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By G. W. Josephson

Since the earliest years of recorded history the durability and protective qualities of asphalt and tar have been known and utilized. The mummies of early Egyptian kings were coated with asphaltic materials, and asphalt mastics were common in Babylon. However, according to various authorities, it was not until 1780 that the first forerunner of present-day composition roofing was discovered,l and the large-scale expansion of the industry has taken place since 1900. Historical Background Development was stimulated by the growing popularity of manufactured gas. The by-product tars from these operations accumulated in large waste piles that had no commercial value and were a source of annoyance and expense to the gas companies. These tars were offered at very attractive terms to anyone who would take them away, and the infant "composition" roofing industry benefited accordingly. At first the process consisted simply of dipping sheets of burlap or other fabric in a tank of molten tar or asphalt. The long strip of roofing was rolled up for convenient handling, and the early experimenters soon found that it was necessary to dust the surface of their new "roll roofing" with some kind of material that would prevent the tarred surfaces from sticking together. Any finely divided, low- priced local material like sand or fine gravel served this purpose and from its application the roofing-granule industry grew. As time went on other characteristics of a properly applied mineral surfacing were recognized. As with wooden shingles, tar and asphalt can be ignited by flying embers from near-by fires. It was found that by increasing the largest particle size to the maximum that could be successfully embedded, and by properly controlling the amount of smaller fractions retained in the grade so as to cover the asphalt completely a high degree of resistance to fire was attained. Needless to say, in this early period asphaltic roofing needed such selling points to gain acceptance in a field dominated by wood, slate, and tile. When asphalt is protected from the sun's rays it is extremely durable, but when exposed to sunlight its surface is comparatively rapidly decomposed. Completely covering asphalt roofing with mineral surfacing protects the asphalt and adds materially to the life of the roof—conservatively, 500 per cent. Slate Graftules In the production of split slate shingles a large quantity of waste slate is accumulated, as 60 to go per cent of the rock quarried is discarded. This waste was a continuing burden on the industry. Some was marketed as ground slate flour for filler in paint and linoleum, and there is a record that as early as 1906 two carloads of coarse screenings from slate flour were marketed as granules for surfacing roofing. This new field appeared to the slate Pro-

Jan 1, 1948

By Bruno V. E. Nordberg

Hoisting is one of the earliest endeavors of man with machinery, for hoisting was probably used by the early Egyptians. Treadmills were used for general hoisting until early in the nineteenth century and it was a short step only to attach a Watt steam engine to the rope drum of a hoist. One of the earliest steam hoists was built for a coal mine at Frisne, near Valenciennes, France. It was a remarkable piece of engineering created by James Watt in 1811, using a wooden drum on a vertical shaft. This followed the crude hoist by Holtzhausen in 1803, which used a drum of wood on a horizontal shaft.' In this country there were examples of crude mine hoists, which have been developed into the efficient machines in use today. African and Australian mines show examples of both extremes, and have an array of fine hoisting equipment exemplified in those built by British manufacturers. The influence of both English and American engineering in hoisting is interestingly evident in Canada. The information available to the writer does not reveal this to be true of South Africa, although American-built hoists have been furnished. Mining camps develop their own style of equipment, adapted to local conditions. For instance, the Butte mining district adheres to the straight drum with friction clutches, because of the great number of levels from which hoisting is done or to which men and material are lowered and the necessity for hoisting or lowering unbalanced. The north Michigan copper country uses both straight and cylindroconical drums and hoists continually in balance, so that the drums are not clutched to the main driving shaft. The Joplin mining district, Missouri, has its own peculiar small hoists. Other individual mines or localities in which a number of mines have been developed show individualistic types of hoists, depending upon their particular problems. In each instance, however, the particular problem must be carefully analyzed, as conditions are seldom so near the same that a number of identical hoists can be used to advantage.

