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By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By T. B. Massalski, C. S. Barett

THAT metals and alloys of the body-centered-cubic structure tend to become unstable at low temperatures is so nearly universal that any exceptions are worthy of special attention. Studies of the exceptions may disclose unrecognized examples of metastability or may shed light on the nature of some of the factors that stabilize the body-centered-cubic phase. Among the structurally analogous body-centered-cubic 3/2 electron compounds, the ß-phase in the Cu-Zn system deserves further attention for, although this phase is known to undergo partial mar-tensitic transformation on cooling below room temperature to the temperature of liquid nitrogen when the composition is less than about 42 wt pct Zn, it does not transform on cooling .when there is more than this amount of zinc present.1-4 The present authors recently found that an alloy containing 48.35 wt pct Zn could be transformed, however, if deformed severely at room temperature or lower temperatures.V his discovery led to the suggestion that the jerky flow of ß-brass single crystals6 and some of the unusual temperature variations of the yield strength and hardness are due to strain-induced transformation during the tensile tests. The present investigation is an extension of that work to cover the entire available range of compositions of Cu-Zn ß-phase alloys and certain interesting compositions of the ß-phase in the Cu-Zn-Ga system. Particular attention is given to the structure of the transformation product resulting from cold work, which is found to vary with alloy composition, and to the temperature range in which transformation can be induced in the various alloys. The composition limits of the body-centered-cubic phase in the Cu-Zn system, based on a recent review by Raynor7 and the precision determinations of Beck and Smith: are shown in Fig. la; in the ß region the alloys are disordered and in the ß region they are ordered. The rate of ordering is so rapid that a high degree of order is found in any of these alloys immediately after quenching. Experimental The nine binary and four ternary alloys of this investigation were prepared from cathode copper (99.99 pct purity), electrolytic zinc (99.99+ pct), and gallium (99.98+ pct). All alloys were cast in transparent Vycor tubing, homogenized at temperatures between 800° and 890°C, and quenched in water. Ternary alloys were cast in small amounts (-5 g) to predetermined compositions to fall along a line of constant electron concentration in the ternary system. Changes of weight during the casting operation of the ternary alloys were not greater than 1 part in 2500 from the intended nominal weights and therefore their compositions were accepted without chemical analyses. All binary alloys were cast in larger amounts (100 to 150 g), homogenized, and hot rolled after preheating to 800°C. The central portion of the rolled strip of each alloy was annealed for eight days and quenched in brine. All binary alloys were analyzed chemically. The compositions, heat treatments, and metallographic appearances of all alloys are tabulated in Table I. Various samples were subjected to heat treatment or cold work at several temperatures and were then examined metallographically or by means of X-rays. Specimens about 6x6x3 mm in size were examined metallographic ally to confirm the presence of the ß-phase after quenching. Cold work was introduced by fastening each sample between two pieces of steel, cooling the assembly to the desired temperature, and transfering it rapidly to a vise where moderate or severe compression was immediately applied. Cold working at liquid helium temperature was done by a chisel-shaped tool mounted on an X-ray spectrometer, described elsewhere.% A!! metal-

Jan 1, 1958

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By H. A. Fisch, A. J. Opinsky, J. L. Bartos

Fort?-six- two-grain bounduries were studied in doped tungsten 1amp wire that had been heated to 3450°K very vapidly. Back-reflection Laue photograms were taken of the grain boundary partners and solved, using a computer. The resulting distribution of large-grain orientations was analyzed. Rotational axes were calculatedfor each grain boundary pair. The axes of least rotation show an anisotropy of rolalional angle. WhILE the orientations of large grains in straight doped tungsten wire have been studied extensively, little has been done to characterize the boundary that separates them. Rosi.1 upon seeing the jagged interlocking boundary in doped tungsten wire. inferred that the grains should have a preferred orientation, and proved it. He interprets his data as indicative of a single ideal orientation—(531)— being parallel to the wire axis. Rieck2, 3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Siegle argue that the data suggest that (211)—a plane-is parallel to the wire axis instead. This (211 ) contains the (531). and hence would appear to be a more general case.5 Ahlborn and wasserman6 report that their orientation data stretch from (110) through (531) to (311). This path is the locus of {211 Recently. Opinsky has suggested that the data can be interpreted as a series of ideal orientations that can be related by coincidence relationships to the (110) fiber texture. All these investigators have determined the orientations of the large grains by the back-reflection Laue technique, and they have all obtained similar results. Only Rieck5 as methodically looked at the large grains along a wire. He was apparently not concerned with the relationships of the large grains across their common boundary, but only with their individual orientations. This research was undertaken to fill this gap in the under standing of the mechanical properties of tungsten wire. Only the crystallographic aspects of the problem will be reported here. In addition, the large number of large-grain orientations, which was accumulated in this study. will also be analyzed. EXPERIMENTAL MATERIAL AND TECHNIQUES All of the data were obtained from four pieces of the same 7-mil-diam General Electric tungsten lamp wire. Twelve-inch lengths of the cleaned wire were heated in vacuum by the flick of a switch to 90 pct of the amperes necessary for fusion (a temperature of approximately 3450°K) and held for 1 min. On the basis of other data. it is estimated that the rise time is of the order of 0.5 sec. The four pieces of wire could have come from anywhere within about 18 ft of wire. Consecutive segments of each piece of wire were mounted in bakelite and polished metallographically The polishing procedure followed that described by woods. "nly boundaries between two grains that each occupied the entire cross section of the wire were photographed and X-rayed. The metallographic sample was mounted accurately with respect to the X-ray unit. Steps were taken to read the films as accurately as possible with the conventional Greninger net. The data were then entered into computer programs that solve the Laue film by precisely the same techniques that are used in the solution of the film by means of the stereographic projection. The use of the computer has probably shifted the main source of error from the stereographic plot to the reading of the film. On the basis of several experiments, it is thought that the error associated with the entire process, from mounting the sample through the computer solution, is of the order of about one-half degree. The output of the computer is the direction cosines of the fiducial direction (the wire axis) and the locations of the three cube axes. The former data were used to calculate the differences in orientation between the two grain boundary partners, and the latter were used in the calculation of the rotational axes that could bring the two grains

