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By G. A. Wiebols, N. G. W. Cook, N. C. Joughin

Discussion R. E. Rarnes (Member): The original concepts and the pioneering work now brought to the practical test stage by the Mining Research Laboratory team deserve our highest praise. The authors of this comprehensive paper rightly stress the urgency of establishing the extent to which the apparent potential can profitably be realised in practice. It is to be hoped that adequate funds will be made available by individual mining companies, the Chamber of Mines and manufacturers to attract the necessary staff and maintain the high rate of achievement of the last two years. From the Seventy-Eighth Annual Report of the Chamber of Mines and its members we see that, in 1967, with a Working Revenue of R759.8 million from gold and R54.6 million pit mouth coal sales and with profits from gold and uranium and pyrite of R307.9 million, only R1.9 million was spent by the Chamber on all forms of Research. It is considered unlikely that the associated mining companies and manufacturers exceeded this investment expenditure. Assuming a total of R4 million spent by the industry on Research and Development, this is less than half of 1 per cent of sales of gold and coal. This percentage, so low in comparison to North America and Europe, is no worse than that of Exploration expenditure which, in 1967, with South Africa's total mineral production of R1,287 million, was estimated to have been R6 million (Pretorius 1968). In a primary industry with ever present depletion of ore deposits and with cost escalation, expenditure on Exploration and on Research and Development is not a risky luxury but a tactical obligation. The potential rate of return on research expenditure into rock breaking is high. Stores consumed by gold and coal mines, members of the Chamber of Mines, totalled R316.2 million in 1967. Except for purchased power costing R42.2 million the highest cost group was explosives, drills and drill steel totalling R33.8 million or 10.7 per cent of the total stores consumed. In the paper under discussion it is claimed that the low 'effective stoping width' should greatly reduce the likelihood of rock falls or rock bursts to the extent that permanent support can be dispensed with. Insofar as this narrow cut is only 12 in. in advance of the working area which, with a 10 in. channel, is unlikely to be much reduced in width from that achieved by current methods, this claim is not readily understandable. Were it to have been based upon the regional support gained from packed waste it would have been more acceptable. Pre-developed stope drives may give serious trouble at depth and for this reason it is questioned whether a stoping area can avoid periodic sub-development blasting-the spoil and fumes from which will interfere with the rock flow and continuous mining of the rock-cutter. If, in the mining method proposed by the authors, stope drives are cut as small as possible (6 ft by 6 ft) then 25 per cent of the total tons handled (excluding resued waste) and 5 per cent of the gold will be blasted conventionally in the stope. At this stage one cannot envisage tunnelling machines economically or practically capable of such work. The various methods described by the authors and subsequent contributors for breaking waste are most interesting. It was noted that the 'bull wedge' and 'explosives' in Fig. 1 of the paper were no further from the ideal point 'A' than was 'cutting'. The writer considers that the bold and imaginative steps taken by the Mining Research Laboratory Team, the mining companies and the manufacturers concerned will eventually lead to a successful rock cutting machine with universal application largely independent of rock type. This may take many years. In the meantime other methods of improving productivity of saleable metal by rock breaking teams should be investigated even if such methods have local applications only. In 1955 the writer conducted tests with a wire saw similar to those used in quarries in the Northern Transvaal and elsewhere. Jeppestown shale, the immediate footwall of much of the East Rand gold field, was cut at the rate of 6 in. per hour using sand, water and a special endless rope driven by a low h.p. motor. A hypothesis on its application was submitted to the Office of the Government Mining Engineer in 1955 and to other mining institutions in 1966 after the writer returned to South Africa. By inference, rope sawing was classed as less promising than other methods tested in the Orange Free State Goldfields (Parker 1969). With highly resilicified hanging and footwall quartzites this was not surprising and confirmed the writers findings when testing hanging wall quartzite from the East Rand in 1955. The relatively uniform conditions, the low strength, hardness, and silica content of the Merensky Reef platinum deposits (Gray and von Bardeleben 1969) and in particular, the existence of overlying Merensky pyroxenite (Cousins 1964) make this and the East Rand attractive areas for larger scale testing of wire saws. It is envisaged that in suitable rock types the 5/8 in. slot would be advanced down dip or down a minor dip. In undisturbed areas 'faces' of up to 200 ft in length could be cut several feet in advance of breaking which could then consist of light blasting to the second free face or some of the methods now being tested for breaking waste in rock-cutting operations. A wire saw is an inexpensive and simple machine which, in some areas, could make significant and early gains in rock breaking efficiency as well as in ground and stoping width control.

