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By H. Hubert

The first attempts at direct utilization of blast-furnace gas in engines were made in 1895. For a considerable time the gas had been burnt in Cowper stoves for heating the blast for the furnace, and under the boilers which supplied steam to the blowing-engines, and others serving the furnaces. It was natural, therefore, that the idea of directly employing it in gas-engines should have occurred simultaneously to several engineers, notably to Lurmann and to Lencauchez, who had pointed out the blast-furnace as a powerful gas-producer. Nevertheless, nowhere had any attempt been made to apply it to this purpose up to the end of 1894, when Thwaite proposed it to Mr. James Riley, of the Glasgom Iron & Steel Company. About the same time investigations were being made in Belgium and in Germany, independently of Thwaite's experiments, which were not generally known on the Continent. The industrial world, which up to that time had hardly favored the idea, had thus been gradually prepared to receive it. The gas-engine, long restricted to small sizes and dependent upon the use of an expensive fuel obtainable only in large centers, now began to make headway. At the Paris Exhibition of 1889 two engines of 100 h.p. were shown and excited much interest among engineers. One had four cylinders, and was made at the celebrated works of the Deutz Company, and the other was a single-cylinder engine, exhibited by two French designers, Messrs. Delamare-Deboutteville and Malandin. In the meanwhile the design of gas-producers had made important progress, completely freeing the new engine from its

Jan 1, 1907

By M. S. Smani, P. Blazy, J. M. Cases

Investigations on the beneficiation of sedimentary Moroccan phosphate ores are reported in four separate parts. The first discusses electrochemical phenomena at the solid-aqueous solution interface for minerals of the apatite group. In the second part, the electrochemical properties of the calcareous gangue associated with the phosphate ore are investigated. The flotation of calcite and phosphate oölites, using both anionic and cationic collectors, is discussed in the third part. It is shown that selective recovery could be obtained for precise concentrations of collectors and pH ranges. Results of work aimed at optimizing depression of phosphate oölites during inverse flotation of the carbonate gangue with sodium oleate are reported in Part 4.

Jan 1, 1976

By B. C. Allen

Liquid surface tensions of copper and 18 Group IV-A to VIII transition metals (Ti, Zr, Hf, V, Cb, Ta, Mo, W, Re, Ru, Rh, Pd, Os, Ir, Pt, Fe, Ni. Co) have been measured by the static pendant-drop and dynamic drop-weight methods on the same rod sample. The drops were formed by electron-bombardment heating in high vacuum. Application of necessary corrections enabled determination of surface tensions to k2 pct and agreement between methods to * 1 to 4 pct for all the metals studied. Evidence is presented that the liquid surface was well screened by metal vapor, suggesting negligible adsorption of gaseous impurities and that the surface tensions measured are characteristic of the metals involved. Correlations between liquid surface tension and melting point, molar volume, heat of vaporization, and atomic number are presented and discussed. Temperature coefficients of surface tension were calculated using Eötvös' law. SURFACE tension and interface energies of metals are the result of incomplete atomic coordination resulting in a force perpendicular to the boundary, tending to minimize its area. These energies are important in many phases of metallurgy, including microstructure, sintering, joining, electronic emission, and lubrication, which in turn affect many physical and mechanical properties of metals. Liquid surface tension refers to the interface between the liquid and its own vapor or nonreactive atmosphere, and is considered a physical property of the liquid. Since equilibrium shapes can be readily obtained with liquids, the units of surface tension (force per length) and interface energy (energy per area) are interchangeable. Thermo-dynamically, the surface tension ?LV is given by the change in free energy F with surface area A at constant pressure P, temperature T, and composition N: for commercially important refractory metals, vanadium, columbium, tantalum,13,14 molybdenum,14 and tungsten,l5 and none for the rare platinum-group metals and rhenium. Measuring the surface tensions of transition metals is difficult because of their high reactivity and melting points. Of the many techniques available,16-18 the pendant-drop 19-21 and drop-weight methods17,22 are considered superior because they can be modified to eliminate persistent sources of contamination such as supports and capillaries necessary in the popular sessile drop, capillary rise, and maximum-bubble-pressure techniques. The necessary modification is to melt a drop on the tip of a vertical rod, which provides support through a solid of the same composition.13,15 The object of the work was to study the surface-tension behavior of copper and transition metals, having reasonably low vapor pressures. Liquid surface tension of each pure metal was systematically determined by using a combination of the static pendant-drop and dynamic drop-weight methods on the same rod. Liquid drops were formed by electron-bombardment heating in high vacuum. EXPERIMENTAL WORK As indicated in Table I, the metals studied were high purity and generally were obtained in rod form. The exceptions were titanium and zirconium, which were machined from crystal bars, and molybdenum (tot 11, osmium, and ruthenium, which were sintered and arc cast into rods. All the metals were ground or swaged to desired sizes between 1- and 7-mm diam, and centerless ground round and smooth to a finish better than 50 µ in., rms. Each rod was thoroughly cleaned with steel wool, degreased, acid etched, and dried. In a typical run, the rod was vertically clamped in a modified floating-zone electron-bombardment furnace designed after Calverley23 and Carlson.24 The specimen was outgassed and maintained positive at several kilovolts in a dynamic vacuum of 10-5 to 10-7 mm. The bottom end was enclosed by a tantalum pillbox and heated by electrons emitted from a hot concentric tungsten filament mounted on a movable bracket. The bombardment power was slowly raised until melting was observed. Power requirements ranged from 30 w for copper to 1300 w for 4-mm tungsten. The stabilized and out-gassed drop of near-maximum size was photographed at 4. 1X on panchromatic film at desired time inter-

