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By Wallace Thorneycroft

This paper by Mr. Thorneycroft, Past President of the Institution of Mining Engineers (Great Britain), and chairman of its Subsidence Committee, is a valuable contribution to the assemblage of data on ground movement and subsidence from coal mining. It deals with the effects of advancing longwall, a method almost universal in Europe but as yet little used in the United States outside of Northern Illinois and in a few scattered places elsewhere in thin coal beds, as in the Lexington field, Missouri. Canon City field, Colorado, and the Birmingham field, Alabama. Although by advancing lougwall, a maximum recovery of coal is obtained and it has to be employed where there are weak shale roofs, especially in deep mines, it is a more expensive method of operation unless the mining conditions are suitable, which is unusual in the United States. On the other hand, there is a growing use in this country of what is essentially retreating longwall, with an approximately straight break-line as described by Rayburn.1 With this method, in which the pillars are substantial, it was shown that the ground movement effect is practically identical with that of advancing longwall, hence the value to mining engineers of the precise data given by Mr. Thorneycroft. His study is unusual in several respects; it deals with conditions connected with the mining of a coal bed 20 in. thick, about 490 ft. below the surface, over a mined-out area in a 5-ft. bed about 90 ft. below, which had been mined about 12 years earlier. Both mines passed under Plean House, a building of massive cut stone construction built over a century ago, in which Mr. Thorneycroft resided throughout the under-mining period. Slight cracks opened in the walls as the longwall face approached the house in mining the upper seam, and closed after the face passed and subsidence took place. In the northwest wall, the last wall the face passed under, some stone blocks were broken, which was attributed to a strike period when the advance of face came nearly to a standstill. Other than this there was no perceptible permanent damage, as indicated by the photographs taken by the undersigned in 1923 (Figs. 1 and 2). Mr. Thorneycroft used a novel means of studying the successive positions of the corners of the building: he hung plumb bobs from the eaves and traced the paths of the respective plumb bob points on level surfaces. The angles made by the house walls with the plumb bob lines gave measures of the slope of the subsidence wave at the respective points. A slight upward wave was indicated by the surveys ahead of the subsidence, which would appear to be due to a tilting over of the massive sandstone stratum in the roof measures near the surface, the edge of the coal face acting as the fulcrum.

Jan 1, 1931

By M. E. Gershon

The development of long-term plans and schedules for strip mines now faces many companies, especially those developing large properties in the West. The rule of mining the lowest strip ratios first, while delaying equipment acquisitions and recouping investment the fastest, sometimes creates the situation where stripping ratios are too high in the latter years of mining operations. A program concept taking life of mine return on investment into account is developed in this paper to optimize mine scheduling and equipment acquisition. In addition, quality considerations (heat content, ash, sulfur, and washability) can be considered by including the appropriate blending constraints to meet contract requirements.

Jan 1, 1984

By Robert T. MacMillan

Of all the mineral substances utilized by man, salt or sodium chloride has one of the longest and most varied histories. Because all animal life is descended from marine organisms, sodium and chlorine became necessary to life, and as sodium chloride meets requirements most readily, common salt has been essential to human and animal diets from earliest times. As civilization progressed, man learned to evaporate sea water and brines of saline lakes and springs to obtain salt, and gradually ceased to depend on the flesh of animals and the occasional salt outcrops or "salt licks" they frequented. He also learned that salt had a multitude of uses, particularly as a preservative of meat and other foods. The importance of salt in the minds of early men may be readily seen from many allusions in the Bible and other ancient writings. Expressions such as "not worth his salt," and "the salt of the earth" are deeply embedded in the English language. Salt has symbolized friendship, fidelity, purity, and hospitality. It has been used as currency; had religious significance; caused wars; and has been a favorite commodity for taxation. The English word "salary" stems from the Latin word for salt, in which Roman soldiers received part of their pay. Although salt today retains its dietary importance, it has thousands of other uses. Of each 100 pounds produced in the United States less than three pounds is for table use. The other 97 pounds goes for agricultural, industrial, and chemical uses. Fortunately, reserves of salt are enormous and reasonably well distributed on the face of the earth. The sea is an inexhaustible source of salt which may be had at prices which vary with climate and other factors. In addition, large underground salt deposits and many salt lakes, springs and playas are scattered throughout the world. Most countries have access to a salt supply, although some are more favored than others. Properties Crystallized sodium chloride or common salt is known as halite. Its molecular weight is 58.454 and it contains, by weight, 39.34 pct sodium and 60.66 pct chlorine. Alternate positions in the cubic lattice are occupied, respectively, by negative chloride and positive sodium ions; the crystal form is isometric. Crystallization from water produces concentric shells, and when broken, a crystal shows conchoidal fracture. Salt has a hardness of 2.5; its specific gravity ranges from 2.1 to 2.6 for rock salt and is 2.165 for the pure crystal. The refractive index is 1.554; it melts at 800.8 ± 0.5°C and boils at 1413°C. Its heat of fusion is 123.59 cal/ gram. Salt is transparent or translucent and highly diathermous. It is colorless when pure and has a vitreous luster. Salt containing traces of iron oxides has varying shades of yellow, orange, brown, pink, or red. The peculiar shade of red sometimes found in that produced by solar evaporation of sea water has been attributed to tiny organisms. Blue mottlings sometimes seen in halite crystals have been attributed to colloidal sodium. Salt is soluble in water to the extent of 35.7 parts per 100 parts of water at 0°C and 39.8 parts per 100 of water at 100°C. The small difference in solubility with increasing temperature is important in the economics of producing salt by evaporating brine. Salt has a negative heat of solution which is 1.281 kg-cal/ mole at 18°C in 200 moles of water.

