangement at room temperature was estimated as about 2030 cal per mole.C. DUCTILITY is an indispensible property in the application of engineering materials, especially steel. During the past two decades the theoretical and experimental approach to the understanding of flow and fracture of metals has been constantly undergoing changes and progress." while the fracture behavior of metals can be influenced by many factors such as chemical Composition,3 second-phase particle mor-phology,4 and dislocation arrangement,5 it is now a general belief that the fundamental understanding of the ductile-brittle fracture phenomena of solid materials must stem from the study of dislocation dv-namics developed under stress conditions.6,7 Most of the traditional ductility tests, such as Charpy impact test, slow bend test, and tensile fracture test, cannot by themselves reveal directly the mechanisms of ductile to brittle transition of materials. In the experimental investigation of tensile ductility it would be ideal to be able to study directly the dynamics of dis-locations in a bulk specimen during the process of deformation. Since the ultrasonic pulse technique is the only satisfactory method for studying dislocations and the fine details of deformation characteristics in metals in the course of a tensile test, it would appear that a comparative study of ultrasonic attenuation changes during tensile tests of metallic materials exhibiting different ductility might be very informative. So far no work comparable to this study has appeared in the literature. Recent progress in both theory and experiment has indicated the feasibility of studying the dislocation mechanisms of ductility behaviors by ultrasonic measurements during tensile test. Granato and Lucke8 have developed a quantitative theory that enables the calculation of dislocation density and their average loop length from the measurements of ultrasonic attenuation and velocity, and several investigators, including Chiao and Gordon,9&apos;10 have shown that simultaneous ultrasonic measurements can be successfully made during a tensile test. Furthermore, many investigators11-13 have repeatedly proposed in the past several decades that deformation and fracture are mutually self-exclusive, and that the ability or inability of a material to deform plastically, i.e., to generate dislocations, is a major factor in determining whether the material will be ductile or brittle. Thus, in the present work an attempt was made to determine whether the generation and extension of dislocations is inherently more difficult in a brittle steel than in a ductile steel. This article is principally concerned with the study of the relation between the propagation of ultrasonic waves and tensile deformation in a steel series which displays quite different toughness at room tempera-turk. changes in attenuation and velocity of ultrasonic waves have been measured as a function of strain during the deformation process. The results have been interpreted in terms of the vibrating string model for dislocation damping as developed by Granato and Lucke, and it has been found that some of the more subtle predications of the model are in good agreement with the experiments. This would be especially meaningful because most of the previous experiments in testfying the model were carried out with single crystals of high-purity materials and little work has been done with polycrystalline steel alloys. EXPERIMENTAL PROCEDURES AND RESULTS Specimen Materials. The tensile specimens used throughout this experiment were of two compositions selected from a series of Fe-Mo-0.77 pct Mn-0.22 pct C steels prepared for a ductile-brittle fracture transition study. One steel contains 0.21 pct Mo and the other 1.03 pct Mo. These two compositions were chosen for the present study because they possess quite different toughness properties at room temperature. The 0.21 pct Mo steel is quite ductile while the 1.03 pct Mo steel is rather brittle, as measured by the standard Charpy impact test. The alloys had been prepared by vacuum induction melting and chill casting in steel molds. The ingots were hammer-forged into 1/2-in.-sq bars from which tensile specimen blanks were cut. These blanks were first normalized under argon atmosphere at 1700°F and then reaus-tenitized and isothermally transformed at 1050°F to a bainitic microstructure. The chemical compositions, heat treatments, hardness measurements, and Charpy transition temperatures of the two steels are listed in Table I.

Jan 1, 1970

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan&apos;s theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By Eugene S. Meieran