Jan 1, 1963

By R. Hoffmann

The Waelz process produces oxides of volatilizable metals from ores, metalliferous products and residues. The process was originally used for recovering zinc and lead, where tailings and residues containing those metals had accumulated at mines or smelters, but it is applicable for obtaining tin, arsenic or other volatilizable metals. It is useful when other methods of obtaining the metals from the ores or residues are too difficult or expensive or show too low a recovery. The Waelz process was developed in 1923 for the treatment of large calamine dumps in Upper Silesia, which showed zinc contents of 8 to 10 per cent. and lead contents up to 3 per cent. The rapid development of the process, from the first trials up to the plants now working or in course of erection, is shown in Fig. 1. The first industrial Waelz plant was started in 1925. Within two years the capacity of the working plants reached 700 tons material per day of 24 hr. During the year 1928 the daily capacity of the plants now at work or in course of erection will rise

Jan 1, 1928

By P. W. Bennett, E. M. Elkin

A new technique for the recovery of palladium and platinum and sludge from go12 electrolyte eliminates many of the drawbacks of the zinc-dust cementation process. In the electrolytic refining of gold by the Wohwill method, the electrolyte contains about 100 gpl gold as AuCl, and 100 gpl free hydrochloric acid. Any palladium and platinum contained in impure gold dissolve and accumulate in the electrolyte. When their concentration approaches that of gold, it becomes desirable to discard the electrolyte and to recover the gold and the palladium and platinum. As practiced at Canadian Copper Refiners until recently, discarded electrolyte was treated with sulfur dioxide to precipitate the gold. 2AuCl3 + 6H2O + 3SO2 —2Au + 6HC1 + 3H2SO4 The gold precipitate was filtered off, washed with water, and melted with scrap anodes. The wash water was added to the gold-free filtrate and treated with zinc dust to cement the palladium and platinum. PdCl2 + Zn — Pd + ZnCl2 PtCl4 + 2Zn—Pt + 2ZnCl2 The precipitate was separated and sold as Pd-Pt concentrate, and the barren filtrate and wash water were discarded. The receipts of palladium and platinum at this company were too small to warrant their refining. The process suffered from a number of disadvantages. Handling the gold-free solution was disagreeable, as it was laden with sulfur dioxide even after blowing with air overnight. Subsequent treatment with zinc dust was also troublesome. A large excess of zinc dust was required. Spray, acid mist, and vigorous evolution of hydrogen accompanied the reaction. The Pd-Pt precipitate was grossly contaminated with occluded unreacted zinc and with yellow granules of sulfur, thought to be formed by the reduction of sulfur dioxide and its derivatives. Repeated boiling of the precipitate with hydrochloric acid and washing with water decreased somewhat, but did not eliminate, the zinc. After drying overnight, the precipitate hardened to a clinkerlike mass that was difficult to grind. Grinding, handling, and packing created heavy dusting. Even weighing in an analytical balance generated dust, indicating that the powder was easily charged with static electricity. The total palladium and platinum content of the powder varied from 56 to 72 pct, with an average of 65 pct. The powder dissolved in aqua regia with difficulty, leaving a small amount of insoluble residue. However, the main drawback of the process was the strongly hygroscopic Pd-Pt product. The powder showed a marked though erratic increase in weight and a corresponding decrease in assay on exposure to air, even during the course of laboratory analysis. Such changes were the source of disagreement between Canadian Copper Refiners and the buyers of concentrate. The cause of the change in weight is believed to be hydrogen, liberated by the action of zinc dust on hydrochloric acid. Some of this hydrogen was adsorbed so strongly by the precipitate that it could not be driven off during the drying. On exposure to air it oxidized catalytically, forming water. Experiments soon showed that the entire process of treatment of discarded electrolyte then in use would have to be changed. A small quantity of apparatus was moved into the gold room, and experimentation was held to a minimum compatible with the development of a new process. PALLADIUM AND PLATINUM PRECIPITATION It was thought that zinc could be replaced with a reagent other than a hydrogen-evolving metal. Semiquantitative experiments showed that platinum and palladium could be precipitated completely from the gold-free solutions with such well-known reagents as sodium formate, formic acid, formaldehyde, and paraformaldehyde. Sodium formate was the preferred reagent, since the other three are volatile and somewhat toxic. The gold-free solutions used were those saturated with sulfur dioxide, partly freed of sulfur dioxide by aerating overnight, completely freed by boiling, as well as strongly and weakly acidic, neutral, and alkaline solutions. The reactions are complex and can be represented by these over-all equations: PdC1, + HCOONa — Pd + NaCl + HC1 + Co2 PtCl4 + 2HCOONa — Pt + 2NaCl + 2HC1 + 2CCX, Strongly acidic solutions required as much as five times the theoretical amount of sodium formate as did solutions neutralized to pH 4.5. Increasing the pH decreased the consumption of