Jan 1, 1940

By Bruno V. E. Nordberg

Hoisting is one of the earliest endeavors of man with machinery, for hoisting was probably used by the early Egyptians. Treadmills were used for general hoisting until early in the nineteenth century and it was a short step only to attach a Watt steam engine to the rope drum of a hoist. One of the earliest steam hoists was built for a coal mine at Frisne, near Valenciennes, France. It was a remarkable piece of engineering created by James Watt in 1811, using a wooden drum on a vertical shaft. This followed the crude hoist by Holtzhausen in 1803, which used a drum of wood on a horizontal shaft.' In this country there were examples of crude mine hoists, which have been developed into the efficient machines in use today. African and Australian mines show examples of both extremes, and have an array of fine hoisting equipment exemplified in those built by British manufacturers. The influence of both English and American engineering in hoisting is interestingly evident in Canada. The information available to the writer does not reveal this to be true of South Africa, although American-built hoists have been furnished. Mining camps develop their own style of equipment, adapted to local conditions. For instance, the Butte mining district adheres to the straight drum with friction clutches, because of the great number of levels from which hoisting is done or to which men and material are lowered and the necessity for hoisting or lowering unbalanced. The north Michigan copper country uses both straight and cylindroconical drums and hoists continually in balance, so that the drums are not clutched to the main driving shaft. The Joplin mining district, Missouri, has its own peculiar small hoists. Other individual mines or localities in which a number of mines have been developed show individualistic types of hoists, depending upon their particular problems. In each instance, however, the particular problem must be carefully analyzed, as conditions are seldom so near the same that a number of identical hoists can be used to advantage.

Jan 1, 1940

By H. Bloom, H. E. Hawkes

STREAMS and rivers are the principal channels into which the weathering products of rocks and their contained ores are funneled. The inorganic load of a stream system is a crude sample of all the earth materials in the drainage basin of the stream, and the heavy mineral assemblage of sediments is one of the oldest and most successful guides to certain kinds of bedrock ore in unexplored terrain. Early application of this method was made possible by the ease of separation and identification of heavy minerals in the field with the simplest equipment. Water analysis for traces of base metals became a practical possibility about eight years ago with the development of rapid chemical tests that could be carried out at the field site.' , Since that time the water method has been widely used in mineral reconnaissance, and a substantial number of discoveries have been reported. Here again, the techniques developed for this work were relatively simple and could be performed easily at the field site. Sediment analysis by chemical methods, as distinguished from mineralogical, has received less at- tention. Some experimental work was done by Lovering and others," but to the authors' knowledge, chemical analysis of sediment samples has not been used in routine exploration programs until very recently. In spite of the obvious promise of this method, it was not pursued vigorously because of the lack of a simple and portable chemical test that could be used conveniently at the field site or in a field camp. Procedures that had been developed for trace analysis of soils all called for a rigorous chemical attack with hot acids—tests more conveniently applied in processing large volumes of routine soil samples at an established field headquarters. Recently an extremely rapid and simple test was developed by Bloom.4,5 The extractant used in this procedure is a cold solution of ammonium citrate. Elements measured are the heavy metals, principally zinc, lead, and copper. This method differs from the established procedures for soil analysis in that it measures only a small fraction, about 5 pct, of the total metal content of the sample. It has been found, however, that the significant pattern of metals in the sediments of streams below a base-metal deposit can be brought out as well and sometimes better by this simple cold-extraction procedure than by the more tedious methods requiring hot acids. To understand fully the significance of the relation between the readily extractable and the total

Jan 1, 1957

By J. Fred Johnson

COROMANT is the trade name of the alloy-steel drill rod tipped with a chisel-type tungsten-carbide bit manufactured by Sandvik Steel Works Co., Ltd. Other names, such as Swedish or air-leg method of drilling, are used in various localities. Coromant drilling in Sweden was the natural sequence of the adaptation of tungsten-carbide inserts to the already established routine of drilling. By the middle thirties the percussion drill had reached practically its highest attainable efficiency as a drilling machine. Since then improvement has been in metallurgy of component parts to increase life or lessen weight, in the development of pneumatic and automatic feeds, in the use of jumbos to more quickly and easily handle machines, and in changes in drill rods and bits. By 1937, drilling in the United States and Canada was done by relatively heavy mounted drifters with positive hand or automatic feeds. In Sweden, on the other hand, emphasis had been placed on light equipment and drifting was done with pneumatic bars and reverse-feed stopers. In 1938, one of the most prominent American drill manufacturers developed an air-leg for successfully drilling the extremely variable but relatively soft iron ores of some of the northern Michigan mines. Also in 1938, a comparative Swedish test, also in soft iron ore, of a 50-lb jackhammer mounted on an air-leg, against a 100-lb reverse-feed drifter on a pneumatic bar, showed the net drilling time was increased by the air-leg set-up from 51 to 71 pct, in drilling 6-ft rounds in a 6 1/2x6 1/2 ft drift. Miners were becoming scarce in Sweden even at that time and, since the lighter equipment made the work easier and more attractive, the airleg was then made use of in some types of soft rock. In 1940, for instance, a large tunnel for a hydroelectric plant was driven with this equipment. By 1943, when tungsten-carbide inserts came into the picture in Sweden, a great many of the kinks in percussion drilling with this hard-metal had been worked out in Germany under the stress of war conditions. However, only 10 pct of the drilling machines manufactured in Sweden were jackhammers for use on air-legs and only the one manufacturer made air-legs in the United States. American practice had largely supplanted integral forging of drill bits by the detachable steel bit. Canada and South Africa were using the one-pass throwaway bit but Sweden was still using the same old integral forged bit. After a long study of the trend toward simplicity

