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By Donald L. Katz, Leslie J. Noaker

Experimental data are presented for hydrate formation conditions for mixtures of hydrogen sulfide and methane. Vapor-solid equilibrium constants for hydrogen sulfide are also presented. Equilibrium constants, defined here as the ratio of the mole fraction of hydrogen sulfide in the vapor phase (dry basis) to the mole fraction of hydrogen sulfide in the solid phase (dry basis), were calculated using the vapor-solid equilibrium constants for methane presented in an earlier paper. The conditions at which a natural gas will form gas hydrates with water may be computed from its composition, when hydrogen sulfide is present in addition to carbon dioxide and the paraffin hydrocarbons. INTRODUCTION Many gases are known to form solid hydrates in the presence of liquid water at temperatures above 32°F. This hydrate formation is of importance to the natural gas industry inasmuch as most of the constituents found in natural gases will form hydrates. The attention of the industry was called to hydrates by Hammer-schmidtl0 in 1934. A number of papers have been written giving the temperatures and pressures at which these hydrates will form3,4,5,6,7,8,9,10,13,14,15,18,19 and a bibliography on the subject has been compiled13. Deaton and Frost4,5,6,7,8 report work for various pure gases and for some natural gases. Katz and co-workers3,4,13,14,18,19 have reported data for various gases at high pressure. They developed a method of predicting conditions for hydrate formation from equilibrium constants3,19 and from gab gravity." The effects of anti-freeze agents on the formation of hydrogen sulfide hydrate were reported by Bond and Nelson.' The hydrogen sulfide-water system, including hydrate, has been the subject of recent investigation by Sage and co-workers." Mixtures of hydrates behave as solid solutions and an equilibrium exists between the vapor phase and the solid phase that appears to be comparable to the equilibrium between vapor and liquid phases.3,10 By means of the vapor-solid equilibrium constants which have been published for methane, ethane, propane, iso-butane, and carbon dioxidel6 it is possible to determine the temperature and pressure at which hydrates will form for a specific gas mixture when water is present. Hydrogen sulfide which is frequently found in natural gases has a very strong tendency to form hydrate and must enter the solid solution when present in a natural gas forming a hydrate. To determine the effect of hydrogen sulfide when computing the conditions for gas hydrate formation, it is necessary to have the equilibrium constant giving the ratio of the concentration of hydrogen sulfide in the gas phase to the concentration in the solid phase. This paper presents data on hydrate formation for mixtures of hydrogen sulfide and methane and presents the equilibrium constants which were calculated from these data. EXPERIMENTAL PROCEDURE The apparatus used to determine the conditions of hydrate formation for the methane-hydrogen sulfide system was similar to that employed by previous investigators.3,18,19 A charge gas cylinder was used to supply the hydrogen sulfide-methane mixtures, called the charge gas, and to supply the pressure up to 1.000 psia. This

Jan 1, 1955

By Yuanbo Zhang, Zijian Su, Bingbing Liu, Guanghui Li, Jicheng Liu, Manman Lu, Tao Jiang

Blast furnace slag (BFS), one kind of typical solid waste in the steel industry, was used as structural materials to synthesize NaNO3/BFS composite phase change materials (C-PCMs) by mixing and sintering method. NaNO3 in the composites functioned as phase change materials (PCMs) and BFS as structural skeleton to maintain a stable external form. In this study, the prepared C-PCMs could remain in the solid state without salt leakage even if operating temperature exceeded the melting temperature of NaNO3. The composition and structure of BFS and the prepared composites were characterized by XRD, FTIR, SEM and TG-DSC analyses. The results showed that NaNO3 was well incorporated in the pores of BFS. The melting temperature and latent heat of the final composites were 300.5 °C and 65.53 J/g, respectively. The product also had good thermal storage performance and durability even after 100 thermal cycles. The energy density of the product was calculated as high as 468.03 J/g for an temperature range of 50–400 °C.

