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By Howard N. Eavenson

Waste of coal, or perhaps more properly the percentage of its recovery in mining, has keenly interested me during an experience of over a half century in coal mining. In the early part of that time and until a few years after World War I the use of better mining plans and supervision resulted in an increased recovery. Since then, and particularly since controlled prices have been effective and mechanized mining has been extensively practiced, the tendency has all been toward lesser recovery in mining. The purpose of this paper is not to criticize the methods being used, which after all are the result of economic forces, nor to point to any particular mining method or to any locality where the best recovery is obtained, but to call attention to the tremendous waste of our national coal resources that is constantly continuing. A possible method of reducing this loss will be suggested, but without any illusions that it will be followed or that such attention will be paid to it. Average Recovery The actual average percentage of recovery of coal in the ground is not known. Many papers giving figures of recovery have been published but no definite base of measurement has been agreed upon by those presenting the data. As an example, the Pittsburgh bed can be considered—it has produced a greater output than any other and has been sold or leased at higher prices in place than any other coal bed. Over a large part of its area where high prices have prevailed it has been customary for many years to draw pillars. In these mines it has been usually assumed that the average recovery was higher than in other beds and percentages of recovery of 85 to 95 per cent are usually said to be realized. In all of these mines, however, it has been customary to leave from 4 to 8 in. in the bottom, and 10 to 16 in. in the roof; thus from 14 to 24 in. of coal has been left in the mines out of a total seam thickness of about 96 in., or 15 to 25 per cent of the total coal. No attempt is made to mine this coal for metallurgical purposes, owing to its impurities, although this unmined coal is of excellent quality and better than much of the coal used for steam purposes. If we add to this discard the coal usually lost in mining and those parts of the bed 'that must be left because of bad seam conditions, barrier pillars, reservations for buildings, gas and oil wells, one can easily see that the actual recovery from this bed cannot be more than 65 to 75 per cent. In addition, the rooster or rider or wild coal over the mining bed—often 3 to 4 ft. of coal, high in ash and sulphur but still good steam coal—is hardly ever mined, nor is any attempt made to mine it. It is safe to say that from a broad economic viewpoint not more than 50 to 60 per cent of the fuel value of this great seam is actually being recovered.

Jan 1, 1947

By Howard N. Evanenson

WASTE of coal, or perhaps more properly the percentage of its recovery in mining, has keenly interested me during an experience of over a half century in coal mining. In the early part of that time and until a few years after World War I the use of better mining plans and supervision resulted in an increased recovery. Since then, and particularly since controlled prices have been effective and mechanized mining has been extensively practiced, the tendency has all been toward lesser recovery in mining. The purpose of this paper is not to criticize the methods being used, which after all are the result of economic forces, nor to point to any particular mining method or to any locality where the best recovery is obtained, but to call attention to the tremendous waste of our national coal resources that is constantly continuing. A possible method of reducing this loss will be suggested, but without any illusions that it will be followed or that such attention will be paid to it. AVERAGE RECOVERY The actual average percentage of recovery of coal in the ground is not known. Many papers giving figures of recovery have been published but no definite base of measurement has been agreed upon by those presenting the data. As an example, the Pittsburgh bed can be considered-it has produced a greater output than any other and has been sold or leased at higher prices in place than any other coal bed. Over a large part of its area where high prices have prevailed it has been customary for many years to draw pillars. In these mines it has been usually assumed that the average recovery was higher than in other beds and percentages of recovery of 85 to 95 per cent are usually said to be realized. In all of these mines, however, it has been customary to leave from 4 to 8 in. in the bottom, and 10 to 16 in. in the roof; thus from 14 to 24 in. of coal has been left in the mines out of a total seam thickness of about 96 in., or 15 to 25 per cent of the total coal. No attempt is made to mine this coal for metallurgical purposes, owing to its impurities, although this unmined coal is of excellent quality and better than much of the coal used for steam purposes. If we add to this discard the coal usually lost in mining and those parts of the bed that must be left because of bad seam conditions, barrier pillars, reservations for buildings, gas and oil wells, one can easily see that the actual recovery from this bed cannot be more than 65 to 75 per cent. In addition, the rooster or rider or wild coal over the mining bed often 3 to 4 ft. of coal, high in ash and sulphur but still good steam coal-is hardly ever mined, nor is any attempt made to mine it. It is safe to say that from a broad economic viewpoint not more than 50 to 60 per cent of the fuel value of this great seam is actually being recovered.