Jan 1, 1952

By William G. [Peryam], Bishop Ottey M., Fred E. Johnson

THE Lepanto Consolidated Mining Company is the largest copper producer in the Philippines, and the only one that makes a concentrate valuable principally for its copper; also, it has the only productive copper mine situated at considerable distance from the sea, and is the only one in the islands operating its own smelter. The Lepanto mine is in the Municipal District of Mankayan, sub-province of Benguet, near the heart of the Mountain Province of Northern Luzon. It is 165 km. from its shipping point at San Fernando, Province of La Union, on the shore of the China Sea. Elevations at the property range from 3200 to 4500 ft. The climate is very mild; temperatures are seldom below 50° or above 80°F. Annual rainfall approaches 170 in. and is mainly confined to a rainy season lasting from May to October. The months from December to April, inclusive, are usually extremely dry. This climatic pecularity entails the problems of landslides on the roads during the rainy season and water shortage during the dry season. The Mountain Trail, an improved rock-surfaced toll road maintained by the Commonwealth Government, gives access to the property. The 105 km. over this road may be traveled in about 4 ½ hr. during the dry season. Very few sections of the road are straight for more than 100 meters, and about one third of it is a one-way road controlled by gates. All freight for the property is delivered by the Manila Railroad Company to Bauang, La Union, 45 km. west of Baguio and at sea level, where it is picked up by freight trucks and hauled via Baguio to Lepanto. Granulated matte is hauled in bulk from Lepanto in four-ton lots on freight trucks to the storage bins at San Fernando. Freight rates from Bauang to the property amount to P8.00 per ton, and from the property to San Fernando the rate is P16.00 per ton. The company pays the road toll, P1.00 per truck, each way. THE CAMP The company maintains a modern camp, well separated from the mine and reduction plant. Comfortable and sanitary living quarters, water, and light, as well as free medical service are provided all employees. A hospital staffed by a doctor and two nurses takes care of all medical treatment. Considering recreational facilities of great importance, the company has provided two tennis courts, two basketball courts, and badminton courts for employees. Bowling alleys and a motion picture theater are operated by the company, the profits being expended for other recreational purposes. A moderate sized recreation hall serves for barrio dances, meetings,

Jan 1, 1942

By Morris Muskat

A general theory has been developed for the effect of permeability stratification on the efficiency of the gas-injection phase of cycling operations. It has been applied to three special types of permeability variation; namely, exponential, probability, and linear. In the case of the exponential permeability distribution the effect of areal pattern sweep efficiency was also taken into account. The exponential permeability distribution can be characterized by the ratio of the maximum to minimum permeability, which has been termed the stratification constant. Curves were calculated for the variation in total wet gas recovery and total gas throughflow, to give that recovery to various abandonment limits of the wet gas content in the produced gas, as a function of the stratification constant. The cumulative wet gas recovery decreases monotonically as the stratification constant increases and is generally higher at the lower values of the wet gas content abandonment limits. The total gas throughflow first rises to a maximum as the stratification increases, and then ultimately declines. The effect of the areal sweep pattern efficiency is relatively minor as compared to that of the stratification constant, except in the region of low values of the latter where the formation is substantially uniform. The probability distribution can be characterized by a "variation" parameter varying from o to I as the formation changes from strict uniformity to extreme variability. The curves of total wet gas recovery and total gas throughflow to different abandonment limits of wet gas content versus the variation parameter have the same general characteristics as for the exponential permeability distribution. In the linear permeability distribution the ratio of maximum to minimum permeability also serves as a stratification constant index defining the distribution. The curves of total wet gas recovery and gas throughflow to fixed abandonment limits versus the stratification constant are similar to those for the exponential permeability distribution. However, for the higher values of the stratification constant the recoveries and throughflows do not asymptotically fall to o as in the latter, but approach constant values determined by the abandonment limit of wet gas content in the produced gas. Introduction It is becoming generally recognized that one of the most important factors determining the economic feasibility of cycling operations is the areal continuity and permeability distribution of the producing formation. While the effects of areal variations in permeability, porosity, thickness, and well pattern on the sweep efficiency can be evaluated by electrical model studies,' those due to permeability stratification require separate treatment. Several studies have been reported2,3 on the' influence of permeability variations on the wet gas recovery by cycling. In these, however, discontinuous permeability variations either have been assumed explicitly, or the analysis has been carried through as if they were discontinuous. While, in fact, the actual permeability profiles will undoubtedly be discontinuous, recent develop-