The effects of methods of crystal growing, wafer sawing, polishing, routine handling, diffusion, and epitaxial growth on the defects in GaAs are reviewed and studied using reflection and transmission X-ray topographic techniques. In general, it was found that boat-grown crystals exhibited fewer defects than Czochralski crystals, although all crystals showed large numbers of precipitates visible when examined in the electron microscope. Mechanical surface treatments such as sawing and mechanical polishing introduce damage to a depth of about 5 µ, most of which can be removed by suitable chemical or chem-mechanical polishing. In addition, defects can be introduced through routine handling of wafers, for example with metallic tweezers. These defects can be quite severe, and have been observed 20 µ below the wafer surface. Defects can also be introduced through diffusion and epitaxial growth. These defects, which include precipitates, growth pyramids, stacking faults, dislocations, and so forth, can be detrimental to device fabrication. It is shown that wafers or films which appear defect-free optically can contain defects visible in the X-ray topographs. WHILE the use of GaAs in the semiconductor industry has increased very rapidly in the last few years, due mainly to the recent development of many important GaAs devices,1,2 the major limit to the production of commercial quantities of many GaAs devices remains a severe lack of suitable materials technology. This lack is apparent in two critical areas. First, production quantities of high-quality GaAs crystals, reproducibly doped and precipitate-free, simply are not available commercially, although some reasonable quality material is available on a limited first-come, first-serve basis. Second, in comparison to silicon technology, little is known about the effects of processing variables on the defects either present in as-grown GaAs or introduced through processing and handling of wafers. These areas are now receiving some attention from semiconductor device manufacturers, who are studying defects in GaAs in order to better understand how either to prevent their occurrence or to cope with their existence. Most investigations of the defects in GaAs have been made by optical microscopy3-5 or transmission electron microscopy techniques.&apos;-&apos; Recently, however, the imaging techniques of X-ray topography, electron mi-croprobe analysis, and scanning electron microscopy are being applied to the study of GaAs.9-14 In the case of X-ray topography, a one-to-one image is obtained that must be photographically enlarged. In compensa- tion, the defects within entire wafers may be imaged by simple scanning (Lang technique15) if the wafer is reasonably perfect, or by using the scan oscillation technique developed by Schwuttke16 if the wafer is warped or distorted. The purpose of this paper is to both review and extend the general application of X-ray topographic techniques to GaAs. Emphasis will be placed on the effects of growth and process variables on the quality and perfection of both bulk and epitaxial GaAs. Reference to optical or electron microscopy results will be made when useful. Since the effects on defects of a wide variety of processing variables such as crystal growing, sawing, polishing, diffusion, and epitaxial growth will be somewhat superficially reviewed, a fairly extensive bibliography of the most important recent results in these areas is included. However, for completeness, important defects will be illustrated here, although such defects have been previously shown by others. While this paper is concerned with defects rather than with the physics of X-ray scattering, the mechanisms of contrast formation in the topographs will of necessity be briefly mentioned. EXPERIMENTAL GaAs crystals, both boat-grown18 and Czochralski-grown,&apos;8 containing a variety of dopants of various concentrations, were purchased from outside vendors. Wafers were sliced from the crystals using a Hamco ID saw and were mechanically polished using 1 µ diamond paste. Chem-mechanical polishing was done in bromine-methanol as described by Sullivan and Kolb.18 Chemical polishing was done using a modified sulfuric-peroxide solution, 11 parts H2SO4, 1 part 30 pct H2O2, 1 part DI water.5 Zinc diffusion was carried out in a closed tube, using a 10 pct Zn-In source at 825°C for 1 hr. Oxide masking techniques were used to select the area to be diffused. Epitaxial wafers were either purchased or prepared here. All epitaxial runs prepared here were carried out using a Ga-GaAs-AsC13 source in a closed tube at a substrate temperature of 750°C. Wafers were chem-mechanically polished and gas-etched prior to deposition. The X-ray topographs were taken on a Krystallos Lang camera, operating in the transmission scanning geometry (Lang technique15) or in the reflection scanning geometry (modified Berg-Barrett technique20,21). MoKa, radiation was used for all transmission topographs using a Jarrell-Ash 100-µ spot focus. CuKal radiation was used for all reflection topographs using a General Electric CA-7 1-mm spot focus X- ray tube. Topographs were printed from an intermediate contrast inversion film, so the contrast shown in all figures here is the same as that of the original 50-µ-thick emulsion L4 Iiford nuclear plate used to record the topograph.