Jan 1, 1965

By R. C. Himes, K. Zanio, J. B. Wagner, J. W. Moody, J. F. Miller, W. Johnson

The recent research with which this paper deals has been concerned with the preparation of pure PbTe crystals suitable for control of radiative processes and othe.v electronic applications. The research has been directed toward the developrnent of methods for the preparation of puve, homogeneous, loul-ca,wier-density PbTe crystals suitable for use in the fabrication of optically pumped and electrically pumped diode lasers. Steps in the preparation of the crystals include 1) purification of the starting materials, 2) synthesis and purification of the PbTe, 3) growoth of PbTe crystals, and 4) adjustt~zertt of composition of the crystals This Paper describes the general preparation procedure employed and discusses some investigntiotzs of purification processes. THE as-received lead and tellurium are nominally 99.999 to 99.9999 pct pure. Assays furnished by the suppliers, obtained by emission spectrographic analysis, show only the presence of about 2 ppm Mg in the tellurium. Such analyses are not very informative, however, since they give no information on the concentrations of normally gaseous impurity elements such as oxygen. Both the lead and the tellurium in the as-received state usually contain appreciable concentrations of oxygen—primarily in the form of oxides on the surfaces of the material. To reduce the oxygen content, the lead is held in the molten state in hydrogen at -700°C for several hours. For this treatment, the lead is contained in a graphite boat which is rf-heated, and the hydrogen is passed through a liquid-nitrogen trap prior to use. Tellurium is subjected to multiple distillation in hydrogen to remove oxygen and other foreign impurities. If, in conducting the distillation, approximately the last 10 pct of the charge at each "stage" is left as the discard cut, purification of the tellurium proceeds as indicated in Fig. 1.l Tellurium used in this work has been distilled two or three times to reduce carrier concentration to about 10" per cu cm. The PbTe is prepared from the purified elements by reacting them in the molten state in sealed, evacuated, or hydrogen-filled silica ampoules. The charge is usually held above the melting point of PbTe (923°C) at 1000 C for 24 hr to ensure that it has been homogenized. Two methods have been employed for the growth of the required single crystals of PbTe: growth from the melt, which will be discussed first, and growth from the vapor phase. Large single crystals of p-type PbTe can be grown readily from the melt by the Bridgman method. For this method of crystal growth, the PbTe is synthesized in situ from proper proportions of the purified elements. Growth (dropping) rates in the range 1.3 to 6.5 mm per hr are employed. Material near the maximum melting composition (about 50.012 at. pct Te) is utilized to avoid composition change on freezing, and thus to obtain crystals of nearly uniform composition. Crystals prepared by use of procedures described up to this point were sufficiently pure and perfect that they could be used for the preparation of laser crystals in studies at Lincoln Laboratory.2-5 ADJUSTMENT OF COMPOSITION Good n-type crystals of PbTe cannot readily be grown from the melt. Further, growth from the melt of crystals of any compositions (n or p type) other than those near the maximum melting composition is difficult because of the large composition changes that must occur on freezing.'" However, melt-grown crystals can rapidly be brought to other desired compositions by isothermal equilibration through the vapor phase with a two-phase Pb-Te stock material, essentially as described by Brebrick and Allgaier.1 The work to be discussed has been concerned with the preparation of n-type crystals; thus, the two-phase stock which was employed contained excess lead, and all ensuing discussion is of the preparation and properties of n-type crystals. The equilibration was designed to the shift composition to the lead-rich limit of stability at the selected temperature. Initial treatment of the crystals at high temperature was employed to minimize the total time required for the equilibration. Final adjustments of the composition and state of the crystals were made by use of low-temperature heat treatment at temperatures in the range 200" to

