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By Thomas Clagett

THE Pocahontas coal field comprises the area in Tazewell County, Va., and Mercer and McDowell Counties, W. Va., in which Nos. 3 and 4 Pocahontas seams of bituminous coal are mined. It is a mountainous region with ridges rising 300 to 1000 ft. (91 to 305m.) above the very narrow valleys and, except for some poorly kept farms along the tops of the ridges and the area occupied by the mining and coking plants and villages, is wooded throughout. First shipments were made from Pocahontas in 1883. There are now, about 100 mines, 95 per cent. of which are drift mines. At the end of 1920, approximately 298,000,000 gross tons of coal had been produced and 35,000 acres of coal mined. No. 3 seam is from 4 to 10 ft. (1.2 to 3 m.) thick, but the change is gradual and the thickness fairly uniform in any particular locality. It has a streak of bone, about 2 in. (5 cm.) thick, io which the coal adheres on both sides. In parts of the field this bone is replaced by hard slate, usually from 2 to 4 in. thick. The seam has a slate or fireclay bottom and a draw-slate top. No. 4 seam is from 65 to 80 ft. (19.8 to 24 m.) above No. 3 seam, and of minable section only in the western part of the field. It is from 3 to 8 ft. thick and has two streaks off bone, each from 1 to 2 in. thick. It has a fireclay or slate bottom and is overlaid by from 4 to 24 in. of a laminated coal and slate, locally termed "black rash," which is separated from the coal seam by about 3 in. of slate. This "black rash" averages about 25 per cent. ash, but contains some clean coal. The coal in both seams is quite soft. Cleavage sufficiently well defined to exert an influence on the mining is rare. Overlying strata are slates, shales, and sandstones, the sandstones predominating, extending from .30 to 1000 ft. above No. 3 seam. The strata directly above the. draw slate of No. 3 seam, or "black rash" of No., 4 seam, and up to the first sandstone are usually slates or shales, about 10 ft. thick over the

Jan 5, 1922

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.' The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By G. H., Wigton

THE present milling operations of the Chief Consolidated Mining Co. consist- of flotation of oxidized minerals from siliceous ores of the Tintic Mining district, Utah. As the lead, silver, and gold minerals that give the ores economic value are almost entirely oxidized; their successful flotation has necessitated the solution of many new problems. Laboratory effort resulted in the selection of a, natural float for the oxidized minerals. 'By "natural float," I mean that no reagent was added to produce a sulfide film on the osidized minerals before or while subjecting them to flotation operations. As compared to methods involving sulfide filming, the natural float was selected because it promised successful treatment of a larger variety, of ores without change in quantity or kind of reagents, as well as a better economic balance between metal recovery and concentration ratio. In explanation, I can, state that with sulfide filming, the efficiency of the method decreases rapidly with increase of hydrated, iron osides in the ore, whereas with the natural float the same effect has not been noted. Evidence shows that although sulfidizing can produce greater metal recoveries, it yields a concentrate so much lower in grade that no advantage results.

Jan 1, 1928

Victor G. Hills, Cripple Creek, Colo. (communication to the Secretary): In continuation of the subject of the perform ance of "baby machine-drills," presented by Mr. Thane, I sub mit the following records of work done with these drills in the Cripple Creek district of Colorado. Two years ago, the Anchoria-Leland mine began to use baby drills ; and, to make the experiment more complete, began by purchasing two machines, of the same size, but of different make. The little drills were first used for stoping and up raising, in which they achieved at once an unqualified success. Soon after, they began to be used for the smaller branch-drifts and prospecting cross-cuts, while the large two-man drills were still used for the main drifts. Now they have almost entirely superseded the large drills, since it has been found that they will do any ordinary work in the mine at less cost, both for labor and for powder, per ton of rock broken. The large drills, of course, make more rapid progress; but it is only where time is a specially important factor that they are now used. The Portland mine, where, until within a year, only the large machines were used, is now using some small drills for stoping, and also for drifting. Mr. Thane speaks of having two men to operate a baby-drill; but in this district the baby-machine is always worked by one man without help. Again, in Prof. Christy's postscript, the quoted extract from a letter of Mr. L. T. Seymour, the South African engineer, mentions a " 2 1/2-inch Little Giant," as though that were the smallest machine used in that region. These statements leave some doubt as to just what Mr. Thane means by a " baby-drill." To avoid any such uncertainty as to the present communication, I will say that the large or two-man drill in common use at Cripple Creek has a 3 1/8-inch cylinder; while a few mines employ a 3-inch, and a few, in running large tunnels, a 3 1/2-inch drill. What we call a baby-drill here has a

Jan 1, 1900

Edgar Hall, Tenterfield, New South Wales (communication to the Secretary): Mr. Klepetko* asks for information showing at what percentage antimony and arsenic, as impurities, begin to affect injuriously the quality of brass.