Jan 5, 1968

By Lawrence P. Bonicatto

The steel industry's increased demand for higher grade pellets has caused the pellet producers to investigate methods of upgrading their product and the Hanna Mining Co.'s Groveland plant on the Upper Peninsula of Michigan is no exception. The low grade iron deposit is a complex mixture of magnetite and hematite with chert, quartz, jasper and various iron silicates.1 Beneficiation is by Humphrey spirals and anionic flotation of the iron minerals.2 Flotation of the spiral tailings makes up about 75% of the concentrate, while a minor amount of concentrate (less than 3%) is produced in magnetic circuits. The concentrate is pelletized at the rate of 1.6 million tpy. The initial concentrating facilities were constructed in 1958 and the concentrate was marketed as sinter feed until a pelletizing plant was added early in 1963. Grade improvement soon became a high priority research project, and several methods of concentration were investigated.

Jan 3, 1968

By Robert L. de Beauchamp

The Bureau of Mines designed a chlorination apparatus to prepare CrCl2 free of CrCl3 by the direct reaction of chlorine and chromium. Equipment and procedures were developed for routine preparation of 25-pound batch quantities of anhydrous CrCl2. Calcium, iron, nickel, and silicon impurities were in the 0.01 to 0.05 percent range, and all other impurities were below 0.01 percent.

Jan 1, 1968

By John Nagy

Dust explosion data obtained in laboratory tests by the Bureau of Mines are presented for 181 miscellaneous materials that present an explosion hazard. Data are given also for 50 dusts that present primarily a fire hazard and for 88 dusts that did not present an explosion hazard.

Jan 1, 1968

By R. K. Koch

The vapor pressures of liquid columbium and liquid hafnium were deter-mined by the Langmuir free evaporation method as a part of the Bureau of Mines program on the study of transition metals. An electron-beam furnace with a water-cooled copper crucible was used for melting. Temperature was measured with a two-color ratio pyrometer. Least-squares analyses of the vapor pres-sure data gave the following equations: [Logp (atm) = 5 .429 -31,310 T] for liquid columbium in the range 2,740° - 3,140° K, and [Log p (atm) = 5,690 28 T] for liquid zirconium in the range 2,500° -2,810° K. Third-law evaluations of each data set gave mean heats of sublimation (298.15° K) of 175.1±3.2 kcal/mole and 148.3±1.2 kcal/mole for columbium and hafnium, respectively. Second-law standard heats of sublimation determined from sigma plots and from sigma-prime plots agreed fairly well with the third-law values. The sigma-prime plots gave standard entropies of sublimation of 30.96±0.84 eu and 33.S6±0.44 eu for columbium and hafnium, respectively.

Jan 1, 1968

By E. A. Gulbransen, A. Pebler

Pressure-composition isotherms have been determinedfor the systems ZrMo2 -H2 between 0" and 900°C at hydrogen pressures between 10-4 and 760 Torr. Tkese studies plus X-ray diffraction analyses of selected compositions show that these intermetallic compounds form a complete series of hydrogen solid solutions within this temperature and pressure range. The partial molar enthalpies and entropies of solution of hydrogen in the three intermetallic compounds were calculated. The solubility of hydrogen in these Laves phases can be related to their free electron concentration. ThE reaction of hydrogen with inter metallic compounds of zirconium with Laves phase-type structure has both theoretical and practical interest. The in-termetallic compounds have structures different from any of the pure metals. In addition the electron to atom ratio of the intermetallics varies appreciably. In the nuclear materials field, these materials are of interest since intermetallic compounds may exist as precipitates in commercial zirconium alloys with transition metals. From studies on the hydrogen reaction, one can establish the stability of the intermetallic compounds relative to the hydrides of the component metals. The intermetallic compounds may also be used as getters for hydrogen and as materials for hydrogen storage. This paper will present the results of equilibrium and structural investigations of the ZrCr2-H2, the ZrV2-H2, and the ZrMo2-H2 systems for the temperature range of 0" to 900°C and the pressure range of Torr to 1 atm. A complete thermochemical analysis will be made of the measurements. Some of the results have been referred to in a survey paper' covering the types of hydrogen behavior observed in zirconium alloys. LITERATURE ZrCr2 is the only intermetallic phase in the Zr-Cr system.' It exists in two allotropic modifications. Between 900" and 1000°C the hexagonal MgZa (C14) structure transforms into the cubic MgCu2 (C15) structure. Beck4 has previously shown that the intermetallic ZrCrz takes up hydrogen into solid solution up to a composition H/ZrCr2 = 1.14 at room temperature and 1 atm hydrogen. A ZrCr2 hydride was stated to have a fcc structure. The binary Zr-V system has been investigated by williams5 although Rostoker and Yamamoto 6 had given earlier a partial phase diagram. ZrV2 was the only intermediate phase found in the system. wallbaum7 reported earlier that the compound ZrV2 hp the MgZm (CJ4) type structure with a = 5.288A and c = 8.664A. This was not comfirmed by Elliot8 nor by Matthias, Compton, and corenzwit9 who reported that ZrV2 has a cubic MgCua LC15) type structure. The latter authors gave a = 7.429A. Also, several authors do not agree on the temperature of the peri-tectic horizontal. It appears that ZrV2 may exist in several modifications. A high capacity for occluding hydrogen was reported by Beck4 who found H/ZrV2 = 1.38 at room temperature and 1 atm of hydrogen. ZrMoz is the only intermetallic phase in the Zr-Mo system.10 ZrMoa is formed by a peritectic reaction of the melt with a molybdenum-rich solid solution. ZrMo2 has the C15-type structure with a = 7.59A. MATERIALS High-purity chromium, vanadium, and molybdenum were used together with grade 1 crystal bar zirconium to prepare the alloys. Table I lists the chemical analysis and the sources for the metals. Ten-gram alloy compacts were levitated and melted in an inert argon