Jan 1, 1946

By R. J. Wasilewski

The variation of elastic modulus with terrzperature between -150° and 600°C has been investigated. Compounds close to equiatomic cornposition exhibit very low modulus values and very high damping near room temperature. The modulus rises steeply with both decreasing and increasing temperature. The modulus minimum and the high damping are believed to be connected with a martensitic transformation of TiNi. In bulk material this transition takes place slightly above room temperature quite rapidly and reversibly, with a hysteresis of some 30°C, depending on the Ti:Ni ratio. Oxygen impurity affects the reaction time. THE inter metallic compound TiNi has been reported to exist in an ordered CsCl (B2) structure,l-6 the homogeneity range varying rather markedly with temperature.7 Some investigators reported this compound to decompose peritectoidally to Ti2Ni and TiNi, between 650° and 800°C,3 or below,',g the latter workers also suggesting the decomposition to be strain-sensitive. Purdy and Parr were the first to report a structural transformation to a new, possibly hexagonal, structure at 36°C,7 a temperature indubitably too low to allow the significant amount of diffusion necessary for a peritectoid reaction. Mechanical-property investigations of compositions close to TiNi just above room temperature have qualitatively shown remarkable anomalies, particularly with respect to clamping,' and to a "memory" effect, that is, plastically deformed material returning to its original shape on being heated through the "decomposition" temperature.9 The original explanation of this effect—based on the apparent experimental observation of Ti2Ni or TiNi, formation in the material subjected to tensile or compressive stresses, respectivelp—does not appear plausible. It appeared more probable that the change involved may be a martensitic, diffusionless structural transformation, similar to those observed in other B2 structures such as 0 brass,'' AuCd,ll and AuZn.12 The existence of such transformation has been established recently,', although the symmetry of the low-temperature structure is not yet known. The present paper describes the elastic modulus and damping behavior of polycrystalline TiNi in both structures. EXPERIMENTAL METHOD 1) Specimens. All the specimens to be investigated were prepared from premelted electrolytic nickel and iodide titanium by nonconsumable arc melting and casting in a water-cooled copper mold. The cast billets were canned in mild steel, extruded, and swaged to approximately 0.375 in. diam. The cans were then removed by pickling or machining. Preliminary material balance checks indicated no significant weight losses on melting (less than 5 mg on a 50-g button); hence nominal compositions have been used throughout. In agreement with previously reported observations7 no single-phase material was obtained at—or close to—Ti 1.00 Ni1.00 a small amount of finely divided second phase always being present. It was found that most of the oxygen impurity was associated with this minor phase, which was identified as oxygen-bearing Ti2Ni—possibly Ti,Ni,O. The amount of this phase—at any given Ti:Ni composi-

Jan 1, 1965

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,' on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By A. J. Phillips, A. A. Smith, J. S. Smart

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By John S. Johnson

The purpose of this article is to describe several types of borehole lining in common use, and especially to offer a relatively new means of reducing the expense of maintaining boreholes where they are subjected to corrosive action of water flowing either inside or outside of their casing. In the Anthracite region of Pennsylvania, boreholes are used for many purposes, the principal ones being: openings between the surface and underground workings through which are passed steam, water and compressed-air lines, ropeways from surface hoists to underground rope haulages, conduits for electric power and signal lines, water-discharge lines from underground pumping stations, and inlets to mine workings for flushing material. Linings for Boreholes The inadequacy of steel pipe for use in boreholes has long been recognized. Various substitute materials have been tried, including screw-joint cast-iron pipe (Fig. I). Cast-iron pipe, while very effective as a discharge line for acid water (mine water) being pumped to the surface, is not so effective when serving as a conduit for silt and crushed rock being flushed underground for filling mine voids. Terra cotta pipe (Fig. 2) has been used in boreholes, and lasts a long time if the glazed inner surface of the pipe remains intact. Its installation in a borehole is very difficult and is recommended only where it is certain that there will be no subsidence of the surrounding territory. Accessibility in order properly to join each section of the pipe is essential to a satisfactory job. In large water holes, where it is possible to lower a man into the hole for sealing the joints of the pipe, glazed terra cotta pipe has been used successfully for delivering mine water from pumps in the mines. For large holes used for flushing refuse into mine workings where the surface wash is shallow, standard paving brick have been used to form a tube through the wash to the bedrock. These brick are laid radially, backed by common brick and cobbles laid in cement. It is obvious that the shaft through the wash must be large enough to permit a man to work in it. The flushing material is carried through bare rock from the juncture at bedrock to the openings underground. This plan has been used particularly where a cast-iron surface line is laid upon the surface to carry the flushing material from the breaker to the hole, and down the hole continuously, with no opening to the air at the top of the hole, thereby eliminating the necessity of an attendant at this point (Fig. 3). Another similar type of borehole lining is constructed of hexagonal pieces of vitrified brick (Fig. 4). This type requires a steel drive pipe through the surface wash large enough to provide a finished tube of the desired size surrounded by a brick wall about 4 in. thick. The special bricks are laid in cement, six to a circle, around a lubricated pipe used as a form, and lowered in sections inside the large drive pipe; the bottom section is seated in a socket drilled in the solid rock, having the same inside