Jan 1, 1899

By K. Harms, T. D. Jones

TO unload large tonnages of lead bullion cast in 100-lb. bars is a problem which has confronted the lead refineries for many years. The bars, on arrival, must be restacked for unloading by truck or hand-charged to charging machines. Selected crews of labor, capable of working at sustained speeds for five- or six-hour periods, are required for this exhausting task. Due to the fatigue involved crew personnel changes rapidly. During the war it became increasingly difficult to maintain crews, especially in critical labor areas, so that the development of casting and shipping ten-ton lead blocks from the smelters to the refineries became a must in our operating program. For many years lead refineries, when making interdepartment or intradepartment transfers, have cast lead blocks weighing five or ten tons which are easily handled by crane by merely attaching the crane hook to a steel anchor embedded in the frozen lead blocks. In previous years, the practice was to use regular smelter slag pots which, due to their rounded shape, produced what were called "buttons" by the refinery personnel. The button-type blocks were unsafe as they rolled and tipped easily and were unsatisfactory for stacking since no piling pattern could be followed. To remedy this situation, flat-bottom molds came into general use and later the bottoms were made concave to prevent slipping.

Jan 1, 1946

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.' The vCO3 structure, which was determined very recently,' has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By J. M. Vonfeld, V. D. Hanson, W. K. Heinlein

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion No. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and - 3/8-in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3/8-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 1/4 in., and 11/4x3/8 in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into 3/8x0 which is cleaned in the fine coal plant and 3x3/8 for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1952

By R. V. Horrigan

High purity ZrC14 (25 to 200 ppm of metallic impurities) can be readily prepared in simple apparatus by thermal decomposition of alkali chlorozirconate fused salts at 500° to 600°C and at atmospheric pressure. Suggested phase diagrams for the systems NaCI-ZrC14 and KCI-ZrCI, are presented. ALKALI chlorozirconate compositions — anhydrous fused mixtures of ZrCl4, NaC1, and KC1— are manufactured commercially and are used by the magnesium industry to introduce zirconium into magnesium alloys. Zirconium refines the grain size and improves the physical properties of many important magnesium alloys. In the course of working with chlorozirconate compositions of high ZrCl4 content, it was noticed that these salts decomposed progressively itwaswith increasing temperature to yield considerable amounts of a ZrCl4 sublimate of high purity together with a solid chlorozirconate residue. Further research led to: 1—improvements in the

Jan 1, 1956

US 4,152,143-Continuous precipitation of cement copper from an aqueous ore leach solution mixed with pieces of iron as the precipitant Copper depositing on the pieces of iron is loosened and removed therefrom by means of constant but regulated oscillating movement of the pieces of iron in a horizontal elongated chamber, and the loosened copper is separated and collected from the mixture E Kausel and R Nissen, assigned to Klockner-Humboldt-Deutz A G May 1, 1979 8 pp (75-100) Filed 1-12-78 (868,981) (Drawings below) [ ] US 4,156,711-Removal of metal impurities from an acidic zinc or cadmium solution prior to electrolysis. Impurities such as manganese, cobalt, nickel, and thallium are selectively precipitated by contacting the solution with persulfuric acid or an ammonium or alkali metal salt thereof while maintaining a pH value of from 1 5 to 4 5 This patent is a continuation-in-

Jan 1, 1980

By C. L. Dake

AN insistent and steadily growing demand is evident for the broadening of undergraduate curricula in engineering. Among suggested additions are training in public speaking, report writing, business law and contracts, accounting, finance, money and banking, scientific management, economics, social and labor problems, psychology, and ethics. The demand for these subjects comes from the older engineers and from the industries that employ our graduates. Of course, many of the men who suggest such changes are influenced largely by their personal needs and contacts, but the demand is sufficiently widespread to merit serious study by educators. In fact, many educators themselves concur in the proposals for broader training. These matters were examined intensively a few years ago in an exhaustive study of engineering education. Opinion at that time was rather strongly against any profound change. Since then, however, the whole economic system has undergone violent disruption. Even if recommendations made a few years ago were appropriate to the conditions then- obtaining, the enormously changed conditions of the present make advisable a further careful study of this problem. In recent years, mergers, to reduce costs, have sharply limited the number of engineers employed and have thereby intensified the struggle to secure positions. In this stiffer competition, engineers with the most adequate training undoubtedly fare the best.