Jan 1, 1970

By Agne Rustan

INTRODUCTION This work is a continuation of the preparatory study by Rustan and Stöckel 1979 (3) and (4) of the possibilities to introduce automatic mine ventilation in Swedish mines and construction works. The preparatory study has been financed by the Swedish Board of Technical Development. In the study it was recommended that an automatic step by step control of the fans near the working place due to diesel exhaust emission would be the best solution. A more advanced alternative would be to regulate the fresh air continuously in proportion to the contamination. The latter alternative has been studied by Boliden Mineral Co in the Udden mine. In this study it was found that the air supply could be regulated continuously but it was very important where the sensors feeling the contamination were placed. An intense study of the environment underground is now being planned by our division together with specialists from the National Board of Health and Safety, The Swedish Work Environment Fund, LKAB and the local Governmental Inspection of the Workers Safety. Different gases, radon, dust, airspeed, moisture temperature and pressure is planned to be measured continuously and correlation between the parameters is going to be established to decide the best measurement parameters for regulating the system. The best situation of sensors is also going to be studied. Despite this work hasn't been done yet this paper covers some of the problems which could be encounted with continuous regulation. In this report the environment has been studied during the test with step by step regulation of fans by radio. Diesel vehicles are the largest polluters under ground in Swedish mines and we have therefore suggested that the large diesel vehicles should regulate the fans. The goal of this study has therefore been to find how active diesel vehicles should be able to start and stop gallery fans at both intake and return air. In this paper different methods for activating fans are discussed. Then the best methods are chosen and tested in the mine. In this study we have found that changes of temperature is a cheap and effective method to start and stop cross cut fans in sublevel caving and radio signals seem to be an attractive system for start and stop of gallery fans. This work has been done in close collaboration between LKAB in Kiruna and the University of Luleå - Division of Electronics and Division of Mining and Rock Excavation. A reference group for the project has been established with ventilation experts from the mines, representatives for the local mine worker's unions and authorities from the local Governmental Inspection of the Workers Safety. VENTILATION SYSTEM STUDIED In the project the ventilation system at LKAB in Kiruna has been studied. The mining method used is sublevel caving with 9-13 m slice height. The air is heated winter time over ground by hot water heat exchanger. The main fans are pushing air down to a main distribution level along the 4000 m long and about 100 m wide orebody. From the distribution level, air is taken through shafts down to the sublevels, where it is pushed through the levels by local gallery fans on both intake and return side, see fig 1. The air ( ~ 8 m3/s) is moving freely through the gallery head. The cross cuts are ventilated with smaller fans, diameter 500 mm, and flexible duct, see fig 2. The aim of this study has been to study how to start and stop gallery- and cross fans and examine the environment when the fans are stopped . In Sweden there are no regulations telling that a minimum of air amount must be supplied. Instead the hygienic limits must be fullfilled.