Jan 1, 1949

By W. S. Morris, R. R. Bradenthaler, G. Wade

Petroleum engineers generally are of the opinion that the flow conditions and, therefore, the formulas that apply to the flow of oil and gas in long pipe lines differ in many ways from flow conditions in oil wells. One of the reasons why the formulas in common use for pipe-line flow do not correctly apply to oil wells is that the flow lines are vertical and not horizontal. Another factor to be considered is that the fluid is a mixture of oil and gas and that the physical characteristics of these two components are affected differently by changing conditions of pressure and temperature during upward flour. Realizing the need for accurate data on flow in vertical pipes under conditions caused both by natural flow and the gas-lift, the U. S: Bureau of Mines has installed equipment at the Petroleum Experiment Station, Bartlesville, Okla., for the purpose of studying this problem. In additon a study will be made of the comparative effects of different natural-flow and gas-lift methods of producing oil on ultimate production from reservoir sands. Experimental Equipment The experimental equipment consists of a regular oil-field steel derrick, a large pressure tank installed in a concrete pit beneath the derrick floor, compressors and pumps, gas separators and absorbers, metering and control devices, and the necessary pipe connections. The crown-block level represents the derrick floor at an oil well, and the "producing sand" is the pressure tank below the derrick floor. The difference in elevation between the crown-block level and the tank is 90 ft. Figs. 1, 2 and 3 show the construction and exterior arrangement of the equipment. The success of the experiment will of course depend largely upon the accuracy of the oil and gas measurements and the temperature and pressure determinations. Because extreme accuracy is necessary, all oil and gas measurements will be checked at least twice, and in some

Jan 1, 1929

By E. O. Wagner, V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pct natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pct of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 1/16 in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F. The necessary heat also can be obtained from 7.5 to 11 cu ft of gas at 2000°F. A description of the design and operation of a pilot plant for flash drying coal dusts is presented. This plant dries 1/16 in. by 0 coal dust in suspension in 1.5 to 2 sec with 600°F gas at a rate of 1300 lb per hour per square foot of column area and operates continuously at an efficiency of about 85 pct. The design and operation of another pilot plant for drying 1/8 in. by 0 coal dusts Is also described. This unit dries coal in the fluidized state using the sensible heat of gases introduced at 2000°F and processes coal at a rate of about 1500 Ib per hour per square foot of grate area at 85 to 90 pct efficiency. Over 90 pct of the bed moisture of low-rank coal dusts can be removed by the methods described. The heating value of lignite can be increased 45 pet and that if subbituminous coal 25 pct in a few seconds. The physical and chemical properties of coal dusts before and after drying are presented in the report, and it is shown that the bulk density of the dried coal is equal to that of the raw coal. This phenomenon makes it possible to ship 25 to 45 pct more heat in a railroad car with consequent savings in freight costs. Introduction For several years the Subbituminous Coal and Lignite Section of the Coal Branch of the Bureau of Mines at Golden, Colo., has been concerned with upgrading low-rank coals by removal of natural bed moisture. These fuels contain 10 to 50 pct total moisture, which reduces their industrial value considerably. In 1938, investigations were initiated in cooperation with the University of North Dakota to study drying of lignite by the Fleissner process with heat derived from high-pressure saturated steam. Two pilot plants were built, and two reports were published giving the results of this work.l,2 It was demonstrated that lump lignite and subbituminous coal

