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By John Mathews

IT is a great honor to be asked by. the Board of Directors of this Institute to deliver the Henry Marion Howe lecture. The invitation carries with it a great responsibility, which I accept with considerable hesitation and with a feeling of unworthiness to perform the duties expected of me in this hour devoted to the memory of the life, character, and work of the late Professor Howe. Many of you recall the scholarly address delivered here a year ago by Prof. Albert Sauveur, and the beautiful tribute he paid-to his friend and colleague of many years in the great work of changing the art of iron making into the science of iron. My association with Professor Howe, was of brief duration-only one year-and the relation was that of pupil to teacher. My feeling toward him in later years was always that of a humble disciple at the feet of a master. He attained his third academic degree in the year that I was born. I recall the pride I felt when, after entering the, steel industry, I received from him, from time to time, letters asking for information or, perchance, asking my opinion, and he was always most punctilious in acknowledging the source of such bits of information in his writings. It was also my good fortune to sit at the feet of another great teacher-Sir William Roberts-Austen, at the Royal School of Mines. I mention him because his name was used by Osmond in coining the word "austenite," which is the subject of this address, and Osmond's suggestion was heartily approved by Howe. These three international metallurgists were the best of friends and delighted to honor the achievements of one another. There are other reasons for mentioning Roberts-Austen at this time. It was an introduction from Howe that opened to me the door of his -laboratory as well as of his heart. It was while at Roberts-Austen's laboratory that I .worked side by side with William Campbell

Jan 4, 1925

By John A. Mathews

It is a great honor to be asked by the Board of Directors of this Institute to deliver the Henry Marion Howe lecture. The invitation carries with it a great responsibility, which I accept with considerable hesitation and with a feeling of unworthiness to perform the duties expected of me in this hour devoted to the memory of the life, character, and work of the late Professor Howe. Many of you recall the scholarly address delivered here a year ago by Prof. Albert Sauveur, and the beautiful tribute he paid to his friend and colleague of many years in the great work of changing the art of iron making into the science of iron. My association with Professor Howe was of brief duration—only one year—and the relation was that of pupil to teacher. My feeling toward him in later years was always that of a humble disciple at the feet of a master. He attained his third academic degree in the year that I was born. I recall the pride I felt when, after entering the steel industry, I received from him, from time to time, letters asking for information or, perchance, asking my opinion, and he was always most punctilious in acknowledging the source of such bits of information in his writings. It was also my good fortune to sit at the feet of another great teacher— Sir William Roberts-Austen, at the Royal School of Mines. I mention him because his name was used by Osmond in coining the word "aus-tenite," which is the subject of this address, and Osmond's suggestion was heartily approved by Howe. These three international metallurgists were the best of friends and delighted to honor the achievements of one another. There are other reasons for mentioning Roberts-Austen at this time. It was an introduction from Howe that opened to me the door of his laboratory as well as of his heart. It was while at Roberts-Austen's laboratory that I worked side by side with William Campbell

Jan 1, 1925

By D. R. Mitchell

MEETING for the thirteenth time in New York as part of the five-ring circus known as the Annual Meeting A.I.M.E., the Coal Division experienced a wartime boom in attendance. Technical sessions were crowded and whereas 65 seats were set up for the annual luncheon meeting of the Division over 100 members showed up, many of whom had to be fed elsewhere. Possibly the Coal Division should adopt "13" as its lucky number. Discussions at technical sessions, formal and informal, were lively. Those papers containing material directly concerned with the war, or containing information that might be usable for war industries, were enthusiastically received. Some criticism was made in regard to the present method of handling discussions and it was suggested that better success would be had in getting discussions in the record by the use of hired reporters. This is being considered by the executive committee of the Coal Division.