Jan 1, 1981

By P. Pietrokowsky

lntermediate phases in the binary metal alloy systems Ti-Zn, Ti-Hg, Zr-Zn, Zr-Cd, and Zr-Hg have been investigated by X-ray powder diffraction methods. Gamma-TiBHg and Zr3Hg have a beta tungsten structure; TiHg and ZrHg are analogous to ordered AuCu (L l0 type); delta-TixHg and ZrHg, are isomorphous with ordered AuCu,, (L l2 type); ZrZnz is face-centered cubic (C 15 type); TiZna crystallizes in a C 14 type structure; and Zrll-, occurs in cubic and tetragonal modifications in which a random distribution of atoms exists. Additional information for the intermediate phase TiZn, is presented. THE physical metallurgy of titanium and zir-conium when alloyed with elements in subgroup 11-B of the periodic table has received comparatively little attention in the literature. Laves and Wallbaum' reported the existence of several intermediate phases in the system Ti-Zn. They identified TiZn as a CsCl (B 2) structure and described TiZn, as an ordered Cu,Au (L 1, type) crystal structure. Gebhardt' investigated very limited zinc-rich regions in the systems Ti-Zn and Zr-Zn. Phase relationships in these partial constitution diagrams were deduced from the results of thermal analysis and metallography, X-ray results being inconclusive. The first zinc-rich intermediate phase in either system was not identified. More recently, Anderson, Boyle, and Ramsey" have had occasion to refer to a partial Ti-Zn phase diagram (unpublished data) covering the region 0 to 10 atomic pct Ti, wherein two intermediate phases corresponding approximately to TiZn,, and TiZn,, were indicated. The metals used in this investigation and typical analyses as determined by the suppliers are given in Table I. The iodide-process zirconium which was used was not hafnium free. Experimental Methods Alloy Preparation: The relative ease with which titanium and zirconium combine with other elements places extensive restrictions on the methods by which alloying can be achieved. The direct current electric arc melting procedure was found to be unsatisfactory for preparing these binary alloys and for this reason solid state diffusion methods were utilized. The iodide process titanium and zirconium rods were filed by hand. Fines were subjected to a magnetic separation and classified as to size as either finer than 200 mesh or coarser than 200 but finer than 80 mesh. Powder mixtures of various binary combinations of titanium and zirconium with zinc and cadmium were compacted in a 12 mm diameter die and then placed in Vycor or quartz vials which were evacuated and sealed. The mercury alloys were prepared in a similar manner; the proper weight of liquid mercury being placed in a vial with minus 200 mesh titanium or zirconium. These ampoules were then heat treated at various temperatures and times depending on the characteristics of the particular alloy system. Upon completion of the heat treatment the ampoules were cooled rapidly and the specimens weighed. The loss in weight varied from 1 to 3 pct (except as noted in the text) and for this reason the calculated compositions were accepted as a fair measure of the actual alloy compositions. X-Ray Dif raction Techniques: Powder diffraction experiments were conducted at room temperature with a 143.2 mm Debye-Scherrer X-ray camera in which the film was placed in the Straumanis arrangement. When copper radiation was used, a nickel filter was employed, and for the cobalt target a filter of iron oxide was used. In both cases, the /i? filter was placed between the X-ray target and the powder specimen which was mounted on a glass fiber. The lack of information based on optical metallography placed reliance on the results obtained from the X-ray experiments for determination of

Jan 1, 1955

By Russell Franks, W. O. Binder

In recent years a considerable tonnage of the 18 per cent chromium and 8 per cent nickel steels has been used in lightweight high-strength structures that must be resistant to deterioration under atmospheric conditions. These steels are austenitic in character and their strength can best be increased by cold-working. Although a marked increase in tensile strength is obtained, claims have been made that the cold-worked steels do not possess fully satisfactory elastic propertics. Under certain conditions, however, this has caused no great concern, because, as explained by Ragsdale,1,2 he cold-rolled steels have been widely applied for construction of lightweight, high-strength trains using spot welding for joining purposes. Ffield3 agrees that the ease with which thin sections of the cold-rolled 18-8 steels can be joined by spot welding is greatly in their favor, but that they would be more satisfactory if higher elastic properties and a higher modulus of elasticity could be obtained. He states that, as far as the mechanical properties are concerned, the straight chromium stainless steel is superior to the cold-worked 18-8 steel, and in order to illustrate, he prcsented the data of Fig. 1, which also give a stress-strain curve for a low-carbon 13 per cent Cr steel. Ffield† proposed that columbium-bearing or titanium-bearing cold-rolled 18-8 steels be given a heat-treatment (preferably for 1 hr.) in the range 400" to 600°C. to precipitate carbides in order to obtain better mechanical properties. Discussions by Sutton,4,5 de Ganahl,6,7,8 Krivobok and Lincoln,' Knerr,l0 and Thaden11 have given further information on the properties of the cold-rolled 18-8 steels compared with other materials used in lightweight, high-strength structures. These investigators and others point out that the ultimate tensile strength of the cold-rolled 18-8 steel can be increased to 200,000 lb. per sq. in. or higher; Krivobok et al. indicate that