Jan 1, 1968

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By E. P. Klier

The work of Klier and Lyman1 on the bainite reaction has led to the full description of this reaction for medium-carbon low-alloy steels. Certain experimental data reported by Klier and Lyman appear, however, to be improbable of obtaining in very high-carbon steels. The study herein reported consists of an analysis of the transformation characteristics of a 3 per cent chromium, I per cent carbon steel by means of X-ray and metallographic methods. From the results obtained it is concluded that the bainite reaction in this steel is more complicated than that reported by Klier and Lyman for the low-carbon low-alloy steels. Henever, the mechanism of bainite formation in this steel appears to be essentially the same as proposed for the low-carbon low-alloy steels with the modification that the first volumes to transform are carbon-rich rather than carbon-poor. Experimental Procedure The analysis of the steel studied was: Cr, 2.89; C, 1.02; Mn, 0.33; Si, o.35; S, 0.012; P, 0.020. The stock was received from the Carpenter Steel Co. in rolled bars. Specimen Preparation Specimens were austenitized at 1200°C. (2192°F.) for 25 min. in purified nitrogen. The resultant A.S.T.M. austenite grain size was 0-1. Isothermal transformation was allowed by quenching the specimens into liquid metal baths controlled to 5°C. at 540°C. (1004°F.) and above, and to 2°C. at 490°C. (914°f.) and below. Following the desired degree of transformation all specimens were water quenched. Metallographic Examination Specimens 1/4 in. round by 1/4 in. were used for nietallographic examination. Etch-ants used were Vilella's reagent (I gram picric acid, 10 ml. hydrochloric acid to make 100 ml. ethyl alcohol solution) and alkalinc sodium picratc (electrolytic). Vilella's reagent was effective in revealing all microconstitucnts, while the alkaline sodium picrate developed the carbon-rich structures or carbides only. X-ray Examination Two X-ray techniques were used—the Debye-Scherrer method and a back-reflection method. 'The small specimens necessary for the Debye-Scherrer method were austenitized and then allowed to transform, or were cut from the larger metallographic specimens. The metallographic specimens were used for the back-reflection X-ray analysis. When it was desirable to determine the structure of the carbide present, sliver specimens were electrolytically etched to develop a carbide coating, then were exposed in the cameras. This technique was frequently necessary to allow positive identification of the carbide.

Jan 1, 1945

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By G. Thodos, E. M. Phillips