Jan 1, 1968

By Mark D. Tabak

Measurments of the transient photoconductivity in fillns of amorphous selenium with blocking- contacts haue been used in studying the transport properties. The results shozu that the transport of free carviers cannot be explained in terms of a model using bulk trapping. Measurments of the photocurrent-applied field characteristic as a unction of sample thickness do not pvoduce the scaling lau,s approps-iate lo a range-limited model. THE investigation described here was undertaken to explore the mechanisms of transport in amorphous selenium films. These films are used in xerography, where a photoconductor is charged electrostatically and then exposed to light to form a latent image. The sensitivity that one can expect when operating in this mode is directly related to the transport properties of the photoconductor material. The study of photoconductivity at high fields in insulating materials is often complicated by contact effects. Injection from the contacts can easily mask the fundamental transport processes that are being studied. A technique is described in this paper that allows a study of photoconductivity and transport processes in amorphous selenium films without the complicating effects introduced by contacts. Accordingly, the samples are prepared using insulating films between the sample and the metal electrodes, where the electrodes are capacitively coupled to the surfaces of the sample under study. A transient measurement is performed with pulsed light, and the photocurrent measured near the beginning of the pulse before the field is distorted by polarization at the blocking elec- trodes. A similar method has been described by Manyl using pulsed electric fields in studying the high field transport in insulating cadmium sulfide. EXPERIMENTAL It is possible to eliminate undesirable contact effects and maintain uniform high fields across the sample by using blocking electrodes and measuring the current-field characteristic under transient conditions. The sample configuration is shown schematically in Fig. 1. Each of the gold electrodes is separated from the amorphous selenium film by a layer of insulating plastic (Formvar) approximately 2000~ thick. The electrode on the front surface is semi-transparent to allow illumination of the sample. The whole configuration is mounted on a KEL-F substrate, which is a transparent insulating plastic having a thermal expansion coefficient that allows low-temperature measurements without cracking the selenium film. Fig. 2 shows a block diagram of the measurement apparatus. Light was obtained from a 450-w Xenon arc lamp, the intensity of which was controlled by stainless-steel screen filters and monitored by a pho-tomultiplier which was calibrated periodically against a thermopile. A camera shutter operated at 1/200 sec provided the light pulse and a synchronized signal to the oscilloscope. The photocurrent transient is ob-served with a high-speed picoammeter (response time of 1 msec) the output of which is displayed on an oscilloscope. The applied voltage is constant throughout the transient measurement. The selenium films were prepared by evaporation of four 9's pure selenium shot supplied by Canadian Copper Refiners. Spectrographic analysis showed about 1 ppm of Te and Fe, 5 ppm of C1, and 0.05 ppm

Jan 1, 1968

By F. A. Renninger

The mineral aggregate industry is the world's largest mining and processing endeavor, yet it is graced with little of the romance or public awareness that accompanies mention of gold, silver, iron, copper, uranium, or aluminum mining efforts. Much of this reaction is undoubtedly due to the fact that the uses to which crushed stone and sand and gravel are normally put are not fully recognized or appreciated by the general public. Few individuals ever have occasion to purchase mineral aggregates for anything other than use for decorative shrubbery beds or walkways. They may, however, buy ready-mix concrete for a new patio, bituminous concrete for a new driveway, concrete blocks, or other building materials for a new room and never realize that the primary ingredients of their purchases are either direct or indirect products of the mineral aggregate industry. The average person driving past an operating crushed stone quarry or an active sand and gravel pit rarely realizes the economic impact the industry, represented by that operation, exercises on the general economy. He is not aware, nor does he really care, that elements of the modern comfortable environment to which he has grown accustomed rely to a great extent on the products of the crushed stone and sand and gravel industries Iron and steel, glass, cement, agriculture, and highway and building construction are but a few of the major industries to whom the products of the mineral aggregate industry are basic. Without these industries or without the stone, sand, and gravel basic to them, most of the major elements of our modern day civilization would be non-existent.