Jan 1, 1940

By Russell Franks, W. O. Binder

In recent years a considerable tonnage of the 18 per cent chromium and 8 per cent nickel steels has been used in lightweight high-strength structures that must be resistant to deterioration under atmospheric conditions. These steels are austenitic in character and their strength can best be increased by cold-working. Although a marked increase in tensile strength is obtained, claims have been made that the cold-worked steels do not possess fully satisfactory elastic propertics. Under certain conditions, however, this has caused no great concern, because, as explained by Ragsdale,1,2 he cold-rolled steels have been widely applied for construction of lightweight, high-strength trains using spot welding for joining purposes. Ffield3 agrees that the ease with which thin sections of the cold-rolled 18-8 steels can be joined by spot welding is greatly in their favor, but that they would be more satisfactory if higher elastic properties and a higher modulus of elasticity could be obtained. He states that, as far as the mechanical properties are concerned, the straight chromium stainless steel is superior to the cold-worked 18-8 steel, and in order to illustrate, he prcsented the data of Fig. 1, which also give a stress-strain curve for a low-carbon 13 per cent Cr steel. Ffield† proposed that columbium-bearing or titanium-bearing cold-rolled 18-8 steels be given a heat-treatment (preferably for 1 hr.) in the range 400" to 600°C. to precipitate carbides in order to obtain better mechanical properties. Discussions by Sutton,4,5 de Ganahl,6,7,8 Krivobok and Lincoln,' Knerr,l0 and Thaden11 have given further information on the properties of the cold-rolled 18-8 steels compared with other materials used in lightweight, high-strength structures. These investigators and others point out that the ultimate tensile strength of the cold-rolled 18-8 steel can be increased to 200,000 lb. per sq. in. or higher; Krivobok et al. indicate that

Jan 1, 1940

By R. Newman

An inexpensive slow-speed data acquisition system has been adapted to digitally record multiple parameters simultaneously at intervals of 15 seconds. The system was built for use with standard soils testing equipment to automatically record load and displacement parameters at predetermined instants in time. Simultaneous readout is achieved by the use of special signal conditioner and sample-and-hold circuits which read the multiple signals simultaneously and hold them until the slow acting system can print out. Three channels of a 10-channel system have been converted and found to operate successfully during a series of direct shear tests. A unique feature of the system, which significantly reduced its cost, is the power supply units. Dummy circuits are used to maintain a constant power demand during sampling) thus eliminating the need for a costly power supply with rapid response characteristics. The entire system, having an overall accuracy of 0.25 percent, was put in operation for a cost under $2,500.

Jan 1, 1970

"Nanisivik Mines Ltd. operates a 10-M W diesel-electric generating plant at its zinc-lead operation on Baffin Island in the Canadian Arctic. This paper provides a description of the plant and the integrated waste heat recovery system. Data is presented detailing the actual costs of operating a plant over a period of seven years. Problems in operation are described as well as the success of the plant in meeting its objectives over the years. IntroductionNanisivik is located on the shore of Strathcona Sound at the north end of Baffin Island (Fig. I). Nanisivik Mines Ltd. has operated a 2,100 tonne per day zinc-lead underground mine and a concentrator, together with supporting infrastructure, at this location since October 1976. Annual production of 100 000 tonnes of zinc and 10 000 tonnes of lead concentrate is transported by ship to Europe during the mid -July to mid October shipping season.All electrical needs of the project are provided by the company-owned and -operated power plant. Facilities served by this electrical system are the underground mining areas, the concentrator and industrial area, a townsite, airport, and shiploading dock complex."

Jan 1, 1986

By G. A. Vissac, R. G. Minet, N. E. Sylvander

R. G. Minet—The authors' description of the remarkable progress made in the last few years in applying the fluidized solids technique to the problem of lignite drying and carbonization clearly demonstrates that engineering techniques available today may make many processes practical and profitable which a few years ago were considered otherwise. As pointed out in the article, the future of the carbonization step hinges on the value and utilization of low temperature tar. On paper, at any rate, this tar looks like a valuable raw material for the chemical industry to use. Some 50 to 60 pct may be converted to pitch for electrodes, roofing, road tars, and other valuable products; the 25 to 30 pct tar acids could conceivably form a basis for a new low cost resin or plastic of the phenolformalde-hyde type. Yet these materials are so new and dissimilar from available sources that much work must be undertaken by the chemical industry before they will be accepted. Now that the work of Dr. Perry and his colleagues has made a large supply of low temperature tar a real possibility, I would expect the chemical industry to accelerate its work in this field. On the basis of certain data available in the literature it appears possible to produce a more aromatic tar, although in smaller yield, by operating at temperatures in the range of 1300" to 1500°F. Operating a fluidized bed process for lignite at these conditions should be technically possible, at least, and could produce a tar having more familiar characteristics. I wonder if Dr. Parry would care to comment on such a possibility. Incidentally, in our own work on carbonizing coking coals in fluidized beds, using Ohio, Pennsylvania, and West Virginia high volatile bituminous coals, we have obtained yields which agree with the correlation given for tar yields vs moisture and ash-free volatile Btu. Our data are slightly under the line, but certainly in the range of the correlation. We have also obtained evidence in support of the authors' statement as to the effect of air on the process. In our pilot plant all the heat required for carbonizing is released by internal combustion of char in the fluidized bed in normal operation. We are also equipped to obtain all carbonization heat by external electric heaters on the shell of the carbonizer while introducing only an inert gas to the process. We note no difference in tar yield or characteristics between the two operations. In the case of the gas, however, it appears that some hydrogen is consumed by the air combustion. We would be interested in hearing in a little more detail about the hot dust and char handling problems at Sandow. Have the authors found char subject to spontaneous combustion? Have they ever tried a coking coal in their pilot plant? V. F. Parry (author's reply)—Production of a more aromatic tar by operation of the carbonizer at 1300" to 1500°F does not appear to be economical. 1) The capacity of a reactor operating at 1500°F would be 30 to 50 pct less than the capacity at 932 °F and the cost of processing would increase materially. 2) The cracking of tar vapors in a reactor requires appreciable time to complete the reactions and it is doubtful that considering the very short time of residence of tar vapors within the reactor (4 to 10 sec after evolution) the basic character of the tar would be changed significantly. This is indicated from the data reported in Table XIV. 3) General studies have shown that it is advisable to operate at the minimum temperature to produce the maximum tar and minimum gas. 4) Operating problems and the maintenance of vessels and reactors, and the hazards of handling hot char, increase with the temperature of carbonization. It is technically possible to operate at temperatures as high as 1500°F, but in my opinion it is not economical or desirable. We believe that the primary tar must be won in the simplest way and then processed alone to change its character for production of desired products. It is interesting to have confirmation of our observations on the reaction of air with the products of carbonization. The major reaction is with the char, fol-