Jan 1, 1942

By I. E. Campbell, R. I. Jaffe

Oxygen, nitrogen, and hydrogen are known to be absorbed by titanium at elevated temperatures. Ehrlichl reports that about 30 at. pct oxygen can be dissolved in solid solution by alpha-titanium. Nitrogen also has a solid solubility in alpha-titanium, but there is no information as to its extent. The solid solubility of hydrogen in titanium also is high. Kirshfeld and Sieverts2 report 50 at. pct soluble, while Hägg3 reports about 33 at. pct hydrogen to be soluble in alpha-titanium. General statements are made in the literature that oxygen, nitrogen, and hydrogen embrittle titanium, but no quantitative measurements have been made of the effect of these gases on the mechanical properties of the metal. One reason for this is the lack of a source of titanium pure enough to be considered a suitable starting material. Iodide-refined titanium, made by thermal decomposition of titanium iodide vapor on an incandescent wire,4 contains small amounts of carbon, silicon, iron, and aluminum, but is very low in oxygen, nitrogen, and hydrogen content, and, therefore, was used in this work. A further reason for the lack of quantitative information on the effect of these gases, particularly oxygen, is the difficulty of carrying out accurate analytical determinations at the low concentrations of interest in this work. For this reason, the oxygen, nitrogen, and hydrogen were added in measured amounts as gases, and diffused into the titanium, to avoid the necessity of chemical analysis. The purpose of the work reported here was to isolate and measure the effects of oxygen, nitrogen, and hydrogen on titanium of the highest purity available at the time. The concentrations studied were 0.25, 0.5, and 1 at. pct in each case. Experimental Work One-half of a 24-in. hairpin of iodide-refined titanium was available for this work. The rod was approximately 0.25-in. in diam and had a 0.003-in.tung sten core. From chemical and spectro-graphic analyses, the purity of the sample was estimated to be between 99.80 and 99.95 wt pct. The chief impurities (aside from the tungsten core) were iron (0.04 pct), silicon (0.01-0.1 pct), aluminum (0.05 pct), carbon (0.03 pct). The tungsten core constituted 0.05 pct by weight of the sample. Although some alloying undoubtedly took place between the tungsten and the titanium during the deposition reaction, the core remained substantially intact in the deposited metal. The initial average hardness of the titanium as deposited was 105 Vickers (10-kg load). The maximum hardness was 116 Vickers and the minimum 91 Vickers. The metal was somewhat harder than that currently being obtained by the iodide process, that is, 75-90 Vickers. The rod was cold swaged to ¼-in. diam and then cold rolled in diamond shaped rolls to about 0.080-in. square, using reductions of 15 pct in area per pass. The 0.080-in.-square wire was cut into 6-in. lengths for the preparation of the alloys by the gaseous absorption and diffusion method. ADDITION OF OXYGEN, NITROGEN, AND HYDROGEN TO TITANIUM A modified Sieverts' absorption apparatus, shown in Fig 1, was used in

Jan 1, 1950

By A. G. Guy

Zinc vapor from a reservoir of liquid zinc maintained at lower temperatures was diffused into sets of copper-zinc alloys at 759° and 870° C and into sets of silver-zinc alloys at 650° and 700° C. Each set of ,four copper-zinc alloys consisted of pure copper and 90/10, 80/20, and 70/30 brass. Similarly the set of silver-base alloys consisted of specimens containing 0, 7, 15, and 20 pct Zn. Natural markers at the initial surfaces of the specimens ware "trapped" under a thin electroplate and their depth of burying was measured after diffusion. The ratio of diffusivities of the two components determined from these data and the chemical diffusion coefficient calculated by the Matano method agreed with previously reported results. The line of markers was irregular and was often discontinuous when a grain boundary was crossed. TECHNIQUES involving the vapor phase have been widely employed in studying diffusion phenomena in metals. Many investigators have evaporated the more volatile component from an alloy, but it is generally believed that the porosity created under these conditions interferes with adequate interpretation of the experimental results. The extensive work of Gertsriken6 has been criticized on this score. Accary1 found that the diffusion coefficient for de-zincification of brass is larger by a factor of five than that for zincification, although he attributed the difference to a higher vacancy concentration under conditions of dezincification. Balluffi and siegle2 thoroughly investigated the technique of adding a more volatile component to a less volatile base metal as a means for studying diffusion. They verified that no porosity forms in a brass under these conditions and that the diffusivities of the two components can be determined from observations of the motion of markers originally placed on the surface of the specimen. The mathematical analysis that they developed for treating the experimental data was modified in a later note, but essentially it involved using the graphical Boltzmann-Matano method that is customarily applied to solid-solid diffusion couples. The experimental method used in the present research was similar to that employed by Balluffi and Siegle except for two modifications. Balluffi and Siegle used alloy chips as the source of metal vapor. This procedure has the disadvantage that the concentration of solute at the surface of the specimen changes during the diffusion experiment as the alloy content of the chips is gradually decreased. This disadvantage was overcome by employing liquid zinc as the source of zinc vapor in a manner similar to that described by Herasymenko.9 There was then no limitation on the amount of solute usefully available, and several relatively large specimens could be diffused in a given experiment. The second modification was the use of natural markers on the surface of the specimen rather than larger, artificial markers, such as the alumina powder employed by Balluffi and Siegle. It was expected that the fine, natural markers would permit more precise measurement of the buried interface as in the case of ordinary sandwich specimens.10 EXPERIMENTAL The experiments were designed so that zinc from the vapor phase would maintain a constant zinc content at the surface of pure copper (or silver) and