Jan 1, 1960

By D. H. Turner, F. A. Crossley

The titanium-rich corner of the system Ti-Al-Si has been studied to determine the phase relationships in the temperature interval 600° to 1200°C. Metallographic examination of long time isothermally annealed specimens was the means of investigation. PART of a program on phase relations and transformation processes of titanium alloy systems included the study of the titanium-rich corner of the Ti-Al-Si system. The investigation covered ternary compositions in the range 2 to 8 pet A1 and 0.1 to 2 pet Si and binary compositions in the range 0.2 to 2 pet Si. Temperatures were in the range of 600" to 1200°C. Alloys containing 6 pet A1-0.1 to 0.5 pet Si were investigated down to 400°C. Partial vertical sections are presented for 2, 4, 6, and 8 pet Al. The Ti-Si system has been reported by Hansen et al.' It is characterized by a eutectoid decomposition, ß = ± a + Ti3Si3, at 860°C. The maximum solubility of silicon in a is reported to be about 0.5 pet at the eutectoid temperature. The solubility of silicon in 0 increases from 0.9 pet at the eutectoid temperature to approximately 3 pet at the eutectic temperature, 1330°C. Several investigations in the composition range of interest have been reported for the Ti-A1 system."' These investigations are in agreement on the phase fields, but differ to small extents on boundary positions. However, very recent, and as yet unpublished, findings" " indicate that there are perhaps two phases which occur at lower aluminum contents than the ? (TiA1) phase, and that the solubility of aluminum in a titanium is less than 6 pet. In the present investigation phase relations found are in agreement with the published literature exemplified by the work of Bumps et al.3 Therefore, it is probable that the partial system reported herein is metastable and does not represent true equilibrium. Experimental Procedure High purity Bureau of Mines titanium sponge of 103 Bhn hardness, granulated aluminum shot of 99.7 pet purity, and silicon powder of 99.8 pet purity were used in making the alloys. For the work in the range from 600" to 1200°C, 100 g ingots were prepared by arc melting. Melting losses were negligible and spot checks by chemical analysis showed good agreement between nominal and analyzed results. Nominal compositions are used throughout this paper. Ingots were forged to 3/8 in. rounds and cut into specimens for heat treatment. Isothermal anneals in the range from 600" to 900°C were preceded by solution treatment at 1000°C for 1 hr, followed by furnace cooling to the annealing temperature. Samples were sealed in evacuated Vycor bulbs for heat treatments up to 1000°C. Higher temperature anneals were done with the samples sealed in quartz bulbs under a partial pressure of argon.