Jan 1, 1950

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By John P. Huger

me phase diagram for the system Ag-Si has been established by thermal analysis. The diagram is a simple eutectic type with a eutectic at 3.0 pct Si and 840°C. From the liquidus curve and with the aid of regular solution theory, the thermodynamic properties of the liquid Ag-Si system at 1420 °C have been determined. Silicon exhibits positive deviations from Raoultain behavior at all compositions, while silver exhibits both positive and negative deviations. MEASUREMENTS of silicon activities in liquid iron alloys by means of distribution studies between the immiscible liquids silver and iron have been reported by Chipman, Fulton, Gokcen, and caskey.' The applicability of this technique is dependent, however, on the accuracy of the silicon activity values in the Ag-Si alloys, particularly in the dilute silicon region. Darken and Gurry2 have shown that log ?si/(1-xSi)2 is approximately linear with composition, but uncertainty exists in the extrapolation to dilute solutions. Their calculations are based on the old Ag-Si phase diagram of Arrivaut3 and any variation in the position of the liquidus curves will strongly influence the extrapolation. The purpose of this study is to redetermine the Ag-Si phase diagram and calculate the associated thermodynamic properties. EXPERIMENTAL The Ag-Si phase diagram was determined by thermal analysis of liquid alloys. The alloys were contained in a 35 mm alumina crucible under a protective stream of purified argon. The crucible was placed inside a 64 mm alumina tube fitted with a gas-tight, water-cooled, copper head. The tube and assembly were heated in a manually controlled globar furnace. The temperature was measured with a Pt, Pt + 10 pct Rh thermocouple in a high-temperature porcelain protection tube. The thermocouple calibration4 was checked against the melting point of pure silver at the start and during the course of the experiments, and against both gold and silver at the completion of the experiments. The alloys were prepared from granular silver analyzing 99.95 pct Ag and powdered silicon analyzing 99.88 pct Si and 0.026 pct Fe. Approximately 150 g of alloy were used for each run. The composition of the alloy was determined by withdrawing samples of the liquid alloy with a vycor tube-aspirator bulb device. Analysis of solidified samples agreed, for alloys containing less than 23 pct Si, within ±0.3 pct Si of the calculated composition. Duplicate samples showed a variance within 50.05 pct Si of the mean analysis. The alloy was heated to 100' to 20pC above the estimated liquidus temperature and then the furnace was adjusted to give an average cooling rate of 2" to 7°C per min. A cooling curve was obtained by taking potentiometer readings at 15-sec intervals. Several analyses were made by recording the thermocouple output on a high-speed, Stip-chart recorder, with the exception of run NO. 11, a minimum of two thermal analyses were made for each alloy and the cooling curves then obtained duplicated the liquidus and eutectic temperatures to about 1°C. RESULTS The results of the thermal analysis are given in Table 1, and are represented as the Ag-Si phase dlagram, Fig. 1. The eutectic composition was found

Jan 1, 1963

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

By P. Ramachandraraa, T. R. Anantharaman

THE technique developed by Duwez, Willens and Kle-ment' for rapid solidification of molten alloys in small quantities by ejecting them on to a highly conducting substrate with the aid of a shock wave has come to be known as "liquid quenching" or "splat cooling" in literature and has already been applied to alloys of many binary systems.' The very high cooling rates of the order of l060 to 1080 per sec obtained in this technique and the consequent drastic undercooling of the melt have led to such striking results as formation of new amorphous and crystalline metastable phases and extension of solid-solubility limits in many alloy systems. The cooling rates in these experiments can, however, be neither accurately measured nor effectively controlled and hence the occurrence of either more than one metastable phase or appreciable differences in constitution in splat-cooled alloys of the same composition cannot be ruled out.3 In fact, workers in two laboratories have reported formation of two different cubic metastable phases in liquid-quenched Au-Si alloys containing 17 to 20 at. pct si.4,5 The present note deals with some new and interesting results obtained in a Ag-21 at. pct Ge alloy and a Au-27 at. pct Ge alloy subjected to the liquid-quenching treatment at different cooling rates. Two alloys of nearly the same composition had earlier been rapidly solidified by the standard "gun technique" in the same laboratory and shown to solidify in nonequilibrium structures, viz., an hcp phase (a = 2.987Å;c =4.718Å) in the Ag-Ge system6,7 and both hcp (a = 2.885Å; c = 4.754Å) and tetragonal (a = 11.627A; c = 22.491Å) phases in the Au-Ge system.3 Apart from different substrates (copper and stainless steel), different melt temperatures (50º to 500°C above the liquidus), and different capillary sizes (0.4 to 1.5 mm diam) in the "gun technique", slower cooling rates of the order of l050C per sec were also obtained in the present work by replacing the substrate by water at room temperature in a modification of the technique due to Olsen and Hultgren.8 No attempt was made to measure the cooling rate in any experiment. The products varied from fine powder (>40 pct by wt—200 mesh) obtained by quenching in water to thin flakes and foils (11.0 sq mm to 4.0 sq cm) produced by splat cooling. They were subjected to the Debye-Scherrer method of X-ray examination in each case. In case of the Ag-Ge alloy, in addition to the expected metastable hcp phase,6 a coexistent tetragonal phase (a = 5.093,Å; c = 7.009Å) was detected in some experiments. Eight weak X-ray reflections from this phase could be identified, two of them being the same as reported earlier.7 With increase in the cooling rate, the dominant hcp phase seems to be first accompanied by traces of silver or germanium and then either homogeneous or mixed with traces of this new tetragonal phase. The splat-cooled Au-Ge alloy showed generally the expected hcp and tetragonal phases,3 but sometimes traces of germanium were also present. Further, two new tetragonal phases with the following lattice param ters could be clearly identified in samples quenched