Jan 1, 1934

By Stanley J. Gasior, Albert J. Forney, Joseph H. Field

Most bituminous coal mined near Eastern industrial areas requiring high-Btu pipeline gas is caking and therefore unsuitable for fixed-bed pres- sure gasification by present techniques. If the caking property of such coal can be destroyed, the resulting fuel can be gasified in a fixed bed at pressure with steam and oxygen as a preliminary step in making a high-Btu gas. To find a practical way to convert strongly caking coals of granular or small lump size to noncaking fuel was the object of this study. In previous work, strongly caking coals of 1/8- to 1½ -in. size were converted to a noncaking coal char by treatment in a static bed in about 3 hours1 and coal of 18-100 Tyler mesh in a fluidized bed in about 5 min.2 An inert gas such as steam, nitrogen, carbon dioxide or a mixture of all three with a small amount of oxygen was used in both studies. In our work a strongly caking bituminous coal from the Pittsburgh seam of 4-8 Tyler mesh size was converted to a noncaking form in free-fall in about 2 sec by dropping it through a countercurrent flow of steam containing 4% to 7% oxygen at 1150º-1200°F and 300 psig. This method should also be applicable to smaller-sized material.

Jan 3, 1965

By T. MacDONALD

ATHOUGH flotation has been a commercial process for over twenty years, the last two years have witnessed a sudden and phenomenal increase in our knowledge of how to separate minerals heretofore not considered amenable to flotation at all. As remarked by Professor Locke in the January issue. "Either commercial or laboratory flotation is reported on zircon, ilmenite, carnotite, kyanite, scheelite, chromite, fluorite, feldspar, cassiterite, wolframite, barite, and clay. Attractive patents on soap flotation are U. S. Nos. 2,000,656 and 2,040.187. A survey by Ralston in the February E. & M. J. adds many other minerals to this impressive list. The simple but pregnant fact is that any mineral can be coated, directly or indirectly, with a water-repellent coating, and since this is true, it follows that any mineral can be floated. Fundamentally, this is no new discovery, where, for instance, is the mineral that cannot he washed from a pair of dirty hands by means of soap and water, given the absence of refractory greases or oils which would have no proper place in flotation ?

Jan 1, 1937

By Gilbert E. Doan

WHEN metallurgists and other engineers meet their college classmates or former teachers, the conversation will frequently become reminiscent and finally turn to engineering education. These graduates have tested the value of their college training in the hurly-burly of the outside world so respectful attention is due their opinions, which, strangely enough, fall into two opposite categories. A member of one group expresses a deep-seated conviction that engineers should have a fuller foundation of physical chemistry, another asks for a more thorough training in mathematics, others wish a more thorough grounding in refractories, a series of courses in petroleum engineering, or in electric welding. Each alumnus of this group

Jan 1, 1937

By J. Hall Carpenter, James E. Lawver

Shortly after the passage of the Taconite Amendment in Minnesota, several mining companies announced their intention to build new magnetite taconite plants and another announced its intention to augment present facilities. It is clear that Minnesota will enjoy an expanding magnetite taconite industry, but despite the fact that the reserves are large, eventually they will have to be supplemented by oxidized deposits. Furthermore, not all producers have magnetite taconite reserves. Due to the extensive oxidation of most of the western part of the Mesabi Range, there are no large blocks of unaltered magnetite taconite that lend themselves to open pit operations. Unless a commercial process can be developed to concentrate the oxidized, or so- called "nonmagnetic", taconite and semi-taconite, the existing mines operating in the western part of the range will be forced to shut down when the direct shipping, wash and gravity ores are depleted, or are no longer salable, because of their poor quality compared to high-grade pellets. KNOWN PROCESSES COSTLY The enormous reserves of the oxidized iron- bearing formation have offered a tantalizing challenge to metallurgists for many years. In fact, several processes for concentrating certain types of oxidized ore have been successful at both laboratory and pilot plant level, but to date no process for concentrating semitaconite or oxidized taconite has reached commercial fruition. Magnetic roasting, followed by low-intensity magnetic separation1, has shown considerable promise because the high iron recovery makes the ratio of concentration of many of the oxidized ores more favorable than that of magnetite taconite. However, the capital and operating costs are high and, in many cases, a high- grade concentrate cannot be made without resorting to flotation of the magnetic concentrate. Hence, most research groups are investigating alternate methods of concentration with the hopes of reducing the cost.

Jan 9, 1965

By William Cruger

OUTLINE SUMMARY A. Brief Description B. Characteristics 1. Can be highly cost effective 2. Restricted in usage 3. Political Controversy 4. Volume of Transactions 5. Users C. Mechanism 1. Five steps D. Investor issues 1. Application 2. Restricted usage 3. Discount 4. Formal or informal process 5. Restricted benefits 6. Recompense 7. Window of opportunity THE VARIOUS PROGRAMS1 A. Brazil B. Chile C. Venezuela D. Argentina E. Mexico USAGE IN THE MINING, METALLURGICAL, AND PETROLEUM INDUSTRIES