Jan 1, 1969

By William A. Kapp

INTRODUCTION Coal is being mined from beneath residential areas, structures, bodies of water and other surface features in the coalfields to the north, south and west of Sydney. The particular problems faced by mine operators in these areas vary considerably due to differences in the overlying strata, the variation in the depths of cover and also depend on the number of seams being mined. Detailed subsidence work first commenced in the Southern Coalfield in 1965 and is now being carried out over areas of extraction at roost collieries. The analysis of the results of the early investigations and of the work which continues in other areas has shown that there is a consistent relationship between subsidence and mine geometry and has led to a reliable empirical method for the prediction of subsidence. In addition, particular aspects of each of the studies in the Southern Coalfield results in a clearer understanding of strata movements and of the resulting subsidence. The features of a subsidence trough apply generally to all areas but the magnitudes of specific features vary according to the stratigraphy of the particular coalfield. The aim of the subsidence work is to quantify the effects of subsidence for a range of mining geometries and mining conditions to enable the maximum safe recovery of coal from beneath surface features. The importance of local subsidence investigations is becoming more evident to mine operators and to authorities or organisations with surface interests. The subsidence work also provides important information on the stabilities of pillars of coal which remain unmined between panels of extracted coal. These pillars are not extracted either because of poor mining or geological conditions, or because pillar extraction is not part of the particular mining operation. Subsidence studies over these coal pillars clearly establish whether the pillars have remained stable or have failed to support the overlying strata. With subsidence studies continuing over several years, it is possible to assess the stabilities of these pillars on a long term basis. BACKGROUND TO THE STUDY OF SUBSIDENCE Geographical setting Most of the black coal production in Australia comes from the Sydney Basin. The coal seams extend for approximately 350 km along the coast of New South Wales and inland for distances up to 150 km. The City of Sydney is located near the centre of the coastal extent of the Basin where coal has been mined at a depth of 900 m. The Sydney Basin is part of the Main Coal Province of NSW and is divided into several coal- fields. The Southern Coalfield to the south of Sydney contained 15 operating mines and produced 12.7 million tonnes of raw coal during the 12 months to June 1981. The collieries discussed later are shown in Fig. 1. The prominent topographical feature of the area is the Illawarra Escarpment which rises to 400 m above sea level, or 300 m above the coastal strip along the South Pacific Ocean. The escarpment is mainly sand- stone and the weathering of the cliff line has resulted in a covering of talus material at its base. Several collieries are located near the seams which outcrop along the escarpment. The city of Wollongong is located in a scenically attractive area on the coastal plain. The suburbs of Wollongong extend north along the coastline, south to beyond Lake Illawarra and west to the lower slopes of the escarpment. The Illawarra Escarpment forms the eastern boundary of the Woronora Plateau. On a regional scale the surface dips gently to the west and thus forms a watershed for the rivers, most of which flow in a general north westerly direction, sometimes forming steep gorges in the sandstone. These rivers join the Nepean and Hawkesbury River system and flow into the Pacific Ocean north of Sydney. Seven dam have been constructed over the Southern Coalfield (Fig. 1) and with one large dam further to the west, their stored waters provide the needs of the Cities of Sydney and Wollongong and the surrounding districts. A large part of the area affected by mining is the undeveloped bushland of the associated catchment areas. In general no special precautions have been required with respect to subsidence with the exception of the dam structures and stored waters. With the increase in coal mining activities and the expanding residential development south of the City of Campbelltown in the outer Sydney Metropolitan area, subsidence is becoming an increasingly important area of research. Structures which have been affected or considered are townships and extensive residential areas, buildings of historical importance, major tollways, and a high pressure natural gas pipeline. The subsidence effects of mining beneath natural features within national parks is coming under study as mining approaches these areas. Geological setting The coal seams of the Southern Coalfield lie within the Illawarra Coal Measures. They contain high rank coking coal used in the local steel industry and for export. The Bulli Seam is mined extensively through- out the Southern Coalfield with the lower Wongawilli Seam being second in importance with regard to coal production. The top of the Bulli Seam is taken to be the marker horizon between the Permian Coal Measures