Jan 1, 1960

By John S. Johnson

The purpose of this article is to describe several types of borehole lining in common use, and especially to offer a relatively new means of reducing the expense of maintaining boreholes where they are subjected to corrosive action of water flowing either inside or outside of their casing. In the Anthracite region of Pennsylvania, boreholes are used for many purposes, the principal ones being: openings between the surface and underground workings through which are passed steam, water and compressed-air lines, ropeways from surface hoists to underground rope haulages, conduits for electric power and signal lines, water-discharge lines from underground pumping stations, and inlets to mine workings for flushing material. Linings for Boreholes The inadequacy of steel pipe for use in boreholes has long been recognized. Various substitute materials have been tried, including screw-joint cast-iron pipe (Fig. I). Cast-iron pipe, while very effective as a discharge line for acid water (mine water) being pumped to the surface, is not so effective when serving as a conduit for silt and crushed rock being flushed underground for filling mine voids. Terra cotta pipe (Fig. 2) has been used in boreholes, and lasts a long time if the glazed inner surface of the pipe remains intact. Its installation in a borehole is very difficult and is recommended only where it is certain that there will be no subsidence of the surrounding territory. Accessibility in order properly to join each section of the pipe is essential to a satisfactory job. In large water holes, where it is possible to lower a man into the hole for sealing the joints of the pipe, glazed terra cotta pipe has been used successfully for delivering mine water from pumps in the mines. For large holes used for flushing refuse into mine workings where the surface wash is shallow, standard paving brick have been used to form a tube through the wash to the bedrock. These brick are laid radially, backed by common brick and cobbles laid in cement. It is obvious that the shaft through the wash must be large enough to permit a man to work in it. The flushing material is carried through bare rock from the juncture at bedrock to the openings underground. This plan has been used particularly where a cast-iron surface line is laid upon the surface to carry the flushing material from the breaker to the hole, and down the hole continuously, with no opening to the air at the top of the hole, thereby eliminating the necessity of an attendant at this point (Fig. 3). Another similar type of borehole lining is constructed of hexagonal pieces of vitrified brick (Fig. 4). This type requires a steel drive pipe through the surface wash large enough to provide a finished tube of the desired size surrounded by a brick wall about 4 in. thick. The special bricks are laid in cement, six to a circle, around a lubricated pipe used as a form, and lowered in sections inside the large drive pipe; the bottom section is seated in a socket drilled in the solid rock, having the same inside

Jan 1, 1942

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By John S. Johnson

THE purpose of this article is to describe several types of borehole lining in common use, and especially to offer a relatively new means of reducing the expense of maintaining boreholes where they are subjected to corrosive action of water flowing either inside or outside of their casing. In the Anthracite region of Pennsylvania, boreholes are used for many purposes, the principal ones being: openings between the surface and underground workings through which are passed steam, water and compressed-air lines, ropeways from surface hoists to underground rope haulages, conduits for electric power and signal lines, water-discharge lines from underground pumping stations, and inlets to mine workings for flushing material. LININGS FOR BOREHOLES The inadequacy of steel pipe for use in boreholes has long been recognized. Various substitute materials have been tried, including screw-joint cast-iron pipe (Fig. I). Cast-iron pipe, while very effective as a discharge line for acid water (mine water) being pumped to the surface, is not so effective when serving as a conduit for silt and crushed rock being flushed underground for filling mine voids. Terra cotta pipe (Fig. 2) has been used in boreholes, and lasts a long time if the glazed inner surface of the pipe remains intact. Its installation in a borehole is very difficult and is recommended only where it is certain that there will be no subsidence of the surrounding territory. Accessibility in order properly to join each section of the pipe is essential to a satisfactory job. In large water holes, where it is possible to lower a man into the hole for sealing the joints of the pipe, glazed terra cotta pipe has been used successfully for delivering mine water from pumps in the mines. For large holes used for flushing refuse into mine workings where the surface wash is shallow, standard paving brick have been used to form a tube through the wash to the bedrock. These brick are laid radially, backed by common brick and cobbles laid in cement. It is obvious that the shaft through the wash must be large enough to permit a man to work in it. The flushing material is carried through bare rock from the juncture at bedrock to the openings underground. This plan has been used, particularly where a cast-iron surface line is laid upon the surface to carry the flushing material from the breaker to the hole, and down the hole continuously, with no opening to the air at the top of the hole, thereby eliminating the necessity of an attendant at this point (Fig. 3). Another similar type of borehole lining is constructed of hexagonal pieces of vitrified brick (Fig. 4). This type requires a steel drive pipe through the surface wash large enough to provide a finished tube of the desired size surrounded by a brick wall about 4 in. thick. The special bricks are laid in cement, six to a circle, around a lubricated pipe used as a form, and lowered in sections inside the large drive pipe; the bottom section is seated in a socket drilled in the solid rock, having the same inside

Jan 1, 1941

By E. B. Hughes, F. G. Norris

Oxidation is characteristic of all processes for making steel from pig iron. This thought has been aptly expressed by H. W. Graham13 in the recent Howe Memorial Lecture, "The process of steel-making consists of using iron oxide to reduce the carbon content of the pig iron to the desired level." Direct oxidation refers to the reaction that results from introducing oxygen either alone or mixed with other gases directly into the steel bath. In working a heat, oxygen in some form is added to the steel to remove the undesirable constituents as oxides. There are two general methods of supplying this oxygen to the open hearth bath. The method in which the oxygen is added as a compound such as Con or iron ore is designated an indirect method because the steel bath must first decompose the compound to attain oxygen in a usable form. The other method in which oxygen is added to the bath in the elemental or gaseous form, more or less diluted by other gases such as nitrogen, is a direct method because no decomposition is necessary before the oxygen reacts with iron to form FeO which is dissolved in the bath in a usable form. Bubble formation (at least of a macroscopic size) presents no problem in case of direct oxidation because the reacting agent (oxygen) is in the form of bubbles when entering the metal. Regardless of whether oxygen is intro- duced into the bath directly or indirectly, several reactions proceed concurrently. In the presence of the bath of molten iron, FeO is formed either by oxidation of iron by oxygen or reduction of oxides by iron. This FeO dissolved in the molten iron is the source of oxygen for the oxidation of manganese, carbon, silicon, and phosphorus if these are present. The oxidation of carbon from steel is the controlling steelmaking reaction. The introduction of oxygen into the bath, its reaction in the elimination of impurities, and its control by the use of de-oxidizing additions have been subjects of importance since steel was first made by the bessemer process. Direct oxidation is, in a sense, an application of the bessemer principle to the open hearth process. Graham13 states: "The use of oxygen or air jets introduced into the metal bath is essentially an effort to approach in the open hearth the turbulence, rapid interface reaction, and high production rate per hour that exists in the bessemer process." The general subject, "Oxygen in Steel-making," was given new life by the studies of Herty and associates starting about1925. The current interest in elemental oxygen is intimately related to the large scale production of oxygen developed during the war period. Some of the first applications were made during the early summer of 1946 at the Steel Co. of Canada using oxygen with the fuel. Such a use is of considerable interest and importance in contributing to faster heats but is not the subject of the present discussion which deals entirely with the introduction of elemental oxygen directly into the open hearth bath.