Mar 1, 2018

By J. Kalynchuk, R. Poulin, R. Pakalnis, D. Peterson

"A market survey of all underground mines in Canada (Fig. 1) was completed to determine the ex1ent to which cable bolts are being used as ground support. One hundred and nine questionnaires were distributed with 65% of them being returned completed. As a result, the quantity, types and locations of cable bolt installations have been determined. In addition, the grout pumps used, time required and cost of installations have been addressed. The popularity of other support types used in underground mines is summarized.IntroductionRock reinforcement consists of installing support within the rock mass (internal) or within the excavation (external). Within the past twenty-five years several new types of ground support have been introduced within the mining industry. Cable bolts were first introduced to the Canadian mining industry in the 19605 (Gramoli, 1975).Cable bolts have gained increased acceptance as a method of ground support during the past decade. The cable bolt is comprised of one central wire surrounded by six slightly smaller outside wires and typically having an over-all diameter of 15.2 nun to 15.9 nun (0.6 in. to 0.625 in.). The cable wires are made from high-strength steel with an ultimate strength of 26 tonnes (58 000 Ibs) (Goris, 1990). Current cable bolting practice consists of cement grouting one or more steel cables within a drill hole in order to reinforce the surrounding rock mass. Cable bolts are a form of internal support and are generally used in open stoping and cut-and-fill mining methods (Fig. 2).They can be either tensioned (active support) or untensioned (passive support) and may be of any length, though for underground mining applications, they are generally less than 20 m (65.5 ft) and are untensioned. A major advantage compared to previously used ground support is that the cables are flexible and can be coiled to approximately 1 m (3.3 ft) diameter coils allowing relatively long support to be installed in areas with limited head room (1.8 m).With the advent of bulk mining methods which require comparatively large stopes, it has necessitated the use of relatively long support tendons to stabilize the large spans being created. As a result, the use of cable bolts for ground support in mines has increased significantly within the past decade."

Jan 1, 1995

By R. V. Ramani

One area of study in the Coal Mine Injury Analysis project was to illustrate and enhance the ability of mine safety management personnel to apply analytical techniques to injury experience data and to justify requests for funds for safety enhancement actions on a cost/benefit and other quantitative basis. Four volumes of this final project report detail (1) the objectives and scope of the mine safety management research, (2) the results of literature review, and case studies, and (3) models developed for mine safety management. The four volumes are titled as Volume III: Mine Safety Management, Volume IV: Analytical Techniques for Mine Safety Management; Volume V: Mine Safety Management Case Studies and Volume IX: Training Cost Model. This volume deals with the development of a microcomputer based training cost model (TCM) which can be used to analyze training cost implications of various types of training. The model has been developed using Aston Tate's dBASE III plus language. The computer program and a test run of the model are presented in this report.

Jan 1, 1993

By Park Wright

THE fact that granite has been encountered by the drill by those in search of oil and gas in Kansas is becoming more and more a matter of interest, not only to the oil producer but to everyone directly and- indirectly connected with the oil business. It is, therefore, time that someone should offer an explanation for its presence and form a definite opinion based on all the data available in regard to the effect it will have on the future prospects of the area affected as probable oil- and gas-producing territory. At present there seems to be no consensus of opinion. To the writer's knowledge, only one attempt has been made to explain; by Erasmus Haworth, State Geologist of Kansas, in a paper entitled Bulletin, Number Two on Crystalline Rocks in Kansas. The purpose of the present paper is to offer a theory for the presence of the granite and to draw conclusions which will aid in determining the prospective oil and gas value of the area in question. In taking up this question it will be well to consider first the tests in which granite has been reported, with a general history of each. The accompanying map (Fig. 1) shows the location of all wells described. The first well in which granite was reported was that drilled just south of Zeandale in section 27, township 10 south, range 9 east, by a local company which had taken up a block of leases in that vicinity. At a depth of 958 ft. (291.99 m.) granite was encountered. Drilling was continued to a depth of 1,093 ft. (333 m.) in the same formation, at which depth the hole was abandoned. Another well was started 1 mile east of the first well and the same rock was found at a depth of 945 ft. (288 m.). Drilling was continued to a depth of 1,200 ft. (365.76 m.) with the bit in the sane formation. Samples of the drill cuttings have been examined and they are undoubtedly crushed granite. The next well in which granite was found was that drilled by DeLaat and Shepard, independent wildcat operators, in section 34, township 19 south,. range 7 east, near the town of Elmdale. Granite was struck at 1,707 ft. (520 m.) and the hole was abandoned in the same formation at 2,525 ft. (769 m.). Mr. DeLaat watched the drilling of this well very closely and he has described to me in some detail the formation immedi-