Jan 1, 1970

By David R. Mitchell

IT is impossible to mention by name all the men and organizations that contributed to this volume. The original manuscripts of the chapters contained acknowledgments of various lengths, but space limitations make it impossible to print them. Suffice it to say that virtually everyone active in coal preparation in the United States contributed directly or indirectly to the contents of the volume. Special thanks are given to manufacturers of preparation machinery for their courtesy and willingness to furnish data, photographs and drawings. I am extremely grateful to Lupo Cinco, Alfred C. Arnold, Alfred E. Flowers, James M. Krese, J. H. Kelley, E. E. Vaccaro, E. J. Sandy, Edward Steidle, Jr., Joseph Fiedorek, David Scanlon, and Joseph T. Weber, former mining engineering students who contributed much of their leisure time for proofreading, checking references, and drafting, and without whose assistance it would have been difficult to prepare the manuscripts for publication this year. All sizes are for round-hole screens and tons are 2000 pounds, unless otherwise stated or indicated. Much of the manuscript material was prepared and edited during the war year of 1942 and I wish to offer my sincere thanks to contributors for their willingness to cooperate during these trying times. No doubt errors and omissions will be found in this book and for these I ask the readers' kindly indulgence.

Jan 1, 1943

By Andrew Roy

THE Mahoning Valley coal region lies on the extreme northern outcrop of the Ohio coal-field, and all the mines, with one exception, are opened on the lower coal of the series, No. 1 of the Ohio Geological Survey. The coal ranges from an inch to five, six, and sometimes seven feet thickness, the workable height being between two and a half and six feet. There are two varieties of coal, known in market as "Briar Hill coal " and " Mineral Ridge coal;" both varieties are drawn from the same seam. The Briar Hill coal is generally called block coal, and is the kind so largely used in a raw state in smelting iron. It pos¬sesses a laminated structure, easily splitting into horizontal sheets, but is very difficult to break in the opposite direction. The faces of the layers are often covered with a soft, dead, carbonaceous material, like charcoal, and the whole seam throughout is marked by alternate layers of dead and bright-looking coal. In the act of combustion the coal neither swells nor changes form, the masses retaining their shapes until they fall to ashes in the furnace. The Mineral Ridge variety is much softer, and is also shorter in the grain than the Briar Hill. kind, and it contains a good deal of

Jan 1, 1876

By Andrew Roy

The Mahoning Valley coal region lies on the extreme northern outcrop of the Ohio coal-field, and all the mines, with one exception, are opened on the lower coal of the series, No. 1 of the Ohio Geological Survey. The coal ranges from an inch to five, six, and sometimes seven feet thickness, the workable height being between two and a half and six feet. There are two varieties of coal, known in market as "Briar Hill coal " and " Mineral Ridge coal;" both varieties are drawn from the same seam. The Briar Hill coal is generally called block coal, and is the kind so largely used in a raw state in smelting iron. It possesses a laminated structure, easily splitting into horizontal sheets, but is very difficult to break in the opposite direction. The faces of the layers are often covered with a soft, dead, carbonaceous material, like charcoal, and the whole seam throughout is marked by alternate layers of dead and bright-looking coal. In the act of combustion the coal neither swells nor changes form, the masses retaining their shapes until they fall to ashes in the furnace. The Mineral Ridge variety is much softer, and is also shorter in the grain than the Briar Hill kind, and it contains a good deal of