Jan 1, 1968

By Donald F. Hammer, Donald W. Peterson

The Magma mine at Superior, Arizona, has produced over 13 million tons of ore yielding 1.5 billion pounds of copper. It is a mesathermal deposit, and, although the bulk of the ore has come from the Magma vein, most of the recent production has come from replacement deposits in limestone. The mine lies in a Precambrian and Paleozoic sequence of rocks that includes schist, diabase, quartzite, shale, and limestone; nearby, these rocks are intruded by igneous bodies of Mesozoic age that were probably the source of the ore-bearing fluids. Locally, these rocks are overlain by Cenozoic volcanic rocks and conglomerate. Layered rocks at the mine dip eastward about 30°. The area is extensively faulted, and surface faults are grouped into an earlier east-trending set and a later northtrending set. An additional set of diagonal faults that trends northwest and northeast is recognized underground. The east-trending Magma vein-fault, with its splits and branches, is the principal mineralized structure of the district. The bulk of the ore occurs in large ore shoots that plunge steeply westward and are sporadically connected by irregular ore shoots dipping gently eastward. The main ore controls apparently are selective zones of permeability related to the transverse faults. A bed of crystalline limestone near the base of the Martin Limestone (Devonian) is the host for the replacement ore bodies-discontinuous tabular pods dipping eastward parallel to the bedding. Selective permeability is again the apparent ore control, caused both by local hydrothermal solution of limestone and by deformation along faults. The principal copper minerals in the vein are chalcopyrite, bornite, enargite, tennantite, chalcocite, and digenite; these minerals vary in abundance according to a distinct zoning pattern. The upper part of the mine yielded considerable zinc as sphalerite, and the oxidized zone was rich in silver. The chief gangue minerals are pyrite, quartz, and hematite. In the limestone replacement bodies, chalcopyrite and bornite are the chief ore minerals.

Jan 1, 1968

By Philip C. Good

Preliminary studies showed that direct hydrolysis of H2SiF6 to SiO2 and HF at elevated temperatures was subject to many mechanical difficulties, and that corrosion of construction materials was a serious problem. Elimination of SiO2 from the HF product was generally poor. An alternative procedure, hydrolysis of lime-neutralized H2SiF6 by steam at 950° to 1,100° C, yielded a product very low in SiO2. Condensates containing up to 300 g/1 HF were prepared.

Jan 1, 1968

By Gordon B. Brox, Joseph F. Mcaleer, Charles C. Goddard, Edward P. Shea, Robert G. Ingersoll, Lester G. Zeihen, George J. Burns, John M. Guilbert, Richard N. Miller, Charles Meyer

The Boulder batholith is a composite intrusive in which the Butte quartz monzonite is the dominant rock type. Quartz porphyry dikes intruded the quartz monzonite in directions which were subsequently followed by the eastwest- striking Anaconda system of veins, the earliest major veins in the district. Anaconda veins are faulted by northwest-striking veins of the Blue system, which are most prominent in the central third of the district. Anaconda veins are the major producers in the western third of the district and also in the eastern third, where the "horsetail" zones break off from them. Individual oreshoots are thousands of feet long as well as deep on both systems of veins, but they are generally more persistent and thicker on the Anaconda veins. Viewed broadly, the mineralization in the big veins is arranged in crudely concentric zones of zinc and manganese around a central zone of copper. Only slightly offset from these zones, but earlier structurally, is a zone in which quartz-molybdenite veinlets are prominent. This zone tops at about the 2800 level and widens downward. The pattern of distribution of Cu-Fe-S series minerals in the large veins of the copper zone is not symmetrical with respect to the metal zones. There is a fringe of chalcopyrite-bornite all around the copper front. However, within the copper zone, pyrite-chalcocite-enargitecovellite- digenite assemblages are prevalent near its eastern edge from the 3800 level to the surface, whereas deep on the large Anaconda veins in the western part of the copper zone, chalcopyrite is dominant. Here the chalcopyrite grades upward into bornite-chalcocite ores and eastward into the high-sulfur assemblages of the Leonard mine. Sericite-biotite-K-feldspar alteration envelopes, containing up to about 2 per cent copper as chalcopyrite, are present on some of the quartz-molybdenite veinlets at deep mine levels in the molybdenite zone. These envelopes contrast sharply mineralogically and chemically with the later sericitic and argillic alteration envelopes around Main Stage veins. K'0-Ar'0 ratios indicate that they may be older by about 4 m.y. Secondarily enriched copper ores are mined in the Berkeley pit in the southeastern part of the district. At the present time they account for about half of Butte's production of copper.

Jan 1, 1968

By Andrew J. Fergus

The purpose of this study was to provide basic information to aid further research on beryllium mineral flotation. Contact-angle and microflotation (Hallimond tube) methods were used to study collector action and flotation response of beryllium minerals and associated gangue minerals with representative commercial surfactants. Chrysoberyl received prime attention. Results indicated that selective flotation of beryl and chrysoberyl from fluorite and quartz is possible with sodium isooctyl phosphate below pH 2, and fluorite and topaz are readily collected by both anionic and cationic surfactants. Several modifying reagents were studied at one pH and one level of collector concentration. Aluminum sulfate, starch, and sodium silicate proved to be depressants in chrysoberyl flotation.