Jan 1, 1957

By W. C. Leslie, R. M. Fisher, K. G. Carroll

A nitride, believed to be Si3N, has been separated from three nitrided silicon steels. Germanium nitride, Ge3N4, has been prepared from pure germanium. Comparison of the diffraction patterns indicates that the two nitrides are isomorphous; on orthorhombic structure is suggested in place of the rhombohedral structure previously reported for Ge3N4. THE possibility that a nitride of silicon may, under appropriate conditions, precipitate in silicon steels or in steels killed with silicon makes it desirable to have some positive means of identifying such a compound. One such means is the X-ray or electron diffraction pattern of the nitride. A review of the meager data in the literature indicates that the nitride most likely to form is Si3N4, a conclusion supported by the results of a study of nitrided silicon steels to be published shortly by L. S. Darken and R. P. Smith, of this Laboratory. Unfortunately, there is available no diffraction pattern for this nitride. Data have been reported, however, for Ge3N4 which, judging from the similarity between germanium and silicon, might be expected to be isomorphous with Si3N4. An effort was made, therefore, to form such a silicon nitride, to determine its composition and diffraction pattern and, if possible, its structure. To this end a series of three silicon steels was nitrided under controlled conditions with the resultant formation of nitride particles which yielded an electron diffraction pattern in situ. The particles were then extracted from the steel and an attempt was made to determine their chemical composition. X-ray and electron diffraction patterns were also obtained from the extracted particles, which indicate that the nitride is isomorphous with Ge3N4, although a complete determination of the structure has not been possible. These results show that a silicon nitride with a well-defined diffraction pattern can form in silicon steels, and they suggest that this nitride is Si3N4. Materials and Procedures The sillicon steels investigated were In the form of thin sheet or strip and had the composition shown in Table I. The 0.58 and 1.21 pct Si steels were nitrided by holding them at 1110°F in an H2-NH3 atmosphere containing 3 pct ammonia for 48 hr. The nitride particle size was increased by subsequent heating at 1500°F for 13 1/2 hr in helium. The resulting microstructure is shown in Fig. 1. The steel containing 3.20 pct Si was nitrided at 1200°F for 16 1/2 hr after which it was held in helium at 1500°F for 4 hr. Its structure as seen under the electron microscope is illustrated by Fig. 2. As would be expected from the higher silicon content and the shorter holding time at 1500 °F, the nitride particles are smaller and more numerous than those in the 1.21 pct Si steel. The ammonia-hydrogen treatment reduced the carbon content of the steels to a very low level, so no interference was encountered from carbon or carbides. In the case of the 3.2 pct Si steel, the carbon was reduced to 0.003 pct before nitriding by heating in dry hydrogen. Attempts to obtain an X-ray diffraction pattern from polished and etched surfaces of the 1.21 and the 3.20 pct Si steels were unsuccessful. However, an electron diffraction pattern was obtained from the surface of the steels. The interplanar spacings obtained from these patterns arc shown in Table 11, col. 5. The nitride particles were then extracted from all three steels by dissolving the ferrite matrix in bromine-methyl acetate, the solution used in the Beeghly method for the extraction of aluminum nitride from steel. X-ray diffraction patterns of these residues, obtained by means of a spectrometer and by a 57 mm Debye-Scherrer powder camera using filtered cobalt or chromium radiation, are given in Table II along with the pattern obtained by

Jan 1, 1953

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry's law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry's law is obeyed, one canthen use the Van't Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors' Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott's results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By F. C. Miller