Jan 1, 1943

By Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By R. R. Sayers

VENTILATION may be defined as the process by which vitiated air of an inclosed or partly inclosed space is continuously replaced by fresh air. Fresh air has been defined as invigorating pure air. Pure dry air at sea level contains the following gases:1 Analysis of Air at Sea Level PER CENT. Oxygen 20.94 Nitrogen 78.09 Carbon dioxide 0.03 Argon 0.94 Helium, krypton, neon, xenon, hydrogen, hydrogen peroxid, ammonia, ozone traces CARBON DIOXIDE LIMIT For many years carbon dioxide was used as an index of the purity of the air vitiated by the metabolism of people. It was, however, well known that the untoward effects produced on those exposed to such air was not due to the concentration of the carbon dioxide. It has been found that the untoward effects on the comfort and efficiency of those so exposed are due to the increased temperature and humidity. It has been found that men can breathe air containing many times the amount of carbon dioxide found in our worst ventilated theaters and assembly halls, which, according to Rosenau, do not contain above 0.5 per cent. carbon dioxide.

Jan 7, 1926

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

US 4,135,913-Extraction of nickel values from iron-containing nickel sulfide ore, particularly pentlandite or nickeliferous pyrrhotite A mixture of raw ore, roasted ore, or iron powder, and coal as a reductant is heated to a temperature of 800- 1000° C in a nonoxidizing atmosphere to convert the bulk of the iron content to metallic iron while diffusing into the iron the bulk of the nickel, the mixture cooled, and the cool material separated into a magnetic fraction containing most of the nickel and a non-magnetic gangue fraction A Illis arid L S Renzoni, assigned to International Nickel Co, Inc Jan 23, 1979 7 pp (75-21) Filed 10-10-75 (621,343) Priority Canada, 10-27-72 (155,032) Same Canadian 981,910, dated Jan 20, 1976 Same British 1,389,145, dated Apr 3, 1975 US 4,135,917-In the recovery of gallium from a solution obtained by the digestion of bauxite or nepheline in an alkali solution for the production of alumina, the digestion solution is neutralized, the neutralized solution evaporated to an op¬timum caustic alkali concentration and adjusted to a ratio of alkali metal oxide to alumina of above 2, the corrected solu¬tion contacted with a gallium-aluminum alloy, arid high-purity gallium recovered from the solution by electrolysis or cemen¬tation K A Badaliants, et al Jan 23, 1979 6 pp (75-109) Filed 12-19-77 (862,201) Priority USSR, 12-22-76 (2,428,¬006) US 4,135,918-Extraction of copper from copper sulfide ore containing also one or more of the metals iron, nickel, arid cobalt Ore is roasted at a temperature of 750-800° C to expel sulfur, the sulfur-free calcine slurried in water containing a sufficient amount of sulfuric acid to supplement any sulfuric acid formed in situ, the slurry heated at 150-165° C in the presence of a reducing gas to form soluble sulfates of metals other than copper while reducing copper to elemental form, arid the slurry filtered to recover copper solids Any precious metals present in the ore will report with the copper solids V A Ettel, A P Devuyst, R Sridhar, arid C. E O'Neill, as¬signed to International Nickel Co, Inc Jan 23, 1979 5 pp (75-117) Filed 3-2-78 (882,610) Priority Canada, 5-13-77 (278,360)

Jan 1, 1980

The income of the Institute is derived from dues, subscriptions to MINING AND METALLURGY and sale of publications. These sources are fortunately supplemented by the interest from invested funds now amounting to over $500,000, a considerable portion constituting endowments for especial purposes. Aside from the medal funds the principal endowments are the James Douglas Fund for support of the Library, the Rocky Mountain Fund and the Seeley W. Mudd Memorial Fund. The income from the two last named is available for the support of research and a variety of other purposes. It is allocated by the Board of Directors upon recommendation of standing committees in each case. An active effort is being made to increase the endowments of the Institute, it being felt that unusual opportunities exist for research and public and professional service through the organization.