Jan 1, 1968

By R. O. Dannenberg

A metallic displacement process, utilizing easily available steel wool or steel window screen, was devised and successfully used for the recovery of silver from waste photographic fixing solutions. Laboratory and prolonged commercial-scale testing established that the iron filament type unit will efficiently precipitate silver, as a high-grade sludge, from acidic waste photographic fixing solutions ranging in grade from less than 1 to over 10 grams of silver per liter. Data and design information are presented to facilitate the construction and operation of a practical unit of any desired size. A smelting process for recovering pure silver from precipitated sludge containing 27 to 80 percent silver was devised.

Jan 1, 1968

By J. W. Leomrd, B. A. Donahue

Results of research are presented examining the extent to which the analytical characteristics of the relatively distinct coal bands from a variety of coal seams can be related to each other. This paper dis-cusses an approach for developing a practical coal petrographic quality control program based on conventional analyses, most of which is part of the standard A.S.T.M. procedure. The work is a final follow-up to Part I of this series which was prepared by the authors as an approach to applying conventional coal petrography to single coal seams. Recent published work by the authors entitled Petrography for Coal Mining and Coal Prepration: Part I dealt with interrelating various chemical and physical properties of coal1 measured using conventional analyses made on distinct petrographic bands taken from single coal seams. Since most coal production facilities process coal from a single coal seam or from very closely related coal seams in the same area,2 emphasis on interrelating the properties within a single seam appeared appropriate. The distinct petrographic bands were analyzed on the assumption that such differentiated data would be more representative of a heterogeneous coal seam than the single analytical value commonly used to characterize each property of an entire seam.34 Effort was directed at demonstrating the extent to which the interrelated chemical and physical properties 5,6 could be developed into nomographs or petrographic standardization graphs. Thus, one analysis, determined on a series of petrographic fractions separated from a single sample, was used to estimate numerous other properties in each fraction by referring to the previously established petrographic standardization graphs. This conventional approach to coal petrography was undertaken as a suggested feasible means by which a few coal analyses could be employed to develope a more penetrating knowledge of the properties of coal from any given seam in order to monitor more extensively its performance at the point of utilization. Such procedures can support development of the type of in- formation commonly sought through automated testing and through the use of computers.7 The broad knowledge which can be developed through these procedures is intended for application in the generation of an analytical profile or broad characterization of coal. These estimates were not intended as replacements for individual coal analytical tests. In this expanded second part of the research program, distinct petrographic bands from nine coal seams in the Central Appalachian Region were physically and chemically analyzed to elucidate the extent to which this concept of conventional petrography could be broadened for application to numerous coal seams. In presenting this second phase of work, the relationships developed are presented individually and not in a connecting series of nomographs or petrographic standardization graphs as in the previous work, thus leaving open the combinations of possibilities to individual interpretation and application. MATERIAL AND EXPERIMENTAL WORK Nine coal seams, representing a wide range of rank, from the Central Appalachian coal fields were used in this study. The distinct petrographic bands from the Kittanning, Pond Creek, Jawbone, Tiller, Poca-hontas No. 3, No. 2 Gas, Eagle, Winifrede, and Pittsburgh coal seams were separated by carefully removing a portion of each band at the face of the seam. The following were determined: ash, sulfur, free swelling index, heating value, bulk specific gravity, volatile matter, Hardgrove Grindability Index, and Gieseler Plastometer measurements. Determinations, where procedures were available, were carried out using ASTM standard procedures.8 Bulk specific gravity was determined using a kerosene volume displacement procedure modified from a method applied by Headlee and McClelland of the West Virginia Geological survey,9 Those bands with a bulk specific gravity greater than 1.60, which is generally above the practical specific gravity cleaning range of bituminous coals, were excluded and no analyses were performed. Much of the initial organization of this second phase of work was developed through the extensive use of a computerized statistical monitoring program (see Ref. 4). However, in order to achieve the closest possible interpretation of results, the final organization of data proceeded mainly from exhaustive trial