A reduced density correlation for the gaseous and liquid regions of ethane has been developed from all the experimental PVT data available in the literature for this substance. Saturated vapor and liquid densities reported for methane, propane and n-butane were utilized to establish the rectilinear-diameter line for ethane. This line was then used with the saturated-vapor data for ethane to produce the saturated envelope for this substance. Most of the saturated liquid data reported for ethane were found to be inconsistent with the saturated-liquid curve resulting from this study. The correlation covers the regions 0.65 < TR <6.0 and 0 < PR < 15. For regions for which no experimental data have been reported, the isobars of the correlation were extended by the use of the theorem of corresponding states. This correlation is presented both on rectilinear and log-log coordinates. INTRODUCTION At the present time, there is considerable interest in the exact PVT behavior of pure hydrocarbons. Matschke and Thodos12 recently have developed a comprehensive compilation of experimental vapor and liquid density data for methane. Similar studies have been conducted for other pure substances.4, 7 In the present study the density data available in the literature for gaseous and liquid ethane have been critically reviewed and utilized to develop a reduced density correlation for this substance. SATURATED LIQUID AND VAPOR DENSITIES The rectilinear-diameter rule proposed by Cailletet and Mathias5 states that the sum of the saturated liquid and vapor densities of a pure substance is a linear function of temperature which passes through the critical point. This law, although empirical, has been well established by continued verification since its conception in 1886. This rule has been applied to the saturated density data of methane,6 propane 17 and n-butane8 to produce the straight lines presented in Fig. 1 which pass through the critical point TR = 1.00, Pr = 2.00. The rectilinear-diameter relationship for ethane was established from the lines for the other substances in Fig. 1 by plotting the quantity p~, + PR against zc for different reduced temperatures. A critical analysis of the saturated vapor and liquid densities reported for ethane by Kuenen,10 Maass and McIntosh,11 and Sage, Webster and Lacey18 revealed that the values of PR1 + pr resulting from these studies were inconsistent with the rectilinear-diameter line obtained from the reliable density data of the other substances, as shown in Fig. 1. In the analysis of these data, reduced quantities were calculated using the critical con-

By Eugene N. Cameron

Pegmatites occur in abundance in certain areas of South West Africa and in adjacent parts of northern Cape Province in the Union of South Africa. Some of the pegmatite deposits were prospected before World War I, and intermittent mining was done during the period between the two World Wars. The deposits of the Jooste lithium mines became an important source of lepidolite, and beryl, columbite-tantalite, wolframite, and other minerals were produced. Since World War I1 prospecting and mining have been carried on vigorously, with the result that South West Africa produced nearly 3000 tons of beryl during 1949 through 1953, together with more than 40,000 tons of lithium minerals, chiefly lepidolite and petalite. Small amounts of tantalite, columbite, and other minerals have also been produced during the postwar period. Most of this mineral production has come from two pegmatite areas roughly outlined in Fig. 1. One is the Karibib-Omaruru area of north central South West Africa. The second is the northeastern part of the Orange River pegmatite area, which extends into adjacent parts of Namaqualand, in northern Cape Province of the Union of South Africa

Sep 1, 1955

By W. C. Maurer

Although millions of feet of rock are drilled annually, the basic drilling mechanisms involved are not well understood. The primary reason for this lack of knowledge is because the basic principles of rock failure are not well understood and rock failure is the primary mechanism in drilling. A better understanding of the drilling mechanisms would enable a more scientific approach to the design and use of drills and bits. The paper reviews several models which have been proposed to explain various aspects of the different drilling methods. These models are described and their limitations and areas of application are discussed. Drilling rate relationships are developed and related to the basic rock failure mechanisms. TYPES OF MECHANICAL DRILLS There are three basic methods of mechanically attacking rock: 1) percussive action, 2) rotary action, and 3) combined rotary-percussive action. A percussion drill applies a force perpendicular to the rock surface and the bit moves into the rock perpendicular to the surface, forming a crater beneath it (Fig. 1). A rotary drill applies a constant thrust to the bit while a torsional force moves the bit parallel to the rock surface, breaking the rock ahead of it. A rotary-percussive drill applies both a rotary force and a percussive force to the bit which moves into the rock at an angle to the surface. The commonly used drills can be classified as: rotary-drag, diamond; percussive-hammer, piston, churn; and combination-rotary-percussive, roller.