The briquetting of fuel is an industry centuries old and has followed the hammer and tongs method of making use of any by-product fuel by the simple process of sticking the mass together with anything that will stick. If fuel briquetting, as an industry, once in the lead over coal mining, had kept pace by introducing science, there would not at this time be the mad scramble to look up the fuel briquette family tree and accept every new method as fruit without the cultivation that makes fruit worth while. Cultivation of industry is a mass of evidence showing a tremendous expenditure of money for mistakes paving the way to success. Cultivation of the mining industry is practiced by nations and low temperature distillation and fuel briquetting will in the near future receive the same consideration. Fuel briquettes were used as a winter fuel in Ireland and Scotland before the discovery of America' or the introduction of coal as a fuel to replace briquettes in Ireland. This industry was practiced by the peasants who collected peat from the bogs and cut it into brick-shaped blocks, which were set up to dry in the sun and stored under cover for use or for sale. Demand for peat briquettes led to competition that resulted in a highly refined fuel. In some localities the peat was ground and purified from the earth by washing before placing in presses to squeeze out the excess moisture and form a block of peat about four inches thick. These blocks, after standing in the sun for a few weeks, were cut into briquettes about four inches square by twelve inches long and moved under cover where they remained until thoroughly dry. In this form peat makes an excellent fuel with considerable heat, small amount of smoke while burning, and tough enough to stand hauling in carts and boats without breakage. Slack from domestic coal, non-coking and anthracite, has until recently commanded a very low price and the attention of briquette men has centered on ways and means of preparing this class of fuel for the market in the form of briquettes. Industrial plants with automatic stokers have taken kindly to cheap slack or slack that was cheap because the price has been boosted to a figure where the cost of slack plus the cost of binder and operation makes fuel briquettes somewhat expensive. However, fuel briquettes are being turned out in commercial quantities to compete with prepared lump coal and the demand is in favor of the briquette man. Science has been called to aid the briquette and it is possible to purchase a complete coal briquetting plant that will turn out between four tons per hour and thirty tons per hour of briquettes at a calculated cost per ton to cover material and every item down to insurance on the plant. A few briquettes are being ' made with a mixture of- Portland cement and pulverized coal, where this class of briquette is cheap in the making, there is the increased amount of ash due to the cement to contend with and the briquette is not one that can compete with lump coal. Most binders have a fuel value, such as coal tar, pitch, asphalt residium, flour, glue and secret binders. Most briquettes are of an egg shape, weighing between one and one-half ounces and five ounces, pressed to form with a pressure varying between 1,000 pounds and 2,500 pounds per square inch. This' pressure, together with the binder, make a lump of fuel harder than most grades of soft coal. Most of the briquettes are free from pitch odor, and any tendency to leave a trace of the binder on the fingers, easy to handle, quick to, ignite, high in heat value and capable of indefinite storage without any change. Evaporative efficiency of briquetted fuel in stationary, marine and locomotive boilers has proved that a great many low-grade coals can be fired successfully in the briquetted form, where the same fuel without briquetting failed to give boiler rating.

Jan 1, 1923

By Dirk van Zyl, S. Chander

Minerals have been critical to human society from the earliest and their use has been intertwined with the development of civilization. In the Western World, the mining, processing and extractive metallurgy associated with ores was first described in detail by Agricola in the 16th century. He considered these collective activities to be the most necessary and the most profitable of professions, and wrote, "without doubt, none of the arts is older than agriculture, but that of the metals is not less ancient; in fact they are at least equal and coeval, for no mortal man ever tilled a field without implements. In truth, in all works of agriculture, as in the other arts, implements are used which are made from metals, or which could not be made without the use of metals; for this reason the metals are of the greatest necessity to man." Ours is still a materials-dependent society that relies heavily on minerals for raw materials. Today our dependence on minerals is exceptionally great. To meet the need for fuel and non-fuel minerals in a representative year, in the United States alone, about one billion tons of coal and 2.7 billion tons of ore are mined. These mineral products are essential for fertilizers, for construction materials, metals and alloys, for manufacturing household and industrial items, for transportation, and for the generation of electric power. It is instructive to consider the diversity of uses found in our society for a single mineral product - silver, for example. Experts believe that in the past 5000 years we have mined about a million tons, or 31.9 billion troy ounces of silver. In 1988, 133 million troy ounces of silver were used in the Unites States. Most of the silver used was for techno- logical, medicinal and industrial purposes, Table 1. X-ray films, for example, carry comparatively large amounts of silver to lessen patient's radiation exposure. Silver does not prevent tooth decay, but each year about two million troy ounces of silver is used for dental work in the United States. In small quantities it is used in medicine. No metal - not even copper conducts heat and electricity so efficiently as silver. Silver wires lace solar cells, and silver oxide batteries power hearing aids, calculators, submarines and satellites. Hardened with tungsten or molybdenum, miniature discs of silver pass current from wire to wire in cars, telephones and computers. A dish- washer timer alone may have 50 such electrical contacts, which open and close without excessive heat or friction. Silver is an important component of solar reflectors, since no other material reflects light so well or uniformly. In our personal lives, silver remains in high esteem to adorn our tables, provide precious objects and jewelry. In many parts of the world, silver in the form of coins, jewelry and bullion is used for financial independence and security against the vagaries of paper currency. In India, silver is used in its purest form as thin foils to decorate sweets and other edibles. It is obvious that this mineral product, silver, is of great value and utility in our society. Minerals and Environment The benefits of minerals do not come without problems. Much of the silver, for example, lies locked up in copper, lead-zinc or precious metal ores; to extract it creates vast quantities of waste material. On the average, in order to recover one ounce of silver about a quarter ton of ore must be mined. To meet the world's annual demand for silver, approximately 100 million tons of waste is generated every Year. The problem with silver is repeated with all minerals. Conversion of mineral ores into usable materials necessitates the generation of large quantities of waste products that create tremendous disposal problems. In addition to waste material discarded during mining, wastes may be generated during processing as gases, liquids or solids that must be subsequently converted into forms more acceptable for disposal. Associated with the handling, treatment and management of waste products are a number of environmental problems. Environmental problems are not new to the minerals industry. In his Geographia, Strabo (63 B.C. - 20 A.D.), gives an account of the conditions of labor under which men