Jan 1, 1959

By Leo D. Jones

The use of the centrifuge for dewaxing lubricating oils grew out of the effort to secure better results than had been attained by the common "cold settling" process. This process was the only known method for dewaxing steam refined cylinder stock (600" F. fire test), the product known as "bright stock" being commonlyused for building up "pressed," i.e., dewaxed neutrals of, say, 200-sec. viscosity [to a higher value. The process consisted of mixing the cylinder stock with approximately one and one-half times its volume of naphtha, heating, to dissolve completely all the oil and wax and then slowly chilling to about 15" F. in large insulated tanks. This caused the wax to precipitate. It was allowed to settle out by gravity. The supernatant liquid was then drawn off and the naphtha distilled off, leaving a still residue of bright stock. The sediment from the settling, of a slushy nature, was withdrawn. After removing the naphtha by distillation the residue was petrolatum. At some point in the process, preferably after the dilution but before chilling, the mixture was decolored by percolation through fuller's earth. The finished bright stock produced by this process had a cold test of about 50" F. Efforts to improve this by chilling to a lower temperature resulted in a considerable reduction in yield, and increased uncertainty of settling. Even when chilling to 15" F. it was not uncommon to find that after a week's waiting a tank had not settled. It was then necessary to heat and rechill. This uncertainty was a serious problem; in one case a refinery superintendent had men riveters hold pneumatic hammers against the tank for hours, hoping thus to cause agglomeration and settling of the wax. Yields of bright stock above 70 per cent, were uncommon. History of Centrifugal Application It is not surprising, therefore, that many attempts were made to improve upon the results obtained by cold settling. George H. Taber, vice-president of the Gulf Refining Co., Pittsburgh, Pa., made a number

Jan 1, 1924

By C. D. Jardine, D. G. Patton

Rapidly increasing energy costs and more rigid customer quality requirements necessitate improved control of pelletizing processes. With the introduction of dedicated microprocessor-based controllers, sophisticated control strategies are now possible. An application of this technology at Carol Project has resulted in fuel savings, improved pellet quality, and standardization of operating procedures. This was accomplished with no production loss by using a "building block" approach to design and equipment selection.

Jan 1, 1985

By AIME AIME

S ULFURIC acid made in the United States during the last four years has averaged approximately 7,000,000 tons of 50" B6 acid a year. This is double the production of the year 1913. About 66 per cent of the acid is made from sulfur, 16 per cent from pyrite, 13 per cent at copper, lead, and zinc smelters, and the remainder from miscellaneous sources it her the chamber process or the contact process, (at some plants both) is used. In 1923, the contact process accounted for nearly 30 per cent of all the sulfuric acid made in this country and since then it has been increasingly employed. It was first introduced here in 1898, and has always .proved less expensive than the chamber process for the manufacture of .acid of high concentration and purity, but the latter produces acid of low strength suitable for many industries.

Jan 1, 1929

By L. R. Jackson, W. T. Lankford, K. F. Smith

ComMercial steel sheet is prepared by a combination of hot and cold rolling and annealing. This treatment usually results in more or less pronounced anisotropy. The anisotropy may manifest itself both as preferred orientation and in the manner in which impurities, segregations, and the like, are aligned in the sheet. The type of preferred orientation and the organization of impurities or segregations may affect the elastic moduli, the yield strength, the tensile strength, and almost always the amount of ductility in different directions. In any case, the most important directions concerned in the anisotropy are along the rolling direction, along the width direction, and along the thickness direction. Considerable data exist on the anisot-ropy of sheet steel as demonstrated by conventional tensile tests; however, few attempts have been made to measure the constants of plastic anisotropy and use them to describe the flow of anisotropic sheet under combined stresses. In this paper, evidence is presented indicating that plastic flow in anisotropic sheet can be described by the shear-strain energy flow theory provided that the anisotropy is properly taken into account. Materials Used in the Investigation Table I lists the sheet materials used in this investigation and describes the condition in which materials were tested. Direction, of Tests and Test Methods Two types of tests were run—tensile tests and hydraulic-bulge tests. Characteristic parameters of anisotropy were determined from the tension tests by methods which will be described later. In all cases, the tensile test pieces were cut from the same quarter line and adjacent to the bulge test pieces in the sheet in order to minimize

Jan 1, 1949

By E. L. Anderson, J. R. Long, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By J. R. Long, E. L. Anderson, R. S. Dean, F. S. Wartman