Jan 1, 1967

By George Boulter

Draglines 8.2-1 Introduction. The nature and characteristics of rock and rock derivatives forming the crust of the earth vary so greatly from place to place that it is impossible to use the same numerical factors to show the, productive ability of excavating equipment on different jobs or projects. Factors for each project must be developed individually and applied as the conditions and requirements dictate. TYPES&apos; OF DRAGLINES. Types of draglines are differentiated by the propelling method used and are generally divided into four classes, as follows: 1. Wagon mounted 3. Crawler mounted 2. Truck mounted 4. Walking Figure 8.2-1 shows a truck-mounted dragline. This type is considered to be the most mobile unit. In order to increase stability over the side, outriggers are installed as part of the truck chassis. This feature is not shown in .this figure. Figure 8.2-2 shows a crawler-mounted dragline. The long, wide crawlers are used to increase the stability and reduce the bearing pressure of this unit. These features allow for use of these units on surfaces too soft for the wagon- or truck-mounted types. Figure 8.2-3 shows a walking-type dragline. The large diameter tub and the well-supported boom through the gantry gives high stability for rugged works over a long life. BASIC PARTS OF A DRAGLINE. The basic parts of a dragline are illustrated in Fig. 8.2-4. A deck layout is shown in Fig. 8.2-5 with the main components named. OPERATION OF A DRAGLINE. Following is a description of the steps and controls present in a typical cycle of operation of a large dragline having independent hoist and drag motors. Starting the cycle with positioning the bucket on the ground under the point of the boom, the next step is

Jan 1, 1968

By C. E. Birchenall

DaVIES and Richardson1 have measured composition changes for Mn1-Owith variation in the equilibrium partial pressure of oxygen at 1500°, 1575°, and 1650°C, where 6 is the deviation from the simple stoichiometric ratio. No trend in this relationship with temperature was observed, so these remarks apply to the whole temperature range. The experimental values and their spread are shown by the bounded straight-line segments in the figure. Davies and Richardson assume that the stoichiometric oxide shows Frenkel disorder, given by the equation Mn2+Mn2+ + Mn" [1] where Mn2+ is a normal lattice ion which moves into an interstitial site (Mni2+) leaving a vacancy (Mn,"). The superscript dashes indicate that there is an excess charge on the anions surrounding the vacancy. Schottky disorder, in which a perfect crystal acquires equal numbers of cation and anion (Ov") vacancies according to leads to equations of exactly the same form in the analysis below. In view of the neutron diffraction results of Roth,2 which shows extensive Frenkel disorder in Fe1-o, Eq. [I] seems more appropriate. The deviations from stoichiometric composition, MnO, result from the addition of oxygen according to In effect Davies and Richardson ignore the variation of Mn3+in constructing equilibrium constants. This approximation might not appear to be very serious if the excess positive charges are really free posi- tive holes (P+) and if the intrinsic conductivity is high as a result of the reaction where e- is a conducting electron. However, the calculations of Buessem and Butler3 indicate that the partition functions of the free charges make a large contribution to the equilibrium constant, and this approximation would not be a desirable one. Furthermore, Morin4 shows that the positive holes are probably localized in MnO and therefore are described better by the mass action principle than by a degenerate gas model. Davies and Richardson&apos;s considerations require that activity corrections be applied beyond a 6 value of about 0.005. It is proposed to show here that the dissociation pressure curve can be calculated reasonably well over the whole composition range studied without activity corrections by choosing appropriate equilibrium constants for reactions 1 and 2. As stoichiometric composition The mass action constant, Ks, for reaction [I.] and the equilibrium constant, K,, for reaction [2] are given by where the concentrations which do not change significantly have been absorbed into the constants. The brackets denote concentrations. The deviation from stoichometric composition is given by gardless of [Mni2 ]. Substituting Eq. [7] in [6]

Jan 1, 1961

By John Griffen

THEORY HYDRAULIC classification as explained by Rittinger and others was largely restricted to conditions wherein the free-falling velocities of the particles were conceived as governing the separations effected (see chapter 9). The laws governing classification under free-falling conditions have been summarized by Chapman and Mott as fo1lows:l Nomenclature r represents, in a particle of irregular shape, the round-hole screen through which the particle would pass, or some other linear dimension of the particle equivalent to d, the diameter of a sphere. s, the specific gravity of the particle. 1, the specific gravity of the water used as a medium. K, a constant. W, the velocity of the water. In an Upward Current of water 1. A particle will move upward if [V > K dr(s - 1)] and, by suit- ably regulating the speed of the water current, the larger and heavier particles may be made to fall downward against the current, leaving the smaller, lighter particles in suspension in the current. 2. Particles such that [- = -] cannot be separated in an upward- current classifier with any one velocity of current. Coal particles having a specific gravity of 1.35 cannot be separated from refuse particles of [2.5 - 1 2.5 sp. gr.] unless the ratio of diameters is less than [ 4.3 to 1, 1.35 – 1] and the raw coal must be screened to size limits within this ratio if they are to be separated. Cone-shaped vessels or vessels of other shapes that allow the use of different velocities of current at different points in the flow are used to modify this limitation.