Jan 1, 1968

By E. J. Fasiska, H. Wagenblast

The dilalion of a ivon by interslilial carbon was measured by two independent techniques —dilatometric mesurements at 719 c and X-ray measurments of the urlil cell parameters a1 room temperature after quenching. The relative expansion per increase in cavbon content by both methods is (2.9 + 0.3) x 10-3 pev at. pcl C nrzd is temperature- independent within experimental error. This corresponds to (6.3 5 0.6) cu cm per g-atom for the partial gram-atomic volume of carbon in a iron-only slightly smaller than the atomic volume for iron in the same temperature vange. THE only previous quantitative study of the dilational effect of carbon dissolved in a iron was performed in 1934 by Burns1 which, at the time, generated some discussion of possible sources of experimental error.2 For a system of such widespread importance, we felt that a new investigation was merited. Both X-ray diffraction and dilation measurements were used to determine the expansion of the a iron lattice by dissolved carbon, avoiding as much as possible any previous experimental problems and deficiencies. The dilation method at solution temperature offers not only measurements which are free of residual strain but also, in conjunction with the room-temperature X-ray measurements, a method to detect any large temperature dependence of the partial gram-atomic volume of carbon. To insure that quenching strains did not affect the room-temperature X-ray measurements, wire specimens of constant carbon content but different diameter were examined for such an effect. SPECIMEN PREPARATION The material used for both experimental techniques was "Ferrovac E" iron received in the form of 19-mm-diam rod and stated as having the following impurity contents: C, Cr, Cu, Mn, P, and V, each in the range of 10 to 50 ppm; Co, O, Mo, S, and Si, 60 to 100 ppm; W, 200 ppm; Ni, 230 ppm; N, 4 ppm. The stock material was cold-swaged to 0.71 mm diam for the Debye-Scherrer X-ray camera specimens and portions were cold-rolled from 6.3 mm diam to 0.79- and 0.25-mm sheet for X-ray diffractometer and dilation measurements. The wires were annealed in wet hydrogen for 6 hr at 840°C and 15 hr at 720°C, and then quenched into 0°C water. A chemical analysis for carbon after this treatment gave 0.0046 + 0.0014 at. pct C. Three portions of these wires were subsequently held at 719°C in three different hydrogen + methane mixtures and then quenched, resulting in carbon concentrations of 0.0283, 0.0598, and 0.1067 at. pct C by chemical analysis. After carburizing, the wires were swaged to 0.48 mm and electroplated with silver to prevent carbon loss during subsequent heat treatment. The final heat treatment consisted of holding the wires at 72 1°C for 5 min in a He-2 pct H mixture followed by quenching into 0°C brine. The wires were held at room temperature for a few minutes to remove the silver plating using a phosphoric acid-hydrogen peroxide solution, and then stored in liquid nitrogen until the measurements were made. EXPERIMENTAL TECHNIQUE A) Dilation Measurement. The dilatometer consisted of a gas-atmosphere vertical tube furnace modified so that length changes of a ribbon-shaped specimen could be measured externally. This was done by installing a gas-tight mercury seal at the top of the furnace as shown schematically in Fig. 1. The specimen (21.0 cm long, 1.27 cm wide, and 0.25 mm thick) was suspended in the center of the furnace by 3-mm-diam quartz rods with the upper one passing through the cap of the mercury seal. Above the cap, the upper quartz rod was coupled to a lever exerting a load of about 25 g (-12 lb per sq in.) on the specimen and having a 10 times mechanical magnification. The vertical position of a marker at the other end of the beam was read with a traveling microscope with a precision of 0.01 mm. The temperature gradient of the furnace was meas-