Titanium has been estimated to comprise about 0.65 per cent of the earth's crust and ranks fourth in abundance among the metallic elements suitable for engineering uses. In spite of this, applications of titanium for structural purposes have not as yet been developed. Its commercial exploitation has been largely confined to the chemical industries and the production of paints and pigments; no doubt because of the difficulties that lie in the way of preparing the pure ductile metal. Published reports, however, indicate that ductile titanium can be prepared and possesses some unique properties. This, together with the occurrence in this country of several important titaniferous deposits, has led the Bureau of Mines to investigate processes for the production of metallic titanium, methods required for its fabrication, and the properties that may be produced in this interesting metal. Methods of Preparing Metallic Titanium Many early investigators claimed to have isolated metallic titanium; but in the light of present knowledge, it seems that they really had produced various mixtures of carbides and nitrides that have a metallic appearance but are brittle, hard, and unworkable. The first metallic titanium pure enough to be malleable when cold was produced by Hunter1 in the early part of the twentieth century. Kroll,~ van Arkel,~ and Fast,4 subsequently confirmed the facts that pure titanium is a. ductile metal and that small amounts of impurities were responsible for previous reports of brittleness. When heated, titanium reacts chemically with various gases, such as hydrogen, oxygen and nitrogen; if the volume of gas thus absorbed is too great, the metal becomes brittle and unworkable. The principal difficulty in making ductile titanium is prevention of such contamination, and the success of a given process may be judged by the completeness with which it solves this difficulty in a practical manner. Of the gases mentioned, hydrogen is the least objectionable, since its absorption by the metal is completely reversible and, although dimensional changes occur and absorption of hydrogen embrittles the metal, the gas may be removed readily by heating in a high vacuum for a short time. On the other hand, the absorption of oxygen or nitrogen results in the formation of permanent solid solutions of the oxide and nitride, which cannot be decomposed by the strongest reducing agentsz with sufticient completeness to restore the inherent ductility of the metal. Because of

Jan 1, 1946

By W. B. Morrison

The principal factors influencing the total percent elongation of a lead-tin eutectic and several low-alloy steels which exhibit superplasticity were investigated. These factors are: a) Strain-rate sensitivity of the stress (m). b) Specimen geometry; in particular, diameter-to-length ratio (d0/l0), and surface irregularity (e.g. notches). A feature of the tensile deformation of a superplastic alloy is the early appearance of a neck which continues to extend throughout the test. As a result the total elongation is directly related to the diameter-to-gage-length ratio. The strain-rate sensitivity of the stress varies during extension, mainly because of microstruc-tural changes. A satisfactory correlation exists between the minimum strain-rate sensitivity and total elongation, as indicated in the equation shown below. Notches cause a considerable reduction in total elongation and their effect is greatest at high values of strain-rate sensitivity. An initial notch depth exists below which there is no appreciable effect on elongation. An equation relating elongation to strain-rate sensitivity and specimen geometry is proposed, THE total percent elongation of a tensile specimen is usually regarded as a measure of superplasticity. However, little attention has been given to the fact that total elongation is also a function of specimen diameter and gage length, even though the importance of geometry has long been recognized in the tensile testing of materials in which elongations are relatively small.* In the present study, the effect on superplas- tic extension of the ratio of specimen diameter to length was investigated and an analysis was made of strain distribution along the gage length. Superplastic alloys are characterized by having a flow stress sensitive to strain rate but relatively insensitive to strain.2"' In an earlier study,5 it was found that the strain-rate sensitivity of several low-alloy steels changed during the test and that the minimum value correlated best with total elongation. In the present study, the variation of strain-rate sensitivity during the straining of a lead-tin alloy was investigated. EXPERIMENTAL PROCEDURE Lead-tin eutectic alloy (32 pct Pb 68 pct Sn), made from high-purity lead and tin, was cast in the form of 1-in. diam rod. The rod was cold-rolled in stages to 0.25 in. diam and then swaged to 0.125 in. diam. Samples were cut from the rod at various stages of the mechanical working process. Tensile test specimens were then made by attaching threaded steel ends to the rods by an epoxy-base thermosetting adhesive which required a setting treatment of 2 days at room temperature. The rods were seated in the steel ends in holes approximately 0.01 in. oversize. The test pieces thus made were of various diameters and gage lengths. These were stored at a temperature of about -70°C (-94°F) until required for testing. The distribution of strain along the gage length of a specimen was determined at various stages of the tensile test. The lead-tin alloy was superplastic at room temperature and direct observations during testing were simple. The gage length was divided by reference marks into five initially equal units. These reference marks were made with ink and were reinforced during the test when the initial marks became faint. Photographs were taken, at intervals, of the deforming specimen and measurements of the elongation in each of the gage units were made on these photographs. Tests were also done on several superplastic low-alloy steels whose properties were described earlier.5 The chemical compositions of these steels are given in Table I. A diagram of the notched tensile specimen used in the steel tests is shown in Fig. 1. The specimens were tested at 900°C (1650°F) in a furnace through which a mixture of He + 2 pct H was continuously circulated.5 RESULTS Strain Distribution. Approximately 20 tests on lead-tin alloy specimens were conducted to determine the strain distribution during the test. An example is shown in Fig. 2 of the strain distribution in the gage