Jan 8, 1917

By M. G. Benz, J. F. Elliott

A new type of solution calorimeter has been constructed to measure heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction at temperatures above 1000°C. With it, measurements hove been made of the partial molar heats of mixing joy tin in the Cu-Sn system from 0 to 13 at. pet Sn at 1127°C and fir nickel in the Cu-Ni system from 0 to 9 at, pet Ni at 1200°C. The integral molar heat of mixing for the Cu-Sn system is strongly negative with a calculated minimum value corresponding to the composition Cu3Sn. The integrnl molar heat of mixing for the Czi-Ni system is slightly positive at these temperatures. These integral molar values have been measured with a probable error less than 30 cal per g-atom at an atom fraction of nickel or tin equal to 0.1. The estimated probable error for the Cu-Sn system is approximately 450 cal for a measured heat of solution of approximately 9000 cal. For the Cu-Ni system it is approximately 700 cal for a measured heat of' solution of approximately 60 cal. A new type of heat of solution calorimeter was designed and constructed to provide a more accurate experimental method for determining heat effects at high temperatures, (T > 1000°C). With it, partial molar heats of mixing, enthalpy increments, heats of fusion, and heats of formation and reaction for metal systems can be measured directly. Previously it has been necessary to rely upon the use of the dropping calorimeter or the van't Hoff equation applied to equilibrium data for this information. For the most part equilibrium data are scarce and difficult to obtain in many cases, and it has been necessary to rely upon the "method of mixtures" for the desired enthalpy measurements. An earlier study1 provides a prototype for this work. The "method of mixtures" as outlined by K. K. kelley,2 "consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a calorimeter operating at or near room temperature.'' In this manner the change in the total heat content (enthalpy) of the substance between the temperature of the furnace and that of the calorimeter is determined. In order to determine high-temperature heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction, it is necessary to take the difference between two such measurements, one before and one after the occurrence of the enthalpy change being studied. The desired enthalpy change is then the small difference between two large numbers. Small errors in the large numbers are included as large errors in this small difference. It is this difficulty that must be avoided for accurate measurement of the desired functions. The procedure with the new solution calorimeter consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a solution calorimeter operating in the temperature range of 1000o to 1200°C. Measurements in the range of 1200" to 1600°C are planned for the future. By selection of the composition and

Jan 1, 1964

By L. M. Howe, J. Gordon Parr, E. Saarema

THE decreasing solid solubility limit at the titanium-rich end of the Ti-Cu constitutional diagram,' Fig. 1, suggests the possibility that titanium-rich alloys may be age-hardenable. However, results obtained by Holden et al. reproduced in Fig. 2 show that after quenching from 790°C the age-hardening of an alloy containing 1.7 pet Cu is very slight, while a 0.8 pet alloy decreases in hardness, during heat treatment at 400°C. It was believed possible that powder samples of alloys might show different results from the lump samples used by Holden et al., since small particles are often more sensitive to diffusion processes than larger samples. Consequently, a 1.9 pet (by weight) Cu alloy was made by the technique of levitation melting," checked for homogeneity, and filings of 48-65 Tyler screen size were cut from it for aging experiments. The filings were helium-quenched (by a technique described previously)' from 790°C, sealed in vacuo in silica tubes and aged at temperatures of 400°, 450°, and 500°C. Microscopic and X-ray examinations failed to reveal any structural changes during the aging process. This is not too surprising since early stages of precipitation do not usually manifest themselves in ways that are readily detectable by metallographic methods, and the extent of precipitation on overaging a 1.9 pet alloy is very small. However, hardness readings (taken on a Bergs-man micro hardness tester, using a 25 g load applied to a diamond indenter) do show a hardness peak at each aging temperature, Fig. 3. About a dozen readings were taken on each heat treated sample; the highest reading and the lowest reading were ignored and an average taken of the remaining values. In