Jan 1, 1968

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By R. T. DeHoff

In any structural transfortnation which is driven by surface tension, the geometric variable of fimdamental importance is the local value of the mean surface curvatuve. Acting through the suvface free energy, this quantity determines the magtnitude of both the pressure and the chemical potential that develops in the neighborhood of an arbitrarily curved surface. A metallographic method which would permit the quaniitatiue estinzation of this propevty is of fundarnerztal irztevest to studies of such processes. In the present paper, it is shoun that the average value of the mean surface curvature in a structuve can be estimated from two simple counting measuretnents made upon a vepresentative metallograpIzic section. No simplifyirlg geonzetric assurmptions are necessary to this deviuation. It is further shoum that the result may be applied to parts of interfaces, e.g., interparticle welds in sintering, or the edge of growing platelets in a phase transformation, without loss of validity. In virtually every metallurgical process in which an interface is important, the local value of the mean surface curvature is the key structural property. This is true because the mean curvature determines the chemical potential of material adjacent to the surface, as well as the state of stress of that material. The theoretical description of such broadly different processes as sintering,1,2 grain growth,3 particle redistrib~tion4,5 and growth of Widmanstatten platelets8 all have as a central geometric variable the "local value of the mean surface curvature". The tools of quantitative metallography currently available permit the statistically precise estimation of the total or extensive geometric properties of a structure: the volume fraction of any distinguishable part:-' the total extent of any observable interface,10,11 and the total length of some three-dimensional lineal feature:' and, if some simplifying assumptions about particle shape are allowed, the total number of particles.'2"3 The size of particles in a structure, specified by a distribution or a mean value, can only be estimated if the particles are all the same shape, and if this shape is relatively simple.14-16 The relationships involved in converting measurements made upon a metallographic section to properties of the three dimensional structure of which the section is a sample are now well-established, and their utility amply demonstrated. In the present paper, another fundamental relationship is added to the tools of quantitative metallography. This relationship is fundamental in the sense that its validity depends only upon the observation of an appropriately representative sample of the structure, and not upon the geometric nature of the structure itself. It involves a new sampling procedure, devised by Rhines, called the "area tangent count". It will first be shown that the "area tangent count" is simply related to the average value of the curvature of particle outline in the two-dimensional section upon which the count is performed. The average curvature of such a section will then be shown to be proportional to the average value of the Mean surface curVature of the structure of which the section is a sample. The final result of the development is thus a relationship which permits the evaluation of the average value of the mean surface curvature from relatively simple counting measurements made upon a representative metallographic section. The result is quite independent of the geometric or even topological nature of the interface being studied. QUANTITATNE EVALUATION OF AVERAGE CURVATURE IN TWO DIMENSIONS The Area Tangent Count. Consider a two-dimen-sional structure composed of two different kinds of distinguishable areas (phases), Fig. l(a). If the system is composed of more than two "phases", it is possible to focus attention upon one phase, and consider the remaining structure as the other phase. The reference phase is separated from the rest of the structure by a set of linear boundaries, of arbitrary shapes and sizes. These boundaries may be totally smooth and continuous, or piecewise smooth and continuous. An element of such a boundary, dA, is shown in Fig. l(b). One may define the "angle subtended" by this arbitrarily curved element of arc, dO, as the angle between the normals erected at its ends, Fig. l(c). Now consider the following experiment. Let a line be swept across this two-dimensional structure, and let the number of tangents that this line forms with elements of arc in the structure be counted. This procedure constitutes the Rhines Area Tangent Count. Suppose that this experiment were repeated a large number of times, with the direction of traverse of the sweeping lines distributed uniformly over the semicircle of orientation.' Those test lines which ap- proach from orientations which lie in the range O to O + dO form a tangent with dA; those outside this range do not, see Fig. l(c). Since the lines are presumed to be uniformly distributed in direction of traverse, the fraction of test lines which form a tangent with dA is the fraction of the circumference of a semicircle which is contained in the orientation range, dO; i.e., vdO/nr or dB/n. If the number of test lines is N, the number forming tangents with dA is N(d0/n). Since each test line sweeps the entire area of the sample, the total area traversed by all N test lines is NL2. The number of tangents formed with dA, per unit area of structure sampled, is therefore

Jan 1, 1968

By R. P. Aikman, F. G. Miller, J. M. Podgursky

As part of a larger study of the mechanism of froth flotation of coal, the rates at which coal particles of various size and specific gravity react to froth flotation were investigated. Results of this study show that in flotation: I) recovery rate increases, but selectivity decreases with a decrease in particle size down to 100 mesh, and 2) recovery rate is constant for all sizes between 100M and 325M. n response to the growing demand for low-sulfur coking coal for iron making, the coal industry is continually striving to perfect methods for cleaning coal to acceptable ash and sulfur levels while maintaining maximum product yield. By present standards the industry has adequate processes for cleaning coarse coal, i.e., + 28 mesh, at almost any desired specific gravity. However, in the case of fine coal, i.e., —28 mesh, neither of the two existing processes - froth flotation or hydrocycloning — in its present state of development yields products that are comparable in ash and/or sulfur content to products normally obtained from coarse coal processes. The work outlined in this paper is part of a larger study directed toward maximum exploitation of froth flotation for fine coal processing. The concepts and data presented are now serving as a basis for designing fine-coal circuits in which improved efficiency is obtained by optimum use of froth flotation with other fine-coal processing methods. The paper includes: 1) A discussion of the value of a detailed wash-ability study as a method of assessing the problems associated with fine coal processing, 2) A general discussion of hydrocyclone principles, included to serve as a basis for understanding the mechanism of coal flotation, and 3) A detailed discussion of the mechanism of coal flotation, as well as the research leading to the optimum use of froth flotation in combination with other fine-coal cleaning methods to provide efficient fine-coal processing. Our study of the rates at which coal particles of various size and specific gravity react to flotation shows that in flotation: 1) recovery rate increases but selectivity decreases with a decrease in particle size down to 100 mesh, 2) recovery rate is constant for all sizes between 100 mesh and 325 mesh, and 3) the flotation process effectively rejects only those extremely fine particles which do not contain surface carbon. (Because of this feature, froth flotation is an excellent method for rejecting clays - the only extreme fines in - 325-mesh coal that are always carbon free.) Washability studies of flotation products are used to assess flotation efficiency. These studies show that: 1) the increase in percent sulfur in flotation products above the theoretical sulfur content as defined by the washability study is due almost entirely to flotation of fine high-specific-gravity particles that are part coal and part pyrite, and 2) in a given size range particle floatability decreases with an increase in particle specific gravity. Error curves are explained and are used to compare the mechanisms of coal flotation and hydrocycloning. These comparisons show that hydrocyclone performance is affected primarily by particle mass, i.e., particle specific gravity and size, whereas coal flotation performance is dependent on both the particle mass and the coal surface available for bubble attachment. Since the error curve is a basic tool for rating the efficiency of any coal processing system, it will be useful to quickly review the principles of error curve construction. RATING COAL-PROCESSING EFFICIENCY BY THE ERROR CURVE The organic component of coal is of lower specific gravity than its impurities, and the most effective principle for coal concentration is therefore separation on the basis of specific gravity. However, since there is no sharp dividing line between pure coal and pure ash components, specific gravity must be closely controlled if the product is to have acceptable quality at maximum yields. In turn, the basis for close control in any coal processing system is the reference standard provided by precise laboratory washability studies. In these studies, coal is carefully separated into a series of progressively higher specific gravity fractions to establish a relationship