Jan 1, 1969

By Wm. J. Wright

RECORDS of crude oil in India date back for nearly 100 years, and modest attempts were made to develop the oilfields of Assam about 75 years ago. We have no record of production until 1892 when the fields near Digboi, Assam, yielded about 700 bbl. Since that time, the production of the Digboi fields has increased slowly, but steadily, and new fields have been opened at Badarpur, in Assam, and Khaur, in the Punjab, until the production in India in 1918 was about 293,700 bbl. and the possible production at the present time is approximately 300,000 bbl. per year. In the meantime, the English oil companies in India have been slowly adding to their holdings until they have taken up practically all of the promising territory that is readily accessible, and only about one-tenth of their properties has been touched by the drill. All the producing oilfields of India, and as far as we know all the prospective fields, are confined to areas underlain by rocks of Tertiary age. These rocks consist of more than 20,000 ft. of dark sandstones and shales, with the Nummulitic (Eocene) limestone at the base. In parts of Assam, the lower measures contain economic deposits of bituminous coal. In the Punjab, the upper part contains thick beds of conglomerate. Visible organic remains are rare; except in the limestone and the coal measures. In general, the hardness of the measures increases from top to bottom, but there is an alternation of relatively hard and soft beds throughout the whole series. The rocks are everywhere folded and, in some instances, severely faulted. The crests of eroded anticlines usually stand up as ranges of hills in which the individual ridges are underlain by the relatively' hard beds. Thus structural features are suggested and often clearly defined on the topographic maps.