Jan 1, 1957

By R. D. Brown

"AbstractIn order to raise the enormous amounts of capital which will be essential for the development of Canada's mineral and petroleum resources, this country's resource industry must be permitted to earn an acceptable rate of return. The existing tax regime, with its high rates, complexities and misdirected incentives, presents a serious obstacle to our resource industries in their development of Canada's immense , but increasingly lean, resources. Government tax and other policies are not the only cause of the crisis now facing the resource sector in Canada, but a reformed tax system, with stable and reasonable tax burdens, is required if Canada's resources of minerals, oil and natural gas are to continue to contribute in the future, as in the past, to our national well-being.An independent task force, organized under the auspices of the Canada West Foundation, has recently completed a wide -ranging report: on the future development of Canada's mineral, oil and gas resources. This five-volume report, completed after almost two years of research and study, concludes that Canada •is facing a major crisis •in the development of our resources, It states that unless corrective action is taken now, mineral production and exports could decline drastically after 1985, at the same time that Canada would face massive bills for imported oil because of inadequate and declining production.The task force, chaired by the author of this article, has put forward recommendations for a fundamental shift in both federal and provincial policies in order that Canada's mineral reserves can be developed in the national interest. This article consists of excerpts from the summary of the task force's report."

Jan 1, 1977

By D Marshall

The sub-level blasthole benching method of mining has been proved to be economical at Willroy Mines. How-ever due to the nature and attitude of the wall rock, this method is susceptible to serious hanging-wall dilution of the ore. Attempts to solve the dilution problem by various means were not satisfactory until long Stressteel bars were employed as rock bolts. The adoption of this de-vice does not require any special skill, and has become routine in the under-ground operation. Since the inception of this method, the dilution of the ore has been greatly reduced and the ov1!r-all costs of controlling this dilution are much lower. INTRODUCTION T HIS is a report describing the successful use of long Stressteel bars as rock bolts in preventing l1anging-wall failure and consequent dilution in open stopes. Willroy Mines Limited is located (Figure 1) near the town of Manitouwadge, Ontario, approximately l1alf-way between Sault Ste. Marie and Port Arthur.

Jan 1, 1963

By T&apos Ke, ing-sui

NUMEROUS investigators have observed that internal friction accompanies cold-working of metals and the effect of annealing is to reduce this internal friction.1,2 However, - most of the experiments were made at high stress amplitudes and the principal purpose was to study the increase of internal friction as a result of the applied cyclic stress during measurement. In order to study the internal friction introduced by cold-working applied prior to the measurement, the stress level applied during the measurement of internal friction must be sufficiently small. The results of measurement are significant and can be used for a base of comparison only when the applied cyclic stress is so small that the internal friction is independent of stress amplitude. Internal friction of cold-worked metals under small stress level has been studied by a number of workers8 -" he internal friction was measured around room temperature with a frequency of vibration of the order of kilocycles per second. The purpose of this paper is to report a study of the change of internal friction when severely cold-worked aluminum was annealed at successively higher temperatures until it was completely recrys-tallized. The measurements of internal friction were made over a range of temperature extending from room temperature up to the temperature of prior anneal. The frequency of vibrations used was about one cycle per second. The apparatus used for the internal friction measurements to be reported in this paper was a torsion pendulum with the specimen in wire form as the suspension fiber. The description of this apparatus and the method of measurement have been previously given.7,8 The applied stress was sufficiently small SO that the magnitude of internal friction is independent of stress level at each temperature range concerned. Corresponding to this stress the maximum shearing strain on the surface of the specimen is of the order of l0-5 and lower. The in- ternal friction (Q-1) is reported as 1/p times the logarithmic decrement. Internal Friction Versus Temperature of Anneal: Fig. 1 shows the internal friction measurements performed upon 99.991 pct aluminum subjected to 95 pct reduction in area. The final diameter of the wire is 0.033 in. This figure gives a general survey of the effect of temperature of anneal and of temperature of measurement. The internal friction of the cold-worked specimen was first measured at room temperature. It was then annealed at 50°C for one hour and the internal friction measured at 50°C and at room temperature. The same wire was successively annealed at higher temperatures for one hour and measurements were taken at the annealing temperatures and lower temperatures as before. Such a procedure was followed in order to stabilize the internal friction at the temperature of measurement so that during the measurement which generally takes about half a minute, there is no detectable change in internal friction. This series of measurements .was made up to 450°C. After each annealing a short test piece of the specimen, which had received the same past thermal and mechanical treatments, was taken out for metallographic examination. It is seen from fig. 1 that up to the annealing temperature of 250°C we have the following observations: for any given temperature of measurement, the internal friction is lower the higher the temperature of prior anneal. When the annealing temperature is 290°C or higher, the internal friction at the annealing temperature drops abruptly to a value which is much smaller than that for the previous curve. Metallographic examinations showed that the recrystallization of the specimen was completed after the annealing at 290°C. Fig. 1 shows that, as far as internal friction is concerned, there is no abrupt transition between the processes of recovery and recrystallization. Averbach has also reached the conclusion that recovery may be a process analogous to recrystallization on the basis of X ray extinction measurements in brass." The effect of annealing temperature upon the internal friction at room temperature is shown by curve I of fig. 2. In this figure the internal friction at room temperature was plotted as a function of annealing temperature. It is seen that the internal friction decreases rapidly at first with an increase