Jan 1, 1992

By J. Washburn, R. Drouard, E. R. Parker

Temperature dependence of the rate of recovery in zinc single crystals after a simple shear deformation at low temperature was investigated. Some tentative suggestions regarding the annealed and strain-hardened states of a crystal are discussed. RECOVERY may be defined as the gradual return of the mechanical and physical properties of strain-hardened metal to those characteristic of the annealed material; an increase in temperature increases the rate of recovery. The annealing process in strain-hardened polycrystalline metals is complicated by the inhomogeneity of strain which always exists in aggregates. Polygonization in bent regions of the crystals and growth of new almost strain-free grains starting at points of severe local distortion1-:' make it almost impossible to isolate and study the recovery process. Homogeneously strained single crystals, however, do not polygonize or re-crystallize and hence they can be used advantageously to study recovery. In such crystals strain hardening is completely removed by recovery alone. Since recovery is a process whereby certain lattice disturbances introduced by plastic flow are gradually reduced, a knowledge of the rate and temperature dependence of this process for various conditions of prestrain might be helpful in formulating a model of the strain-hardened state. For simplicity it seemed desirable to limit the type of prestrain to the simplest obtainable, i.e., simple shear strain. In the experiments to be described, recovery was studied by observing changes in the stress-strain curve of prestrained zinc single crystals held for various times at temperatures above that employed for straining. Single crystals were grown from the melt by a modified Bridgeman technique from Horse Head Special zinc 99.99 pct pure, and from spectrographically pure zinc 99.999 pct pure. They were grown as 1 in. diameter spheres and acid-machined' to the final specimen contour. The test section was a cylinder about 1/8 in. high and 3/4 in. in diameter. The conical sections adjacent to the test section were cemented into the grips so the load could be transmitted to the crystal as uniformly as possible. The specimens were oriented so that in testing the maximum shear stress was applied along one of the slip directions, [2110], in the (0001) plane. Details of the production and testing of such specimens have been presented.' Each test was carried out according to the following schedule: 1—The crystal was strained at — 50°C until it reached a maximum shear stress, ,,,. The strain rate was approximately 5 pct per min in all cases. 2—After straining, the crystal was unloaded before the temperature was changed. Unloading required about 3 min. 3—The temperature of the specimen was then increased from — 50°C to the temperature, T, of recovery. This change in temperature was completed in a time of less than 2 min. The specimen remained at temperature, T, for a time, t, which differed for the various specimens. 4—Thereafter the temperature was again reduced to — 50 °C in approximately 3 min. 5—While at —50°C, the stress-strain curve after recovery was obtained. 6—The specimen was then unloaded and annealed for 1 hr at 375 °C in a helium atmosphere to bring about complete recovery. Cooling to room temperature after anneal required 90 min. 7—The same crystal could be re-used for another test because the plastic properties after annealing closely duplicated those of the original crystal. The specimen was immersed during the test in a bath of methyl alcohol which, through a system of tubes, could be pumped through either of two heat exchangers to regulate the temperature; this was accomplished by circulating the liquid through coils immersed in a bath of acetone and dry ice for cooling or in a bath of warm water for heating. Test temperatures were thus maintained constant within ±1°C. The — 50°C temperature was low enough so that no measurable recovery occurred during unloading and reloading. The stress-strain curve continued after recovery along a path below, but approximately parallel to, the path of a curve obtained in an uninterrupted test. Fig. 1 shows some of the results from a specimen of 99.999 pct Zn. The amount of downward displacement of the curve due to recovery was a