Jan 3, 1924

By C. Norman Cochran

The pllnse diagvam for the NaF-AlF3 system was used to calcutate an ionic model for the NaF-AlF3 system. Assuming an ideal solution,a series of simultaneous equations expressing equilibria be-tween solid and liquid phases at the euleclic, perilec-tic, and melting points were solved for the activities of the ionic species, the dissociation constants, and the entropies and heats of fusion. The calculations suggest the existence of A13F1415 ions in addition to the F-1+AlF6-3 , and AlF4-4 ions previously proposed by others. The calculaled valnes give better agreement with vapor pressures than the previous model without Al3Fl14-5. Additional possible vefinements of the model are proposed. CRYOSCOPIC1 investigations and density data2 for the NaF-A1F3 system have previously been used to study the dissociation mechanism of Na3A1F6 and to derive equilibrium constants for its dissociation to NaF and NaAlF,. Depending primarily on the heat of fusion assumed for cryolite, the dissociation constants ranged between 0.02 and 0.18 from cryoscopic studies, and from 0.09 at 1273°K to 0.16 at 1363°K from density data. In most cases the values were unable to reproduce satisfactorily the experimental liquidus lines very far on the A1F3 side of the Na3A1Fe composition. This suggested the existence of at least one other ionized compound in the melt besides NaA1F4 in the Na3A1F6-A1F3 side of the system. This is assumed to be liquid Na&13F14 (chiolite), which is already established as a stable solid in phase studies of this system. MODEL FOR THE MELT The melt is assumed to be an ideal solution with ion activities equal to anion fractions. The only cation in the model is sodium so that Temkin and simple anionic activities are identical. Although the compounds are completely ionized to Na' and the respective anion in the melt, molecular rather than ionic notation is used throughout this work. The Na3A1Fe is assumed to dissociate to NaA1F4 and NaF as in the former model, and Na&13F14 to dissociate to Na3A1Fe and NaA1F4. Other valid dissociation equilibria can be written involving these four compounds, but all of these can be obtained by combinations of the two described dissociation reactions and, thus, are automatically considered in these calculations. The model allows for no free AlF3 so that compositions for NAIF3 > 0.5 (mole fraction A1F3 on the NaF-A1F3 basis) cannot be treated. The question of the existence of free AlF3 in the melt will be discussed again later. The constants in the model were evaluated from points along the entire known liquidus line of the NaF-A1F3 system. Previous work employed only the liquidus line or densi- ties near the Na3A1F, composition. The liquidus line compositions used in the solution of the model are from unpublished work by Mr. P. A. Foster, Jr., for compositions between the Na3A1F6 melting point and the Na&13F14-A1F3 eutectic, and from the published works of Grjotheim,1 Phillips,3 and Foster4 for the remainder of the system. The relationships used in solving for the desired dissociation constants and heats and entropies of fusion are listed in Table I, and the points along the liquidus line at which each apply are indicated to the right of the relationships. The mole fractions of each of the separate species in the melt are symbolized by N. Relationships [I] and [2] are the respective dissocia-ation constants, Kl and K2, of Na3AIF6 and Na5A13F14 for this model. For simplicity, these constants will be assumed to be independent of temperature. Relationship [3] follows from the assumption of the ideal solution. The expression relating the values of N to the experimental values of NAIf3, is given in Relationship (41. Relationships [5], [6], and [7] each state the equilibrium between a compound in the melt and its pure solid phase for the portion of the liquidus lines where it precipitates. The heats of melting, AH,, and entropies of melting, AS,, used in [5], [6], and [7] are assumed to be independent of temperature. The compositions and temperatures of all five invariant points (two melting points, two eutectics, and one peritectic) along the liquidus lines from NAIF3 = 0 to NAIF3 = 0.5 were employed in the solution. The eutectic and peritectic compositions were particularly useful because each of these is involved in one more equation than other points along the liquidus lines and thus reduces the number of points required to solve for the constants. Also, their use assures that the inflection points in the derived liquidus line will correspond exactly with those on the experimental liquidus line. The total number of equations is 5k1 — 1, where n is the number of experimental composition points used. The number of unknowns is 4n + 5 (4n- 3 values of N, 3 values each of AH, and AS,, and 2 values of K). Thus, six points must be used in the solution to obtain an equal number of equations and unknowns. The one additional required experimental composition was taken on the liquidus line between the Na3A1Fe melting point and the Na3A1F6-Na5A13F14 peritectic. Previous work indicated this was a difficult portion of the curve to fit. The temperature used for the point was 1161°K, the same as for the NaF-Na3A1Fe eutectic. This choice of temperature gave two points with identical NNa3AIF6 values which simplifies the algebraic solution. The second point at this temperature is denoted 1161°'K. PROCEDURE FOR SOLUTION OF EQUATIONS Values were assumed for NNa,AIF and NNaF at the NaF-Na3A1F6 eutectic at 1161°k. By an iterative procedure, the corresponding values for NNa5A13F14 and NNaAlF4 at 1161°K were determined from 131 and 141. A value was assumed for NNaAlF4 at 1161°'K and

Jan 1, 1968

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10'1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.' only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

By W. L. Phillips

Aluminum and copper single crystals were strained in shear, unloaded and rotated 60, 120, and 180 deg. The magnitude of the Bauschinger strain increased rapidly during the easy glide region and became constant as the easy glide limit was reached. An increment in stress was not required to continue slip in any close-packed plane or in the reverse direction during easy glide. A qualitative theory is proposed to explain the present results. FOLLOWING the initial work on tin by Bausch,' there have been several investigatorsB7 who have employed the shear test to study the deformation of aluminum. In all cases the shear technique was employed in an attempt to obtain a more homogeneous shear than in the conventional tension test The direct shear technique has the obvious advantage, relative to the tension test, that a crystal may be stressed in any predetermined plane and direction, including the reversal of strain sense. In the present investigation the shear technique was employed with aluminum and copper single crystals and their behavior was studied with respect to deformation in all close-packed directions in the octahedral plane. In contrast to previous investigations, the shear technique was used in an attempt to obtain a stress-strain curve in shear which is identical with the corresponding tension curve and then to use the additional degree of freedom of the shear test to study the mechanical behavior of crystals in all close-packed directions in the octahedral plane. PREPARATION OF CRYSTALS Single crystals 1/2 in. in diam and 6 to 7 in. long, were prepared from aluminum containing 0.001 pct Si, 0.001 pct Fe, and 0.001 pct Zn, by spectro-graphic ana1ysis and from OFHC copper. Crystals were grown from the melt in graphite at a rate of 1 5 in. per hr. The copper crystals were grown under an argon atmosphere. No lineage structure was observed in Laue patterns, though small angle boundaries were present in the crystals. The aluminum and copper crystals were annealed at 640" and 900°C, respectively, for 24 hr and furnace-