Jan 1, 1936

By Charles D. Walcott

The following acts of the Directors are reported for the information of members At a meeting held June 20, 1907, Dr. Charles D. Walcott, Director of the U. S. Geological Survey, Washington, D. C., having been recommended by unanimous vote of the Council, was unanimously elected an Honorary Member of the American Institute of Mining Engineers, in recognition of his personal services to American geology, and of his generous co-operation with this Institute, to the Transactions of which he has not only himself made valuable contributions, but has also encouraged the preparation of such contributions by the members of the U. S. Geological Survey under his charge, his liberal policy in this respect having gone so far as to permit the preliminary publication by the Institute of important results reached by the geologists of that Survey, even before their final and full publication as public documents. This wise and generous course has not only brought the U. S. Geological Survey into intimate and sympathetic relations with the mining industry of the world, but has also enriched the Transactions of the Institute, especially in the department of the science of ore-deposits, with many valuable papers. At a meeting held Jan. 14, 1908, Mr. Charles Kirchhoff was unanimously re-elected a Trustee of the United Engineering Society, to serve for a second term of three years. At a meeting held Feb. 18, 1908, directly after the adjournment of the annual meeting of the Institute, the following officers were elected for the ensuing year: President, James Gayley: Vice-President, James Douglas; Secretary, R. W. Raymond; Treasurer, Frank Lyman.

Mar 1, 1908

By M. A. Selim, W. H. Somerton

Thermal expansions and heats of reaction of three typical sandstones were measured in the temperature range of 25°to 1,000°C. The significance of these data in subsurface heat-transfer calculations is discussed. Linear thermal expansions were measured both parallel and perpendicular to the bedding planes. Volume expansions are reported as the perpendicular expansion plus two times the parallel expansion. Expansion behavior of the sandstones was found to be controlled by the expansion characteristics of the quartz content. Differential expansion of the quartz grains and other minerals included in the sandstones caused permanent deformation of the heated samples after they were cooled to room temperature. Structural damage resulting from heating is probably an important cause of the reduction of thermal conductivity of heated samples. Measurements of heats of reaction were based on the known heat required for a- quartz inversion. Thermal reactions, which probably include deby-droxylation of clay minerals and decomposition of carbonate minerals contained within the samples, were found to require more than one-fourth of the amount of heat necessary to raise the temperature of the rock alone. In shales and limestones, the reaction heat could be substantially greater than that required from specific heat considerations alone. INTRODUCTION In earlier work, l-3 methods of measuring thermal properties were developed and thermal data for several sedimentary-rock types were reported. Data included thermal conductivity, specific heat and thermal diffusivity. In addition, calculations of heat transfer in subsurface formations may require data on the thermal-expansion characteristics of rock and the heats of reaction of mineral constituents. Thermal expansion of rocks is relatively small in magnitucle and, from the standpoint of change in bulk density, has only minor effects on heat-transfer cliaracteristics. Thermal-expansion behavior, however, may have significant effects on the structure of rocks. Differential expansion of different minerals and along different crystal-lographic axes may result in structural damage which could effectively reduce the thermal conductivity of the rock. Many mineral constituents of sedimentary rocks undergo phase or related changes when heated to sufficiently high temperatures. Although some of these reactions (such as the a-ß quartz inversion) are reversible and the heat absorbed is returned to the system upon cooling, many of the major reactions are irreversible. Through certain temperature ranges, the additional heat energy required to complete the reactions may be nearly as great as that necessary to raise the temperature of the rock in the absence of thermal reactions. If the heat requirements for these reactions are not considered, serious errors in heat-transfer calculations may result. Thermal-tzxpansion and thermal-reaction data have been obtained for three typical sandstones. Methods of measurement and results obtained are reported and discussed in the following. THERMAL EXPANSION OF SANDSTONES The linear expansions of three outcrop sandstones (Bandera, Berea and Boise) have been measured in the temptbratue range of 25° to 1,000° C. Expansion measurements were made in the directions parallel and perpendicular to the bedding. The differential expansion apparatus used is that described by Mitoff and Pask.4 The test sample is heated in an electric furnace with a temperature rise of 6°C/minute. The lengthening of the samples upon heating is compared with the small and known expansion of a fused silica rod. The change in length is transmitted to an X-Y recorder by means of a Statham transducer. A maximum error of ± 1.5 per cent has been obtained with this apparatus