Jan 1, 1943

By Edwin R. Phelps, Charles W. Porterfield

BACKGROUND OF SURFACE MINING Surface mining refers to the process of removing the material (over- burden) overlying a coal seam and exposing the coal so that it can be loaded out and conveyed by trucks or other methods to the preparation plant or other facility. Surface mining has not always been important in the coal industry. In the early 1900s, almost all of the coal mined in the United States was mined by underground methods. In 1900, about 192 Mt (212 million st) of bituminous coal mere mined and less than 1% was mined by surface methods. The development and use of larger equipment has allowed surface mining to gain prominence throughout the years. Table 1 shows the total production of coal by mining method in the United States for ten-pear periods since 1920 and indicates the growth of surface-mined coal production. Surface mining will undoubtedly continue to account for a large percentage of the coal production in the US for many years because: 1) The capacity of surface mining excavators has continued to increase. Today, mining companies are using shovels (see Fig. 1) which are able to move up to 137.6 m3 (180 cu pd) in each bite and draglines (see Fig. 2) which move up to 168.2 m3 (220 cu pd) in each bucketful. 2) Increasing tonnage from the thick western coal seams is being produced by surface mining methods. 3) Surface mining has normally had lower costs and a better safety record than underground mining. 4) Surface mining normally recovers a much higher percentage of the coal reserve than can recovered by underground mining. 5) Some coal measures call best be extracted by surface mining

Jan 1, 1981

By G. B. Kasik, George Sachs, George Espey

IT has been reported frequently that the hardness and strength vary over the cross section of cold-worked, particularly cold-drawn, material. Brass rod and wire usually has been found to possess a maximum strength and hardness near the surface.1,2 According to Sachs,1 the center fiber has about the same strength as a wire stretched by the same amount in a tensile-test machine, the strength increasing toward the surface (Fig. I). These differences are particularly large for wire given a small reduction on drawing through a die with a wide opening. However, with increasing reduction and hardness, a tendency to form a thin soft surface skin becomes apparent. On the contrary, copper wire has usually been found to possess a soft surface skin" and it has been reported by Harris3 that during the cold-drawing of hot-rolled wire the surface layer becomes increasingly softer than the core, while the layer of maximum strength moves toward the core, it being found near the surface at first. The increase of strength and hardness from the core to the skin is readily explained by the observation that, in addition to the stretching, the layers of a rod or wire are sheared more the closer they are to the surface.1,6-8 However, the presence of a soft surface layer can be attributed only to an annealing effect. The source of such a softening might be the extremely high temperature that originates from the friction between [ ]

Jan 1, 1941

By Robert F. Mehl, Edward L. McCandless

Oriented overgrowths and intergrowths among both metallic and nonmetallic substances have been recognized and studied for well over a century. The work of Widmanstätten in 1808 on the geometrical structure in meteorites, a structure known by his name, demonstrated that oriented intergrowths can occur in purely metallic systems. This fact led to much of the early microscopic study of alloys, contributing greatly to the advance of physical metallurgy. The problem has been attacked again in recent years in a comprehensive fashion, with the object of discovering what atomic movements may occur during phase changes in alloy systems. Much of this work has appeared in the A.I.M.E. Transactions in a series of papers published by Mehl and coworkers beginning in 19311. Although many aspects of this general problem remain unsolved, it may be said that the orientation of a new phase forming by precipitation from solid solution or by transformation invariably bears a unique relationship to the orientation of the phase from which it formed, and that similarity in atomic patterns on atomic planes in the two phases play an important part in determining the orientation relationship. Analogous orientation relationships exist in oriented intergrowths in nonmetallic systems—mineral or inorganic. In 1827 Haidinger2 discovered natural intergrowths of hematite and magnetite, and demonstrated that the rough form of the magnetite octahedrons was delineated by small crystals of hematite, of which the basal (00.1) planes lay parallel to the octahedral cleavage planes of the magnetite. The description of this orientation relationship was later completed by von Rath3, who showed that the edge (00.1): (10.1) in hematite lies normal to the [Ill]

Jan 1, 1937

By Earl W. Palmer, Cyril Stanley Smith

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors&apos; conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935

By Cyril Stanley Smith, Earl W. Palmer

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors&apos; conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935