Jan 1, 1990

By Hsun Hu, R. S. Cline

In an earlier publication1 it was shown that a single crystal of Cu-4 wt pct Al cold-rolled in the (110)[112] orientation was stable up to 95 pct reduction, although the orientation spread was considerable larger than in a similarly oriented and cold-rolled copper single crystal. When rolled to 99 pct reduction, the copper crystal retained its initial orientation and a high degree of sharpness of texture, whereas the Cu-4 pct

Jan 1, 1969

US 4,181,703-Removal of magnesium impurity from phosphate rock. Crushed screened ore containing more than 0.3% by weight of magnesium is slurried with sea water, acidified with sulfuric acid to a pH value not lower than 2 5, and filtered and washed before the neutralization point is reached. W. Wengeler, F. Wolstein, and E. Hoffman, assigned to Uhde G.m.b.H. Jan. 1, 1980 4 pp (423-167) Filed: 11-18-77 (852,918)

Jan 1, 1982

By Charles F. Hickey, Eric B. Kula

Thermomechanical treatments applied to the maraging steels include a) cold working in the austenitic condition at 650°F, followed by transformation to martensite and aging, b) cold working in the murtensitic condition and aging, and c) cold working in the aged condition with and without subsequent reaging. The strength increases in these steels are very small compared to the increases observed in conventional carbon and alloy steels. The changes that are observed are compatible with the strengthening mechanisms operative during thermomechanical treatment of conventional steels, however. Differences are caused by the absence of a carbide precipitate and the low work-hardening rate in both the solution-treated and the aged conditions. ThE 18 pct Ni maraging steels represent a class of steels which are finding great interest for high-strength applications.1~2 They are essentially carbon-free, and contain 7 to 9 pct Co, 3 to 5 pct Mo, and 0.2 to 0.8 pct Ti. Although austenitic at elevated temperatures, they can be air-cooled to room temperature to form a martensite, which because of the absence of carbon is relatively soft. On subsequent reheating age hardening occurs and strength levels of 250 to 300 ksi yield strength can be attained. These steels appear to be particularly suitable for studying the response to various thermome-chanical treatments for additional reasons other than the obvious one of attempting to improve their already attractive properties. Thermomechanical treatments can be defined as treatments whereby plastic deformation, generally below the recrystal-lization temperature, is introduced into the heat-treatment cycle of a steel in order to improve the properties. With an absence of intermediate transformation products on air cooling the maraging steels have good hardenability and hence can readily be cold-worked in the austenitic condition prior to transformation to martensite. Further, they can be worked in the martensitic condition prior to aging, and even can be deformed in the fully aged condition. Finally, it is of interest to compare their re- sponse to that of the more conventional alloy and carbon steels, where the role of carbides is important in the strength increase by thermomechani-cal treatments. The thermomechanical treatment of conventional steels has been the subject of a recent review.' I) MATERIALS AND PROCEDURE The steel used in this investigation was a commercially produced vacuum-melt heat, which had been rolled to 0.090 in. and mill-annealed. The composition of the alloy was as follows: 0.02 C, 0.08 Mn, 0.10 Si, 0.009 P, 0.009 S, 18.96 Ni, 7.34 Co, 5.04 Mo, 0.29 Ti, 0.05 Al, 0.004 B, 0.01 Zr, and 0.05 Ca. Unless otherwise stated the heat treatments used were the standai-d solution treatment at 1500°F for 1 hr, air cool, followed by a 900°F, 3 hr age. In this condition, the material exhibited 232 ksi yield strength and 239 ksi tensile strength. Mechanical properties were determined by Vicker's hardness measurement (20 kg) and by tensile tests on standard 1/2-in.-wide, 2-in.-gage-length sheet tensile specimens. Notch tensile tests were run using the 1-in.-wide NASA type, edge-notched specimen.4 Fracture-toughness determinations were made on 3-in.-wide, center-notched, fatigue-cracked specimens, following the recommendations of the ASTM Committee on Fracture-Toughness Testing.4 An electric-potential technique was used for measuring the crack size at the onset of rapid crack propagation5 which is necessary for calculations of Kc, the critical stress-intensity factor under plane-stress conditions. The critical stress-intensity factor under plane-strain conditions KI, was also calculated, using the stress at which the first observable crack growth occurred. 11) RESULTS A) Cold-Worked in the Austenitic Condition. The reported M, temperature for the 18 pct Ni maraging steel is about 310°F.1 Therefore, a temperature of 650°F was selected as suitable for rolling in the austenitic condition. Specimens were solution-treated at 1500°F for 1 hr, air-cooled to 650°F, and rolled varying percentages from 0 to 60 pct, at 20 pct reduction per pass. Tensile and hardness properties after aging at 900°F for 3 hr are shown in Fig. 1. The tensile strength increases from 253 to 271 ksi and the yield strength from 247 to 265 ksi as a result of a reduc-

Jan 1, 1964

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß') does not change significantly between 322o and 8000 K, confirming that the ß' alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp's law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß') has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß') were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968