Jan 1, 1961

By Paul Merica

ONE of the most useful, and at the same time least commonly used, methods of thermal analysis for the determination of transformations in metals and alloys consists in the recording of the tune intervals required for successive increments of temperature change during heating or cooling, the temperature of the furnace containing the specimen being altered at a uniform rate. The curve obtained by plotting these time intervals as a function of the mean temperature of the specimen during the interval is called the inverse-rate curve. It is probably due to the fact that no simple and convenient method has apparently been available for the measurement of the successive time intervals that this method has not been so generally used as, for example, the differential method, for which several tykes of automatic or semi-automatic apparatus have been designed. Whenever this method has been used, the intervals have usually been measured with the use of a chronograph; its operation as practised at the Bureau of Standards' is as follows: The temperature of the specimen is measured by a thermocouple and a dial potentiometer. The operator sets the potentiometer at successive values of the electromotive force differing by equal increments, usually 0.02 millivolt, and records the exact instant on the chronograph, by pressing a contact key, at which the galvanometer coil passes through its null position. Two-second intervals are also recorded on the chronograph record, and the number of 'seconds elapsing between successive signals is afterward counted from the record and plotted as a function of the electromotive force or of the temperature. This is an admirable method and by it most minute thermal arrests may be detected, but it requires a good chronograph, which is generally difficult to obtain, and the time of one operator during the recording and, subsequently, to read the intervals from the record; the latter operation often takes from one to two hours.

Jan 7, 1919

By Eckley B. Coxe

I wish to call the attention of the Institute to a peculiar variety of anthracite which occurs in the Buck Mountain vein at our collieries at Drifton, and in the same and other veins in different localities in the anthracite coal-fields. It is known among the workmen as iron-gray or cast-iron. It has a dull, greasy appearance, as if a piece of ordinary anthracite had been rubbed with a dirty and greasy rag and allowed to dry. It was formerly considered a very impure coal containing a high percentage of ash, and was picked out of the coal and thrown away. But the following analysis of it and of its ash, made by Mr. J. Blodget Britton, of Philadelphia, shows that such is not the case, the percentage of ash not being much higher than that of the ordinary anthracites as they are prepared for market. ANALYSIS OF COAL. Water,.........4.36 Fixed carbon, by difference,.. 84.90 Volatile combustible matter,. . 3 48 Ash,..........7.26 100.00 The carbon proved to some extent to be of the nature of graphite, and slowly combustible. ANALYSIS OF ASH. Silica,.........25.66 Sulphur,........ .17 Alumina,........27.03 Phosphoric acid,.......21 Ferric oxide,.......42.83 Alkali, undetermined matter and Lime,.........1.56 loss,.........60 Magnesia,........1.83 Manganous oxide,......11 100.00 We recently collected a quantity of the substance and made a fire with it, in an ordinary stove, which was kept up several days. We found that it burned with intense heat, and apparently as freely as our other coal does. Mr. Britton is probably right in his view, that the difference in appearance is not due to impurities in the coal, but to the fact that the carbon is in a more or less graphitic form, as many of the standard coals are no purer. I bring this before the Institute as I know that a large quantity of this valuable fuel is thrown away every year, on account of its supposed impurities.

Jan 1, 1879

Bill S.1431 for the creation of a Department of Natural Resources has received a propitious hearing before the Senate Committee on Government Operations. Interior Secretary Rogers C. B. Morton was one of the prominent witnesses who testified in favor. The department had been proposed, Morton said, with "the conviction that the development of all natural resources would be harmonized with the most practicable possible means to protect and preserve the environment, consistent with the social and economic needs of the Nation." Another opinion on the pro side came from Atomic Energy Commissioner Clarence E. Larson, who said that a "total picture" had become essential to the establishment of a policy for developing energy resources in the best public interest. Commissioner James T. Ramey, on the other hand, was one of the AEC dissenters. Ramey said he believed the reorganization of resource responsibilities would hinder efforts to deal with energy-environmental problems and prevent the use of AEC "expertise and facilities" to the greatest advantage. As Arnold Weber, associated director of the Office of Management and Budget, pointed out, however, retiring AEC Chairman Glenn T. Seaborg is in favor of the new department. Another supporter, and one who can cast a vote on the bill, is Sen. Frank E. Moss. Final Standards for emissions from new stationary sources will be published by the Environmental Protection Agency on October 27. The initial proposals, appearing in the Federal Register on August 17, called for limiting emissions per million Btu of heat input (maximum 2-hr average) to 0.2 lb of particulate matter, and, where solid fuel is burned, to 1.2 lb of sulfur dioxide and 0.7 lb of nitrogen dioxide. While the new rules are mainly for new plants, the EPA is also proposing them for "existing plants which are modified in such a way as to increase or alter. . . their emissions."