Jan 1, 1949

By T. B. Massalski, Horace Pops

The occurrence and the temperature dependence of the athermal martensitic transformation in bcc Cu-Zn ß-phase alloys have been studied by cold-state microscopy, differential thermal analysis, and electrical -resistivity measurements. CinenzatograpJzic studies have shown that in the majority of alloys the transformation occurs in two stages. A thermoelastic phase, having a 'needlelike" uppearance, forms initially at the MS temperature and grows relatively slowly, chiefly in the edge (lengthwise) direction. With further cooling, an additional martensitic phase forms in rapid bursts at a lower temperature, MB, Both martensitic phases appear to have the same cry stallographic habit hut their modes of formation and growth are different. For the composition range studied, between 38.55 and 41.49 wt pct Zn, the habit planes determined are close to the (2.17 ,12) plane of the matrix, in general agreement with the prediction of the phenomenological theory of martensite formation. Thermal cycling through the MB temperature produces permanent plastic deformation in the 0 matrix and gradutally eliminates the typical burst phenomena. Thermal cycling only through the MS temperature produces no noticeable deformation effects. THE bcc Cu-Zn ß-phase alloys tend to become unstable at low temperatures and undergo a martensitic transformation,'-3 but the details of the transformation have not been completely determined. Following earlier metal log raphic and X-ray work1 Tichener and ever' determined by means of electrical-resistivity measurements the temperature range of the martensite transformation during continuous cooling. The transformation temperature was found to decrease with increasing zinc content, becoming about -130°C for an alloy containing 40.04 wt pct Zn. Hull and Garwood3 made a metallo-graphic study of Cu-Zn 0 brasses at temperatures down to -160°C, and determined the habit plane of the transformation product for an alloy containing 38.88 wt pct Zn. No metallographic studies below liquid-nitrogen temperatures have been reported. The martensitic transformation in ß-brass alloys can also be induced by deformation.1,4 The MD temperature corresponding to the appearance of the strain-induced martensite is some 300°C higher than that observed without strain, and hence the transformation can be strain-induced in alloys containing a higher percentage of zinc. Massalski and Barrett4 found that alloys containing as much as 51.89 wt pct Zn could be transformed into a faulted hcp structure by cold working at liquid-helium temperature. Because the details of the MS temperature and morphology reported in the literature are somewhat incomplete, a further study has been made of some of the above features. A design of a cryogenic stage for optical metallography5 has permitted the examination of specimens at temperatures down to 4.2oK, and the use of a cinecamera has permitted a study of the morphology on cooling and heating. The particular aim of the present work was to examine the transformation temperatures, the habit planes, and the growth morphology over a wide composition range in the ß-phase field. The effect of thermal cycling upon the subsequent transformation was also examined.

Jan 1, 1964

By D. D. Pollock, D. I. Finch

PREVIOUS work' on a four-component system (Cu-Mn-Ni-Fe) resulted in the development of consistent relationships between the chemical composition and the electrical properties of these manganin-type alloys. The present study was undertaken to develop alloys with temperature coefficients of resistivity and thermoelectric properties more desirable than those of the manganin type, and to determine whether the relationships which had been found for the Cu-Mn-Ni-Fe alloys could be extended to five-and six-component alloy systems. PREPARATION OF ALLOYS The five- and six-component alloys were made from OFHC copper rod, ARMCO iron, electrolytic nickel, manganese cathode chip, and special high-purity aluminum and indium. A Cu-Mg master was used for deoxidation. The compositions of these materials are given in Table I. The alloys were melted and cast as indicated previously,' except that no cover was used and the melts were teemed. EXPERIMENTAL PROCEDURE The finished wire size of 0.0808 in. diam was again selected for the reason that the test specimens would be self-supporting, thus eliminating any extraneous effects which might have been introduced by winding smaller diameter wire on spools or forms. The following tests were performed on the finished wires: A) Chemical Analyses—All of the components of these alloys were determined by premium gravimetric methods. The principle residual impurity contained in these alloys is 0.008 pct Mg (by weight), maximum. Tables II and 111 present the mean analyses computed from at least four determinations of each constituent. B) Electrical Characteristics—The test procedures forthe determination of the thermal emf vs copper, resistivity, and the resistance-temperature relationship are given in detail in Ref. 1. It was also shown that the resistance-temperature relationship is of the form Pt = P,n + At -B/2, [1] where P, is the resistance at t C expressed in percent of a given standard resistance, P, is this per- 0 centage at 0°C, and A and B are constants for a given, properly treated, composition. The results of the electrical tests are also given in Tables II and 111. INTERPRETATION OF DATA The modified Linde2 formula, known to be valid for dilute binary solid solutions, was applied to the complex Cu-Mn-Ni-Fe type alloys. This relationship is of the form where Ap is the increase in resistivity. Zb the valence of the solute, Zn the valence of the solvent, and K and K are designations assigned by Robinson and Dorn3 to the constants for the periodic group to which solute element belongs. The units of K, are -cm per valence difference squared per at. pct; those of K2 are pa-cm per at. pct. For the sake of brevity, these units are not repeated in the following discussion. Calculations were made to determine if this formula was accurate for five-component systems. No experimental studies were made of the Cu-In and Cu-A1 binary systems. The effects of indium additions upon the resistivity of copper are given by Linde. These data, along with those of the effects of Mn and Fe, permitted the calculation of the effects of Al.