Jan 1, 1951

By S. P. Sandoval

Previous research by the U.S. Bureau of Mines demonstrated that nonionic surfactants increased the leaching rate of copper in the flask leaching of chalcopyrite with ferric sulfate if sufficient ferric sulfate was present. This research was continued by the Bureau in Part 2 to further explore the application of nonionic surfactants to the dump leaching of chalcopyrite. A polyoxyethylene lauryl ether was selected as the superior nonionic surfactant tested at 25° and 50° C. The addition of the surfactant increased copper leaching by 116 pct at 25° C and 1.0 pct solids and by 61 pct at 50° C and 0.5 pct solids at Fe 3+ concentrations greater than 1 g/L. At 0.1.0 g/L Fe 3+ and below, the addition of the surfactant produced as much as a 35 pct decrease in leaching. Each of the nonionic surfactants studied was found to be heavily adsorbed by a typical chalcopyrite ore, which poses a serious barrier to the application of nonionic surfactants in an actual chalcopyrite dump.

Jan 1, 2010

By J. C. Allen, E. V. Herring

CHILE EXPLORATION CO's. oxide plant at Chuquicamata, the largest of its kind, started in 1915 with initial operations at the rate of 10,000 tons of ore per day. Anaconda Copper Mining Co. acquired the controlling interest in 1923 and in the next few years modernized the plant and mine, extending operations to a nominal capacity of 490 million lb of electrolytic copper yearly by 1942. Plant production averaging 495.7 million lb of copper per year was maintained for the eight-year period extending from 1941 to 1948 inclusive. During the World War II production reached its highest level when in 1944 the output was 531.8 million lb. The maximum production for any one month was 49.6 million lb, achieved in May 1947. E. A. Cappelen Smith, consulting metallurgist for M. Guggenheim's Sons, worked out the first process for the treatment of Chuquicamata copper oxide ore about 1913, and directed a staff of 20 young engineers operating a pilot plant at Perth Amboy, N. J., on three shifts for an entire year. The copper is extracted from the oxide ore by a hydro-metallurgical treatment described in detail by T. A. Campbell in AIME Transactions, Vol. 106, Copper Metallurgy, 1933. The Oxide Plant is divided into five main operations as follows: (1) Crushing, (2) Leaching, including dechloridizing and sulphur dioxide treatment, (3) Tailing disposal, (4) Electrolytic precipitation, (5) Smelting and melting. Crushing The present Primary Crushing Plant has been in operation 25 years, during which time 4,342,112 cars of 70 tons net capacity have passed through the dumpers. The ore as received from the mine is frequently blocky and up to 5 feet in section. It is reduced to 9-in. size by two 60-in. gyratory crushers, and transported to the east and west ore bins by 60-in. conveyors. In the secondary crushing operation the ore is first reduced to 2 to 3-in. size by five standard 7-ft cone crushers and two No. 10 gyratories. This product is then reduced to 3/8-in. size by fifty-two 48-in. vertical Symons disc crushers and is transported by belt conveyors to the loading bridges from which it is charged° into the leaching vats. Conveyor belt No. 14 which serves the eight vats in the east section of the leaching plant has transported over 125 million tons of ore, which is a record for any type of conveyor. This 60-in. belt travels at a speed of 600 fpm and carries loads up to 5500 tons per hr. Leaching The ore is leached in 14 vats, averaging 13,500 short tons net capacity each. These vats are lined with a natural mastic which adequately resists the sulphuric acid leaching solutions. The leaching process as presently conducted comprises soaking the ore with successive volumes of leaching solution and spent electrolyte and withdrawing successive volumes of enriched solution from the vat to a total of approximately 3.2 million gal. The first 1.6 million gal of this volume withdrawn is called strong solution and contains about 35 parts of copper per 1000. The balance of 1.6 million gal subsequently withdrawn is stored in a