Jan 1, 1982

By F. D. George, M. J. Salkind

Al3Ni whisker-reinforced aluminum was found to exhibit good Charpy impact toughness and little notch sensitivity even though its room-temperature tensile elongation parallel to the whiskers is only 2 pct. This impact behavior was maintained d liquid nitrogen temperature (-196"C). It is postulated that this behavior is due primarily to the presence of the continuous aluminum matrix which provides sufficient 10calized ductility in the vicinity of the crack tip to absorb considerable energy from the advancing crack. The impact behavior of Al-Alni was found to be quite anisotropic. Of six orientations studied, the transverse orientation having the notch normal to the whisker axis was found to exhibit the lowest impact energy, whereas the transverse orientation having the notch parallel to the whisker axis was found to exhibit the highest impact energy. A significant differnce was noted between the impact behavior of material containing needlelike whiskers and that containing bladelike whiskers. Only two of the six orientations studied exhibited complete fracture for the material containing needlelike whiskers. On the other had, most of the specimens containing bladelike whiskers exhibited complete fracture. It was postulated that the bladelike whiskers block transverse flow, thus reducing the amount of plastic deformation ahead of the crack tip. One of the more significant advantages of composite materials is the prospect of combining high strength with toughness. In general, toughness is associated with materials which exhibit considerable ductility and can deform plastically in the presence of a stress concentration. Very strong materials which resist plastic deformation generally exhibit low toughness. At first glance, then, it would appear as though strength and toughness are mutually incompatible so that useful engineering materials would have to be a compromise between the two. One approach to the problem of combining the high intrinsic strength of ceramics with the toughness of metals was to mix them together to form a cermet. Unfortunately, the toughness of cermets was found to be rather disappointing. Whisker reinforcement of metals, however, appears to be a more promising approach. It has been demonstrated that whisker-reinforced metals produced by unidirectional solidification exhibit enhanced strength due to the presence of high strength nonmetallic whiskers. The total strain capacity of these composites in the direction of fiber alignment is limited to that of the fibers, the matrix being unable to carry the load once the fibers have failed. A characteristic, then, of whisker composites is low ductility in the direction of whisker alignment, on the order of a few percent elongation. This low elongation, which is usually associated with brittle behavior, should not be taken as an indication of low toughness. Such a material can exhibit significant ductility in directions other than parallel to the fibers7 and can therefore possess significant intrinsic toughness. Toughness in a fiber-reinforced metal is derived from several mechanisms. The first is due to the toughness of the matrix itself. A continuous ductile metal matrix can act as an effective crack arrest medium by undergoing localized plastic deformation. Cracks initiated from the surface of the composite or from a brittle fiber failure must travel through the matrix before reaching another brittle phase particle. A second crack arrest mechanism peculiar to fiber composites is due to the fact that, as a crack travels through the matrix and approaches a fiber, the plastic deformation ahead of the crack tip will result in loading of the fiber. This causes the matrix shear strength in the plastic zone to be apparently higher, thus extracting more energy from the crack and diverting the crack at an angle to the original direction of propagation. A third crack arrest mechanism occurs in fiber composites which exhibit a weak bond between fiber and matrix. The idea was proposed by Cook and Gordons that if a crack propagating transversely in a fiber composite were made to turn and run along the fibers by decohesion of the fiber-matrix bond, then toughness would be imparted by the blunting of the crack tip and the creation of new surfaces. The last mechanism, interfacial decohesion, is commonly noted in naturally occurring fiber composites such as wood, bone, and bamboo, and has been observed in man-made composites such as glass fiber-reinforced resins,g silica fiber-reinforced aluminum," laminated steel," and tungsten and silica fiber-reinforced electroplated copper.&apos;&apos; The first mechanism, crack arrest by plastic deformation in the matrix, has been noted in tungsten wire reinforced cast copper." The purpose of this investigation was to quantitatively assess the toughness of a whisker-reinforced metal as a function of orientation. Previous investigation considered only cracks propagating nominally perpendicular to the reinforcement. In this investigation, crack propagation in three mutually perpendicular directions as well as three intermediate orientations was investigated. The system chosen for study was the unidirectionally solidified A1-A13Ni eu-tectic alloy which has a microstructure consisting of 10 pct by volume of A13Ni whiskers in a matrix of aluminum This material exhibits two different kinds of whisker morphology, depending upon the rate at which it is solidified.&apos; At low rates of solidification (less than 2 cm per hr) the whiskers are bladelike, whereas at higher rates of solidification they are

Jan 1, 1969

By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes&apos; expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers&apos; mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.&apos; Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1&apos; with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967