Jan 1, 1959

By C. G. Dunn, F. W. Daniels, M. J. Bolton

IN recent papers on interface energies in metals¹,² the concept of an equilibrium of forces has been used in the measurement of interfacial tensions. Mathematically the equilibrium of three forces is given by the relations: where the 2's are the interfacial tensions (interface energies per unit area of interface) of three phases or grains meeting at angles 21 22 and 23 (212 relates to the 1-2 boundary formed by grains 1 and 2;223 to the 2-3 boundary, etc.). If these relationships are valid, one can calculate relative values of the interface energies from measured boundary angles on specimens which have been brought to equilibrium. Since Eq 1 may be derived through a mathematical process of minimizing the grain boundary energy under the restriction that the ?'s be independent of boundary orientation: the concepts of surface tensions and equilibrium of forces are not particularly essential. To deal with the general case involving dependence of boundary energy on boundary orientation, it becomes desirable to drop certain concepts formerly held (namely that energy per unit area is identical with force per unit length or surface tension) and to use the energy concept alone. It is appropriate, therefore, to use E in place of ? in deriving and using the more general equations that express the anisotropic nature of the grain boundary energy. Herring3# ' recently has derived the required general equations using the principle of minimization of energy. Specifying the boundary orientations in terms of angles (4) measured with reference to crystal axes within the grains, Herring's equations take the form E23 + E21 cos?8 + E12 cos?2 — sin ?12 + sin?2-?E12/?12 =O [2] where the partial derivatives are measured in the direction of counterclockwise rotation of the boundaries. Eq 2 implies that an infinitesimal displacement of the triple point along the 2-3 boundary produces no change in the boundary energy. Similar equations apply for infinitesimal displacements along each of the other two boundaries. From such equations Herring obtains the following general relationship (1 + E1 E2) sin?8 + (E2 — E1) cos?3 ________ E38______________ = (1+ E2 E8) sin ?1+ (E3— E2) cos ?1 __________^5____________[3] (1 + E sin ?2, + (E1 — E8,) COS ?2 1 E28 where E1 = 1/E23- E25 and PC and c8 have similar expressions. It is apparent that Eq 3 reduces to Eq 1 when the c's vanish. Eq 3 also reduces to Eq 1 when the E'S are all equal. Shockley and Read' have pointed out one limitation to these equations. When E plotted versus 4 appears as an energy cusp, as their theory requires, for example, for the energy near a twin boundary position, then Eq 3 (and therefore Eq 1 also) no longer applies if one boundary is in the minimum energy position. One of the equations of form Eq 2, however, applies if the infinitesimal displacement is along the boundary associated with the energy cusp. From the foregoing treatment it will be apparent that equilibrium angles alone are not sufficient in general for calculating relative interface energies.

Jan 1, 1951

By G. W. P. Rengstorff, L. E. Olds

High purity molybdenum ingots containing controlled amounts of a single impurity element (oxygen, nitrogen, or carbon) were prepared. These ingots were tested for ductility by bending test specimens at various temperatures. The relationship between the plastic behavior of the ingots and their chemical composition has been determined. MANY proposed applications for molybdenum require ductility at or near room temperature. At the present time, it is possible to obtain wrought molybdenum with considerable ductility only if special fabrication techniques are used to control the grain structure. Starting with are-cast or powder metallurgy ingots, the usual methods for obtaining ductility rely on fabrication procedures that result in fibered microstructures in the finished product. Recently, it has been found that the ductility of either powder metallurgy or are-cast molybdenum can be improved by uniform recrystallization of the metal to a very fine equiaxed grain structure.' The need for a fibered or a fine grained structure may limit the practical usefulness of molybdenum. For example, welding. which may be used in fabricating the metal, generally produces coarse grained structures that lead to brittleness. This applies, certainly, to currently available commercial molybdenum. Although commercial molybdenum is brittle when the grains are coarse, it has been shown experimentally that fine grained structures are not always essential for ductility. For instance, as-cast molybdenum with a coarse columnar grain structure is ductile if it is sufficiently pure.' Because high purity cast molybdenum has good ductility even when coarse grained, it is probable that the brittleness in coarse grained commercial molybdenum is caused by the impurity content of the metal. Although the general effects of impurities on the cold ductility of molybdenum have been known in a qualitative manner for some time, no quantitative evaluation of these effects has been available. The present investigation was made in order to determine more accurately the effects of oxygen, nitrogen, and carbon on the cold ductility of cast molybdenum. Oxygen has long been known to be detrimental to ductility, although the minimum amount which will embrittle molybdenum has been open to speculation. Parke and Ham" showed that ingots with oxygen contents above 0.003 pct could not be forged. Maringer and Schwope have described the embrittle-ment of molybdenum wire by oxygen. A discussion on the effects of heat treatment on the distribution of oxygen in molybdenum has been given by Perry, Spacil, and Wulff." Although nitrogen would also be expected to have harmful effects on ductility, no extensive work has been done previously to determine whether this is so. However, Tury and Krausz" found that wires presumably with less than 0.007 pct N were brittle. Carbon is added to commercial cast molybdenum for deoxidation. Parke and Ham" have shown that molybdenum containing as much as 0.06 pct C could be forged if the oxygen was kept below 0.003 pct. Also, Bruckart and others' found that the room temperature ductility of sintered molybdenum improved with carbon contents up to 0.84 pct. However, Rengstorff and Fischer' found that residual carbide particles in cast molybdenum apparently had an unfavorable effect on room temperature ductility.