By E. Miller, J. M. Eldridge, K. L. Komarek

The thermodynamic properties of- liquid Mg-Pb allojs have been determined by an isopiestic method from 18 to 42 at. pct Pb and by a thevmodynumic analysis of the phase diagram frofiz 0 to 100 at. pct Pb. In the overlapping composition range the magneszupn activity values derived by the two methods are in excellent agreement, thus mutually supporting the correctness of the Mg-Pb phase diagram previously determined by the authors and of the acticitzes deriz~ed isopiestically. SEVERAL studies have been made of the thermody-namic properties of liquid Mg-Pb alloys. Wagner and Engelhardt,1 Lantratov,2 Knappwost,3 Sryvalin et al.* and Wilson5 used the electromotive-force method, Scheil and Wolf8 and Schmahl and Sieben" applied the transpiration technique, and the present authors8 utilized the phase diagram to determine the activity of magnesium in the Mg-Pb system. The results of these studies are not in very good agreement and could not be incorporated into a general systematic analysis of the thermodynamic properties of the homologous series of the Mg-Group IV B systems Mg-Pb,8 Mg-Sn,° Mg-Ge,10and Mg-Si.11 The thermodynamic properties of the Mg-Pb system were therefore re investigated by an isopiestic technique which has been developed for similar studies in the Mg-SnB and Mg-Ge10 systems- Lead specimens, contained in iron or graphite crucibles, were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure to form alloys of compositions which depended on their temperatures, the temperature of the magnesium vapor source, and the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE Magnesium (Dominion Magnesium Ltd., Toronto, Canada) of 99.99+ pct purity and lead (American Smelting and Refining Co.) of 99.999 pct purity were used. In the early experiments, Runs 2 and 3, the alloys were contained in uncovered high-purity iron crucibles. Alloys formed in the uncovered iron crucibles had to be chemically analyzed owing to the slight volatility of lead under the imposed experimental equilibration conditions. The compositions of these alloys were determined by a gravimetric analysis of lead as lead chromate. To avoid this problem, the remaining runs were made in covered graphite crucibles machined from high-density (1.92 g per cu cm) graphite rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The non- i reactivity of graphite with lead and magnesium has been previously established,' and the experimental procedure has been described in full detail.' In the runs using covered graphite crucibles it was found that the weight increases of the crucibles and their contents after equilibration equaled the magnesium contents of the alloys within the accuracy of the chemical analysis (i0.3 at. pct Pb). Clearly, the small lid openings of the graphite crucibles prevented significant lead losses during a run, and the weight increase was therefore taken as the magnesium content of the alloys. EXPERIMENTAL RESULTS At thermodynamic equilibrium the magnesium partial pressure of the specimens equaled that of the reservoir. Since the magnesium reservoir was always maintained at the temperature minimum of the system, the activity of magnesium of any specimen was given by the ratio of the magnesium reservoir pressure to the vapor pressure of pure magnesium at the specimen temperature. The standard state was chosen as liquid magnesium and the vapor pressure of liquid magnesium

Jan 1, 1968

By R. Shuttleworth, R. Smith

A Knudsen effusion tnethod I~as been used lo measure the vapor pressure of pure iron in the temperature range 1000° to 1500°C. Neutron-irradiated , natural iron was used and the Mn'~proclzdced by the (n, p) reaction removed by evaporation at high temperature. The results can be represented by the equation: where pM - 1.088 x 107 atm and T, = 20,890°K. A value of 100.2 kcal per g- atom was obtained for AH;. THE vapor pressure of pure iron in the temperature range 1000" to 1500°C has been measured. Radioactive iron and a Knudsen cell technique were used and the Mn' produced by an (n, p) reaction removed by evaporation at high temperature. From the variation of vapor pressure with temperature values of the enthalpy and entropy of solid iron have been found. Previous workers2 used a Lang-muir method and measurements were made over a smaller temperature range than that in this work. EXPERIMENTAL The apparatus used was similar to that of Pyle and Shuttleworth, and McLellan and Shuttle worth. However, because of the higher temperatures the Knudsen cell was machined from tungsten bar and the flanged furnace tube was beryllia. Heating was by passing a high current (70 amp at 7 v for 1500°K) through a strip of tantalum foil laid across the top of the cell and through a turn of molybdenum wire around the furnace tube. This method of heating ensured that the top of the cell was slightly hotter than the base and prevented condensation and re-evaporation from the orifice. The temperature was measured by means of a pt/Pt 13 pct Rh thermocouple spot-welded to the base of the crucible. To ensure accurate temperature measurement the iron was in the form of a thin disc (0.75 cm diam by 0.075 cm) which lay on the base of the cell. The high-purity iron was irradiated in the Harwell pile for a week at a neutron flux of 1.2 X 10" neutrons per sq cm per sec. The isotopes fe'~ and Fe" are produced by (n! y) reactions but only Fe", half-life 45.1 days, is a emitter; Mn which is also a y emitter, half-life 300 days, is produced simultaneously by an (n,p) reaction.' Immediately after irradiation of natural iron the ratio of ~e" to Mn y activity was 100:l. However, manganese is very much more volatile than iron and almost all the y activity of the condensate is due to Mn'~. Thus it was essential to eliminate all the manganeses before any measurement of the vapor pressure of iron was made and this was done by preliminary heating for 20 hr at 1400°C. For each determination the iron was dissolved from the target with acid and the y activity compared to a known weight of iron. By means of a y-ray spectrometer the y-activity measurements were made at the 1.09-mev peak of the 17e5' spectrum where the background was of the order of 3 cpm. Despite the low specific activity of ~e" a mass of 10- " g of iron could be determined corresponding to a vapor pressure of about l0-'' atm. RESULTS The vapor pressures were calculated from the equation: Where m is the mass of iron effusing in a time t through an orifice of area a2, r is the radius of the target, Z is the distance from the orifice to the