Jan 1, 1968

By E. P. Sadowski, L. P. Trudeau, C. R. Cupp

The apparent high radiation resistance of two varieties of maraging steel is described and an indication is given of some phenomena that require further study. Two aspects were included in this work: a) effects of neutron irradiation on the room-ternperature tensile properties of 18 Ni (250) maraging steel; b) effects of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5pct Cr-3 pct Mo maraging steel. Subsize tensile and impact test specimens were used. The 18 pct Ni steel was irradiated to a neutron fluence of 3.3 x 10 n per sq cm (>1 mev). The 12-5-3 variety was irradiated to two neutron fluence levels: 1) 1.5 x 10 per sq CTTL (>I mev) 2) 3.1 x 10'9nper sq cm (>1 mev) In all respects both varieties showed unusually high resistance to change in strength and ductility after neutron irradiation. There was no noteuorthy over-aging in fully aged specimens. The aged 18 pct Ni variety showed a 4 pct drop in yield strength upon irradiation with little or no decrease in ductility. The aged 12-5-3 variety showed a 5 pct increase in yield strength on irradiation with a very slight decrease in ductility. The impact transition of the 12-5-3 variety only increased 35 to 45 Co upon irradiation, and the shear energy fracture value for the subsized specimens decreased only half as much as expected frorn experience with conventional steels. THE development of new reactor concepts and nuclear technology now depends to a large extent on the availability of new alloys capable of operating in stringent reactor environments. One of the most important new types of metallurgical material that has been developed in recent years is the maraging steels. This type of alloy is notable for its remarkable retention of toughness at high strength levels. In the course of a research program which incorporated ambient temperature radiation effects studies to determine the mechanisms of strengthening of 18 pct nickel maraging steel,' it became evident that the resistance of the alloy to neutron-induced changes in mechanical properties should be studied. This paper is to present evidence for the apparent high radiation resistance of maraging steel. The experimental program was in two parts: a) Effect of neutron irradiation on the room-temperature tensile properties of 18 Ni (250) maraging steel. b) Effect of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5 pct Cr-3 pct Mo maraging steel, a cobalt-free alloy. EXPERIMENTAL PROCEDURE 18 Ni (250) Maraging Steel. Tensile test specimens were machined to the dimensions shown in Fig. 1 from $-in.-diam hot-rolled bar of the composition shown in Table I. All specimens were austenitized for 1 hr at 1500°F (815°C) in argon and water-quenched. Half of the specimens were then mar aged for 3 hr at 900° F (482°C) in argon. The specimens were irradiated in a fast neutron transformer rod at approximately 120°F (50°C) to a neutron fluence of 3.3 x 10 10 n per sq cm (>1 mev). The irradiation was performed in the NRX reactor of Atomic Energy of Canada, Ltd., at Chalk River, Ontario, Canada. In all cases, the thermal neutron flux was three times as high as the reported (> 1 mev) fluxes. The room-temperature tensile tests were performed with an Instron tensile testing machine operating at a crosshead speed of 0.05 in. per min. The loading frame of the machine, mounted in a hot cell, was remotely controlled. The specimens were tested either

Jan 1, 1968

By G. V. Sirianni, G. E. Viens, R. A. Campbell, G. N. Banks, R. L. Sachdeva

"A combined shaft-electric furnace for the smelting of ores and the melting of metallized iron pellets is being developed. The materials are preheated, and in some cases pre-reduced, in the shaft before being transferred to the electric furnace, where melting or smelting is completed. It has been demonstrated that this combination of equipment will enable much of the relatively expensive electrical energy to be replaced by cheaper energy in the form of oil or natural gas, and preliminary experiments indicate that the total energy requirements for a melting or smelting operation are significantly reduced. Projections based on results obtained from the preliminary experiments indicate that further improvements will be possible when certain modifications to the equipment are completed."

Jan 1, 1968