Jan 1, 1957

By P. Marier, T. R. Ingraham

When cylindrical powder compacts of nickelous oxide (NiO) are heated in an equilibrated stream of SO3, SO,, and 02, in the temperature range 500°to 800°c, tlickelous suljate (NiSO4) is formed as an adherent layer on the oxide. The reaction is diffusion-controlled, with an activation energy of 13 ± 3 kcal per mole. When cylindrical powder compacts of NiSO4 are heated in a stream of dry nitrogen in the temperature range 1000 0to 11500C, NiO is formed at a well-defined interface between the sulfate and oxide. The interjhce migrates into the sulfate at a constant rate at a constant temperature and gas flow. The reaction rate increases with increasing gas flow and decreases with increasing partial pressure of SO3 in the gas stream. Resolution of the partial-pressure data with a Lang-itzliir Adsorption Isothern suggests that about 80 pct of the NiO interface is covered with SO3. The heat of adsovption is about 68 kcal per mole. The activation energy of the decomposition process is 61 ± 3 kcal per mole. MOST of the work reported on the formation and decomposition of nickel sulfate is related to thermodynamics.1-3 No quantitative work has been reported on the decomposition process. The only kinetic work reported on the formation is that by Fletcher and shelef.4-6 whose main purpose was to study the effects of alkali metal sulfate additions on increasing the rate of nickel sulfate formation. They found that, in the absence of an additive, only small amounts of sulfate were formed and the kinetic data were difficult to interpret. However, they suggested that the sulfa-tion of nickel oxide is a diffusion-controlled process for which the activation energy is approximately 17 kcal per mole.6 In this paper, both the formation and decomposition reactions will be examined; and based on the effects of temperature, flow rate, interfacial area, and partial-pressure of sulfur trioxide, mechanisms and activation energies will be suggested for both processes. EXPERIMENTAL Material. The nickel source material used in all experiments was Baker and Adamson Reagent Grade NiSO4. 6H2O, for which the following analysis was supplied by the manufacturer: C1, 0.001 pct; NO3, 0.005 pct; Co, 0.02 pct; Cu, 0.005 pct; Pb, 0.002 pct; Fe, 0.001 pct: insol, 0.005 pct. The anhydrous sulfate was prepared by heating the hydrate at 420°C in a muffle furnace for 5 hr. Nickel oxide was prepared by decomposing the sulfate at 950°C over a period of 10 hr. Method. The technique used for measuring the rates of formation and decomposition was developed earlier in these laboratories.7-8 The method is based on the observation that the kinetic parameters of a reaction can be established in a flow system, with specimens prepared by compacting powder to a uniform pellet shape. The results are identical with those established with solid polycrystalline specimens or single

Jan 1, 1967

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

The a-p type alloys are subject to a loss of tensile ductility with increasing hydrogen content. No hydride phase is visible in embrittled a-B type alloys. The embrittlement encountered appeared to be of the strain-aging type. Both compositional and structural factors are shown to influence the hydrogen tolerance of a-B type alloys. IN previous papers by the authors, the effects of hydrogen on the structure and mechanical properties of high-purity and commercial-purity titanium were described. It was shown that the presence of hydrogen in these materials results in a hydride phase having low solubility at room temperature. This insoluble phase had little effect on the room temperature tensile properties, but did decrease the notch-bar toughness to a large degree. The binary Ti-H systemz indicates that hydrogen is much more soluble in £ than in a-titanium. Hence, it is not expected that the embrittling effects of hydrogen in a-fi alloys will be similar to that found in a alloys. Materials of this type studied in the present investigation included two commercial a-/3 alloys, Ti-8Mn and Ti-4A1-4Mn; three high-purity Ti-Mn alloys containing 3, 6, and 9 pct Mn; and four high-purity Ti-Mo alloys, Ti-SMo, Ti-10.9M0, Ti-13.1 M0, and Ti-20M0, of the a-B and B types. Materials and Fabrication—The high-purity base alloys, composed of iodide titanium and high-purity metals, were prepared by double arc melting under argon in a water-cooled copper crucible, using a water-cooled tungsten electrode. Radiographic examination showed homogeneous Ti-Mo alloys. The analyses of the alloys used in this investigation and their as-fabricated hydrogen content, where determined, are listed in Table I. The two commercial alloys were 1/2 and % in. diam bar stock. No analyses other than hydrogen content were made. In order to maintain the a-B relationship existing in the two commercial alloys, vacuum annealing and hydrogenation were carried out in the B field prior to final fabrication. Fabrication then was done by The three high-purity Ti-Mn alloys were forged to 3/4 in. diam rods at 1600°F, and hot swaged to 1/2 in. diam at 1380°F. Machined and degreased bar stock was vacuum annealed or hydrogenated, fabricated to 1/8 in. diam rod by hot swaging, annealed in argon for 1 hr at 1380°F !75O°C), and water quenched. The six yz lb Ti-Mo ingots were forged to Wi in. diam rods at 1600°F and then hot swaged to % in. diam. Machined and degreased specimens were vacuum annealed or hydrogenated in the /3 field, prior to fabrication, by swaging to Y4 in. rod at 1400°F. After fabrication, the 5 and 10.9 pct Mo alloys were annealed in argon for 16 hr at 1290°F and water quenched to give equiaxed a-B structures. The higher molybdenum content alloys were argon annealed 4 hr at 1470°F and water quenched to give all £ structures.