Jan 1, 1954

By Margaret V. Doyle, R. W. Powers

INTERNAL friction measurements, carried out as functions of temperature, have been used extensively to obtain data on the mobility of interstitial impurities in the Group V metals, vanadium, colum-bium, and tantalum. For a given frequency of vibration, the internal friction peaks at a temperature which depends principally on the particular metal and interstitial impurity. Relaxation times and corresponding activation energies are determined from a knowledge of such peak temperatures for various vibration frequencies. These experimentally determined relaxation times are related to the average jump frequencies of the interstitial impurity atoms using the model of Snoek1 and can be related to macroscopic diffusion coefficients as shown by Polder.2 In these Group V elements, the impurity whose diffusion rate has been the hardest to pin down by the internal friction technique has been carbon. The experimental difficulties associated with carbon in these metals were not evident in the earliest investigation carried out by Ke on tantalum.3 The carbon peak was thought to occur near 140°C at 1 cps on the basis of the enhancement of the height of this peak measured on specimens which had been coated with colloidal carbon and heated in vacuo at 1200°C. Presumably on the basis of similar evidence, Wert identified a peak also near 140°C at 1 cps in columbium with the diffusion of carbon in that element." Later, the difficulties of admitting carbon into these metals without simultaneously introducing oxygen were pointed out by Ang and Wert- nd by Marx, Baker, and Sivertsen.6 The latter suggested that the peaks attributed to carbon in tantalum and columbium might arise from the presence of traces of oxygen, adventitiously absorbed during the carburization. Such suspicion was confirmed, at least in tantalum, when it was found possible to prepare C-Ta specimens without contamination by oxygen. Specimens sci prepared, aitnough high in carbon content, gave no evidence of a damping peak near 140°C.7 Recently, the authors were able to Show that carbon diffuses in tantalum at a rate only slightly slower than that for nitrogen.8 At 1 cps, the carbon peak lies at 34g °C, only a few degrees above the nitrogen peak at 341 °C. However, the two could be distinguished by a different stability with respect to aging at 400 °C and by a different dependence of peak height on solute concentration. On the basis of this experience with tantalum, it appeared worthwhile to search also for a carbon peak in columbium in the vicinity of the nitrogen peak." In this report, the location of the carbon peak in columbium is made known and its position relative to the nitrogen peak is compared with the authors' previous findings in tantalum. In addition, a second source of internal friction seen only in specimens of very high purity is discussed. Columbium was obtained from the Fansteel Metallurgical Corp. as either 30 or 40 mil diam stock. The manufacturer gives the following analysis as typical of this material: 99.4 pct minimum Cb, 0.10 pct maximum C, 0.5 pct Ta, 0.04 pct Ti, 0.02 pct maximum Si, and 0.01 pct maximum Fe. Wires 13 in. long were degassed near 2200°C for 4 to 16 hr in an ultimate vacuum better than 2.10" mm Hg in an apparatus described previously.8 This treatment reduced the oxygen and nitrogen damping peaks observed in the as-received material to less than 0.0001 in Q-1 above background. The latter value varied somewhat from specimen to specimen in the range 0.0004 to 0.0008, depending chiefly on the wire diameter and the frequency of vibration. The high temperature evacuation left the specimen in a rather soft condition, the Vhn being reduced to 40 from a value near 121 in the as-received conGi~iur~. The gram size was about the diameter of the specimen. After outgassing, specimens were loaded with carbon by absorption of such hydracarbons as methane or ethylene. Carbon was also added to a few speclrnens by heating them at

Jan 1, 1958

By K. R. Gardner, P. B. Altringer, R. H. Lien, B. E. Dinsdale

The Bureau of Mines, U.S. Department of the Interior, is investigating chemical and biological decontamination of complex wastewaters such as tailings pond water containing 280 ppm CN and 5 ppm Se as well as significant concentrations of arsenic, copper, iron, silver, and zinc. The most effective chemical procedure involves cyanide oxidation using hydrogen peroxide or sodium hypochlorite followed by selenium reduction using ferrous hydroxide. The effluent contains ?1 ppm CN and 20 ppb Se; concentrations of other - major contaminants meet National Drinking Water Standards. Preliminary research indicates that biological cyanide oxidation is possible even in highly alkaline solutions (pH 10.5) containing high cyanide concentrations; indigenous bacteria destroyed 85% of the cyanide. Exploratory research shows that other bacteria removed up to 79% of the selenium from chemically oxidized, low- cyanide water. These promising results may lead to a final processing scheme that involves a combination of chemical and biological techniques.

Jan 1, 1990

By J. D. Sargent

Selenium might be described as a paradoxical element, being either a metal or a nonmetal, a conductor or nonconductor, amorphous or crystalline, colorant or decolorant, and a hydrogenator or dehydrogenator. Selenium was discovered in 1817 by the Swedish chemist, Berzelius, while studying flue dust from the lead chambers of the sulfuric acid works at Gripsholm, Sweden, The ordinary stable form of selenium is a crystalline, grayish solid with semi-metallic luster. It melts at 217° C., boils at 684.8° C., and has a density of 4.79.

Jan 1, 1955

By B. P. Martinez

In response to a request from the President, the Department of the Interior joined with other agencies in a comprehensive study of the land and water resources of the New England-New York region. As part of this study, chemical engineers of the Bureau of Mines have visited 1,025 mineral-industries plants to inventory the waterborne wastes of mineral origin, discharged by the mineral industries of the New England-New York region. Four-hundred and sixty-two of these plants disposed their wastes to a public sewer of some type, but waste control remains a problem for moat of them. The 1,025 plants are discussed in main industry groups according to their production: Chemical and allied products. Stone, clay, and glass products. Iron and steel and their products (except machinery). Nonferrous metals and their products. Electrical machinery. Machinery (except electrical). Transportation equipment. Miscellaneous mineral industries.

Jan 1, 1956