Jan 1, 1962

By Benjamin Lustman, Robert F. Mehl

THE study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation-i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from o to 1000-2000 Angstroms-has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difference may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations. 3,4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 EXPERIMENTAL PROCEDURE Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and reproducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900º to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal.

Jan 1, 1941

By T. A. Wright

THE-Institute of Metals Division opened on Tuesday afternoon with Wheeler P. Davey as chairman and G. E. Edmunds as vice-chairman. Four papers were on the program, two being of a fundamental character. A paper on "Internal Surface in Minerals and Metals," by R. S. Dean and J. Roster, was presented by the latter; C. H. Gottschalk discussed coercive forces in powders. In answer to a question by the chairman. The author stated that he had not investigated [he temperature coefficient of resistance. A paper on "Recrystallization and Grain Growth in Cold Worked Polycrystalline Metals," by L. W. Eastwood, Arthur E. Bousu, 'and C. T. Eddy, was presented by Mr. Eastwood. A. great many quantitative data were given, with little reference to the theory. Theoretical considerations were discussed by Dr. Gottschalk, and C. A. Edwards of the University College of Wales, contributed very interesting comment on the relationship of size and critical strain. Dr. Edwards discussed the necessity of considering strain with time and temperature.

Jan 1, 1935

By W. J. Shearer

A COMPARISON of statistics relating to coal min-ing in Great Britain and the United States leads one to suspect widely differing conditions and practice. A brief review of some of the conditions may enable American mining men to appreciate more fully the difficulties with which British engineers are faced, and to some extent explain why American, coal can be sold f.o.b. mine at the present time at about 50 to 60 per cent of the cost of British coal at the mine, and why British man-shift outputs fall far below American at present being less than 30 per cent. Bulman gives the average depth of 6-ft. seams. in Britain at 1350 ft., and of 2-ft. seams at 517 ft. George S. Rice states that 90 per cent of American coal 'is taken from less than 600 ft. Much English coal is taken below 2000 ft. and some below 3000 ft. The total influence of depth on cost is not always evident. Room work as known in America becomes less advisable with increasing depth, as pillars crush badly if left -for any length of time. A limited amount of bord and pillar work, taking very small amounts of coal in the first working, takes the place of room work, with rapid working of the pillars as soon as the panels are broken. Ventilation difficulties increase tremendously with depth and thinning coal. In America the chief use of air underground is to dilute gas. In Britain it serves a dual purpose, in many cases the amount of air cir-culated being far in excess of the quantity necessary to dilute gas to reasonable proportions. At great .depths rock temperatures exceed-95 deg. F., and great volumes of air are necessary for rock cooling. At these high temperatures humidity becomes an important factor. At present a great deal of research is under way to find methods of overcoming the troubles experienced with high temperature and humidity in deep mines.

Jan 8, 1928

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By P. A. Laxen, H. R. Spedden

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.'*' Study of the adsorption of sodium from an aqueous solution oftheon quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained."." Three main factors which appeared likely to affect the adsorption of sodium are: l—concentration of sodium in the solution, 2—concentration of onotherof cations in the solution, and 3—anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in thesethe amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxyl-ion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory' except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying." To minimize the laborious preparation of quartz, experiments were made to determine .whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na" activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot 11) and 2000 (lot 111) as determined by the Bloecher method." Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.' It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß+ radiation and a 1.30 mev r radiation. The decay scheme is illustrated in the following equation: ß+ NaR-------'8'77NeZ2 3 years The /3 radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang.R The original active material was 1 ml of solution containing 1 millicurie of Na" as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen." In brief, it included the following steps: 1—Ascertainment of linearity between concentration of Na" and activity measured. 2—Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3—Taking precautions to avoid evaporation of water during centrifuging

Jan 1, 1953