Jan 1, 1952

By G. T. Lapidus

One of Society’s major concerns with hydrometallurgical processing is the large amount of water that is quintessential to its nature. This is especially troubling in arid areas, where the population struggles to procure potable water for their daily needs. For that reason, it has become our responsibility to conceive, design and implement processing schemes that not only use as little water as possible, but recycle streams within the plant itself and minimize waste that exits its perimeter. With this in mind, the conference will center on the importance of selecting the appropriate chemical systems and integrating material balances to avoid reagent overkill and to detect impurity accumulation. The three “R’s” (reuse, recycle and recovery) of aqueous solutions within the processes are emphasized. Examples of processes for the recovery of lead, copper, precious and PG metals from minerals and waste materials will be presented.

By G. Prabhulingaiah, D. M. R. Sekhar

"A phosphate deposit of estimated 6 billion tons of P2O5 is located 180 to 300 meters below the sea level, 185 kilometers north of port Luderitz, Namibia. The ore bed is 6 kilometers wide and 220 kilometers long. The ore deposit analyzing 16% P2O5 is loose sediment of 1.5 meters thick without over burden. Sizing of the ore to - 1.4 mm + 0.150 mm improves the grade to 23.54% P2O5 with a P2O5 recovery at 83.75% containing phosphate pellets and flakes of sea shells. Clay, bacterial debris as organic matter, flakes of broken sea shells and fine phosphate containing particles report to - 0.150 mm fraction and + 1.4 mm fraction contains sea shells and few phosphate containing pellets. The mineralogical composition of phosphate containing pellets is estimated (Droste, T.C., 2004) 80% frankolite, 6% pyrite, 4% illite, 3% quartz, 3% amorphous SiO2, 1% carbonates, 1% organic carbon and = 1% ilmenite, magnetite, zircon etc. The phosphate content in the pellets is around 27.7% P2O5. Trials to separate by gravity or flotation processes were not successful. Leaching of carbonates (sea shell flakes) under mild acidic condition (= 2% acetic acid or HCl solutions) or calcinations followed by leaching however yielded residues (concentrates) of grades 27.85 - 32.74% P2O5 at P2O5 recoveries ranging from 78.45 - 96.8% P2O5."

Jan 1, 2014

By Eleanor Abshire

This bibliography is the second in a series that covers the current technical literature relating to the metallurgy of zirconium. The rapid advance in zirconium technology makes it mandatory that abstracts be prepared and compiled as soon as possible to have maximum value; therefore, the information in this volume is not arranged chronologically. As a service to research and production groups, succeeding bibliographies will be issued as new acquisitions accumulate in the Zirconium Information Center sponsored by the Department of the Navy, Bureau of Ships and the Bureau of Mines at the Bureau's Northwest Electrodevelopment Laboratory, Albany, Oreg. The initial volume, Information Circular 7771, Bibliography of Zirconium, covering 969 abstracted reports and 645 United States and foreign patents, was published in April 1957.