Jan 1, 1957

By J. T. Mackenzie

Henry Marion Howe, in whose memory we are gathered together, was one of the great thinkers who develop from time to time to whom is given the rare gift of synthesis. Analysis is given to few, but synthesis, the ability to show the relation of all parts to each other and thus to give a clear picture of the whole, is reserved for the very few. Analysis can be achieved by honesty, intelligence, and industry, but synthesis is only given to genius. Professor Howe's crowning achievement is the picture of the whole iron-carbon series shown in Fig. I, which places steel, malleable, gray iron, mottled and chilled irons in their proper relation to each other and shows the essential unity of the series. Perhaps his best statement of the case is found on page go of the Metallography of Steel and Cast Iron in these words: " Each member of the gray cast-iron series consists of the metallic matrix approximately equivalent to that member of the steel-white-cast-iron series to which it corresponds in percentage of combined carbon with its continuity broken up—by masses of graphite ..." Apparently he had taken considerable interest in this idea around the turn of the century, for he refers to a discussion at the Franklin Institute in I900 in which he said: "Though many others had probably conceived this relation between the steels and cast irons, it was here enunciated for the first time, so far as I know. It was received with great incredulity." The concept was explained in some detail in a paper on "The Constitution of Cast Iron" presented before the A.S.T.M. in 1902 when Professor Howe was retiring president of that young society. In the discussion Dr. Sauveur stated that he was "very well acquainted with Professor Howe's theory of the constitution of cast iron," and went on to say that while he "shared it to the fullest extent, some foundrymen . . . claim cast iron is a metal entirely different from steel . . . that steel and cast iron have very little in common, and that therefore the knowledge gained in the study of steel is of little or no value in the study of cast iron." Dr. Moldenke, in discussing the same paper, said he had been working on the same theory for 12 years but he laid no claim to publication. Discussing the difference in the micro-structure of the metallic matrix, Professor Howe pointed out that "such minor structural differences are indeed to be expected, because of the difference in the conditions under which these constituents are generated. "One difference in these conditions is that the steel of most micrographs has been either forged or at least treated thermally in such a way as to give a new structure radically different from that which formed during the initial solidification, whereas the cast irons have not. Hence what we see in the steels is a transformation structure, but in the cast irons a solidification structure. By giving the cast

Jan 1, 1944

By J. T. Mackenzie

Henry Marion Howe, in whose memory we are gathered together, was one of the great thinkers who develop from time to time to whom is given the rare gift of synthesis. Analysis is given to few, but synthesis, the ability to show the relation of all parts to each other and thus to give a clear picture of the whole, is reserved for the very few. Analysis can be achieved by honesty, intelligence, and industry, but synthesis is only given to genius. Professor Howe's crowning achievement is the picture of the whole iron-carbon series shown in Fig. I, which places steel, malleable, gray iron, mottled and chilled irons in their proper relation to each other and shows the essential unity of the series. Perhaps his best statement of the case is found on page go of the Metallography of Steel and Cast Iron in these words: " Each member of the gray cast-iron series consists of the metallic matrix approximately equivalent to that member of the steel-white-cast-iron series to which it corresponds in percentage of combined carbon with its continuity broken up—by masses of graphite ..." Apparently he had taken considerable interest in this idea around the turn of the century, for he refers to a discussion at the Franklin Institute in I900 in which he said: "Though many others had probably conceived this relation between the steels and cast irons, it was here enunciated for the first time, so far as I know. It was received with great incredulity." The concept was explained in some detail in a paper on "The Constitution of Cast Iron" presented before the A.S.T.M. in 1902 when Professor Howe was retiring president of that young society. In the discussion Dr. Sauveur stated that he was "very well acquainted with Professor Howe's theory of the constitution of cast iron," and went on to say that while he "shared it to the fullest extent, some foundrymen . . . claim cast iron is a metal entirely different from steel . . . that steel and cast iron have very little in common, and that therefore the knowledge gained in the study of steel is of little or no value in the study of cast iron." Dr. Moldenke, in discussing the same paper, said he had been working on the same theory for 12 years but he laid no claim to publication. Discussing the difference in the micro-structure of the metallic matrix, Professor Howe pointed out that "such minor structural differences are indeed to be expected, because of the difference in the conditions under which these constituents are generated. "One difference in these conditions is that the steel of most micrographs has been either forged or at least treated thermally in such a way as to give a new structure radically different from that which formed during the initial solidification, whereas the cast irons have not. Hence what we see in the steels is a transformation structure, but in the cast irons a solidification structure. By giving the cast

Jan 1, 1944