Jan 1, 1965

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By H. Warlimont

Precipitation of cementite plates from carbon-rich austenite gives rise to localized formation of martensite in the matrix next to the precipitate upon quenching. The growth of this martensite is urmsually restricted. A distinct lattice relationship is found between this martensite and the cementite phase. It is concluded that the martensite is nacleated in the region of lowest carbon concentration at the austenite-cementite integace, with low-energy matching to the cementite lattice. The restriction of the growth of the martensite phase to the vicinity of the cementite plates can be explained by misfit in the austenite -martensite glissile interface and the uphill carbon gradient in the austenite. The investigation was carried out by light- and electron-microscopy and by electron-diffraction of thin foils. THE precipitation of cementite from carbon-rich austenite gives rise to a localized formation of martensite in the matrix next to the precipitate upon quenching. This behavior has been described previously by A. B. Greninger and A. R. Troiano1 for a 1.78 pct C steel ("pseudomorphic martensite"), and by A. Hultgren2 for a Fe-0.99 pct C—5.20 pct Mn steel. By measuring the axial ratio of the martensite phase,' it was found that the carbon content of this martensite was lower than that of the martensite which formed without prior partial transformation to cementite. Therefore, it was concluded that lowering of the carbon concentration in the matrix next to the precipitate raised the M, temperature locally and thus led to nucleation of martensite at the ce-mentite-austenite interface. However, the restriction of the growth of the martensite phase to the vicinity of the cementite plates cannot be explained by localized carbon impoverishment alone. Under ordinary conditions a martensite plate which has been nucleated in a favorable site can continue to grow until it encounters a physical barrier, or until it encounters a compositional barrier in the matrix, where the total free-energy change for the reaction is not negative, since it has been shown by numerous experiments that the activation energy for growth of ordinary martensite is virtually zero.' An investigation was conducted by transmission electron microscopy and electron diffraction to study this extraordinary martensite. It was expected that crystallographic in addition to compo- sitional conditions caused this abnormal mode of martensite formation. MATERIAL AND PROCEDURE An Fe-C-Mn alloy containing 1.15 pct C and 5.1 pct Mn was used for most of the experiments. For metallographic work, specimens 15 by 15 by 3 mm were used. For preparation of thin films, the initial specimen size was 15 by 15 by 0.7 mm. The heat treatment of each specimen consisted of austenitizing for 1/2hr at 1100'~ in an argon atmosphere, subsequent isothermal holding in a lead bath at one of a series of different temperatures, and, finally, quenching into brine at room temperature. For metallographic examination, the specimens were mounted in bakelite (slight tempering effects resulted from the heat in the mounting press) ground, polished, and etched in nital. Thin films for transmission electron microscopy and electron diffraction were obtained by grinding the specimens to approximately 0.2 mm thickness and subsequent electrolytical thinning. The orientation relationships were evaluated from sets of electron micrographs and selected-area electron diffraction patterns of single units of the transformation products and the adjacent matrix. RESULTS In the alloy which was used for the experiments, proeutectoid carbide precipitates over a wide tem-

Jan 1, 1962