Jan 1, 1958

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith' and of A. G. H. Andersen .2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford," using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,1,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates h in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942

By Kim A. Lapakko, William W. III White

The ASTM standard method D 5744-96 was developed to provide a well-defined kinetic test protocol, conducted under controlled reaction conditions, with the intent of generating reproducible results. A preliminary indication of the repeatability of a simplified alternative method (MN DNR method) was assessed and results from the MN DNR method were compared to those from the ASTM method. To provide an indication of repeatability, six samples from three different rock types were subjected to dissolution testing for periods of 20 to 68 weeks. Drainage pH values at the end of the tests were within 0.5 units in all cases and within 0.05 units in four cases. The percent difference from the mean for overall sulfate rates from paired cells ranged from 0.04 to 1756, with a median of 6.3%. Nine samples from four rock types were subjected to both MN DNR and ASTM tests for periods of 20 to 132 weeks. The difference in final drainage pH values forsix of the samples was less than 0.1 unit, and these values were less than pH 3.65 or greater than pH 8.0. The final drainage pH difference for the last three samples ranged from 0.15 to 0.4, and these values were ill the pH range of 6.2 to 7.2. The sulfate release rates for the periods of record for the MN DNR method were 70 to 150% of those for the ASTM method, with a median value of 110%. Sulfate and calcium release from the two methods was not substantially different. The MN DNR method typically produced higher magnesium release.

Jan 1, 2000

By L. Burris, C. H. Stockman, I. G. Dillion

Zone melting is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Equations are presented which 1—predict the concentration profiles after successive passes of the zone and 2—give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing in the last zone length. These equations were solved numerically using an electronic computer, and the concentration profiles are presented as a function of the solute distribution coefficient and the ratio of molten zone to total bar length. ZONE MELTING is a purification process in which separation of impurities is effected by slowly moving a narrow melted zone through a bar of solid material. Separation occurs if the solid freezing from a solution at any moment has a composition different from that of the liquid from which it is freezing. Solutes which lower the freezing point will tend to remain in solution and will be moved in the direction of zone travel. Solutes which raise the freezing point will preferentially freeze out, and they will be moved in a direction opposite to that of zone travel. After repeated unidirectional passage of a molten zone through a bar of material, impurities will be concentrated in the ends of the bar. A limiting concentration gradient will be reached in the bar after a large number of passes of the molten zone. Both the magnitude of this limiting concentration gradient and the rate of movement of solute in any pass depend on the zone length and on the equilibrium concentrations of solute in the liquid and solid phases. The basic theory of zone melting was thoroughly covered by Pfann.1 The purpose of this paper is to extend the theory of zone melting by presenting 1—equations which relate the concentration profiles in successive passes of the zone and 2—equations which give the limiting distribution of solute along the bar after an infinite number of passes of the molten zone. These equations take into account the effect of normal freezing* in the last zone length concentration of a given solute in the solid to the concentration of the same solute in the liquid. Analytical methods for determining the concentration profiles after any pass have been developed by Lord2 and Reiss. The method developed by Lord does not take into account normal freezing in the last zone and also becomes very complicated when the number of passes becomes large. The method developed by Reiss enables the direct calculation of the complete concentration profiles (including that in the last zone) after any pass for values of k close to unity (0.9 < k < 1.1). Both methods are useful and provide valuable insight into the zone melting process. The equations given in this article are based on the same assumptions used by Pfann. These are: 1—uniform composition in the liquid, 2—negligible diffusion in the solid, 3—constant distribution coefficient, 4—constant length of the liquid zone (except at the ends), and 5—solubility of the solute in the melt is not exceeded at any point. Equations for Concentrations in Successive Passes For a melted zone of length 1 at the left-hand end of a bar of uniform unit cross-section, the amount of solute in the liquid is J0Cn-1(x) dx [1] where the subscript is the number of the pass. Cn-1(x) represents the concentration (expressed as weight per unit volume) obtained in the previous

Jan 1, 1956

By Shiou-Chuan Sun

THE presence of an excessive amount of tough froth in the flotation of minerals, particularly coals, may create trouble in dewatering, filtering, and handling. Froth is also a nuisance in many chemical industries.&apos; This paper presents a study on the destruction of extremely tough froths with intense high-frequency sound. The data indicate that sound waves can be employed for continuous atandsoundwavescan instantaneous defrothing. A powerful high-frequency siren was used in obtaining the data. Also tested was an ultrasonorator of the crystal type with a frequency range of 400, 700, 1000, and 1500 kc per sec and a maximum power output from its amplifier of 198 w. The results, not presented, indicate that as now designed this machine is not suitable for defrothing. Although the sound generators of the magnetostriction type2,3 and of the electromagnetic type&apos;.&apos; were not available, it is beelectromagneticlieved they are capable of producing the required sound intensity for defrothing. The use of ultrasonics for defrothing was suggested by Ross and McBain1 in 1944. Ramsey8 reported in 1948 that E. H. Rose mentioned a supersonic device that broke down flotation froth but with low capacity. The writer has not been able to find any published literature containing practical experiments. Theoretical Considerations The mechanism of defrothing by sound is attributed to the periodically collapsing force of the propagated sound waves and the induced resonant vibration of the bubbles. The collapse of froth is further facilitated by the sonic wind and the heat of the siren. Sound waves can exert a radiation pressure&apos;," against any obstacle upon which they impinge. When a froth surface is subjected to the periodic puncturing of sound waves, the bubbles are broken. According to Rayleigh9 and Bergmann,12 the radiation pressure of sound, P, in dynes per sq cm is given as: P = 1/2 (r+1)i/v where r is the ratio of the specific heats of the medium through which sound is traveling and is equal to 1 on the basis of Boyle&apos;s law; i is the sound intensity in ergs per sec per sq cm, and v is the sound velocity in cm per sec. In this case, the accuracy of the formula is only approximate, because a perfect reflection can hardly result from a column of froth. In addition to the radiation pressure, the propagated sound waves cause the bubbles of the froth to have a resonant vibration.&apos;" he vibratory motion of the bubbles causes collision and coalescence, thereby weakening if not breaking the bubble walls. Sonic wind and heat were also generated." The sonic wind can exert pressure on the froth surface, and the heat can evaporate the moisture content of the bubble walls as well as expand the enclosed air. Apparatus The defrothing apparatus, shown in Figs. 1 and 2, consists of a powerful high-frequency siren, a glass or stainless steel beaker of 2-liter capacity with 12.4 cm diam and 17.1 cm height, and a metal reflector. The beaker was placed 2 in. above the top point of the siren. The metal reflector was adjusted to reflect and focus the generated sound waves into the central part of the beaker. Fig. 2 shows the crystal probe microphone used to measure the acoustic intensity and the mandler bacteriological filter employed to introduce compressed air into the beaker for frothing. The apparatus was enclosed in a soundproof cabinet equipped with a glass window. The siren, shown in Fig. 3, consists of a rotor that interrupts the flow of air through the orifices in a stator. The rotor, a 6-in. diam disk with 100 equally spaced slots, is driven by a 2/3 hp, Dumore W2 motor at 133 rps. The frequency of the siren can be varied from 3 to 34 kc. The maximum chamber pressure is about 2 atm, yielding acoustic outputs of approximately 2 kw at an efficiency of about 20 pct. The siren itself is relatively small and can be operated in any orientation. A detailed description of the siren has been given by Allen and Rudnick.11 Collapse of Froth To study the sequence of the collapse of froth, the glass beaker was partially filled with 920 cc water, 100 g of —150 mesh bituminous coal, 0.3 cc petroleum light oil, 0.2 cc pine oil and 1.54 cc Pyrene foam compound. This mineral pulp was agitated for 5 min and then aerated through a mandler filter until the empty space of the beaker, approximately 9 cm high, was filled completely with min-

Jan 1, 1952

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,12, 7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 3 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942