Jan 1, 1971

By J. Gordon Parr, L. P. Srivastava

DUWEZ1 has shown that pure titanium and pure zirconium transform martensitically during rapid cooling at temperatures about 30° and 15°C re spectively below their To temperatures. Holden et al.2 determined M, temperatures of Ti-Cu alloys by a metallographic technique applied to isothermally treated samples. Their results, superposed on the McQuillan3 version of the partial Ti-Cu diagram are shown in Fig. 1. Sources of metals were: Titanium: Iodide bar; Foote Mineral Co. Ltd. Zirconium: Iodide bar; Foote Mineral Co. LM. Copper: Spectrographic Standard; Johnson Matthey and Co. Ltd. Alloys were prepared by levitation melting under argon to the following nominal compositions:* 0.5, Quenching, at rates to about 8000°C per sec, was performed by cooling in a stream of helium (99.999 pct pure) a 3/64 in. cube of material previously heated by a tungsten coil in a system operating at. 10-5 mm Hg. Cooling rates below 200°C per sec w were obtained by controlling the current to the heater coil. The specimen was supported on a 32 gage Pt, Pt-Rh thermocouple attached through a DC amplifier to an Edin magnetic oscillograph (Model 8082) with a maximum chart speed of 250 mm per sec. Transformation temperatures were read off the oscillograph charts at the location of the beginning of the thermal arrest. The same specimen was quenched several times, and all runs were repeated on new samples. Regular calibrations of the oscillograph against a potentiometer were made between quenching experiments. The criterion of martensite formation was the effect of surface rumpling. Previously polished samples that showed a rumpled surface after transformation are assumed to have undergone martens itic transformation: transformations of a diffusion type produce no surface disturbance, Figs. 2 and 3. Electrochemical measurements were made in a cell described elsewhere4 whose electrodes were the martensitic and the diffusion-transformed materials in the following electrolytes:

Jan 1, 1962

By J. B. Mackintosh

THE present note is intended as an addition to my previous communication on the volumetric determination of manganese, read at the Roanoke meeting," it having been suggested that the circumstances under which my experiments had been conducted, were essentially different from those met with in the analysis of irons. The method used in these experiments is the same in all its details as that described in the paper referred to. I have made seven experiments in all: two of these were in duplicate on half a gramme of a sample of spiegel dissolved in hydrochloric acid; one was on the same amount of spiegel with the addition of 25 C.C. of a standard solution of potassium permanganate; one was on the same amount of spiegel with the addition of 35 C.C. permanganate and much organic matter, viz., one drop of castor-oil, two or three drops of coal-tar benzol arid of gasolene (petroleum), about ten of alcohol, portions of starch and of sugar about the size of a small pea, and about half an inch of a common match cut into shavings. This organic matter was added to the manganese solution after the hydrochloric acid had been replaced by nitric, and the solution was heated until the wood-shavings had disappeared. The fifth experiment was made by dissolving half a gramme of spiegel alone in nitric acid; the sixth by dissolving half a gramme of spiegel in nitric acid with the addition of 25 C.C. potassium permanganate, some oxalic acid, half an inch of a match, one filter-paper 7 cm. in diameter, and two drops each of castor-oil and turpentine; and the seventh experiment by dissolving half a gramme of spiegel in hydrochloric acid and adding 35 C.C. permanganate, without however taking the precaution to evaporate off all the excess of hydrochloric acid. Under these circumstances, one would expect that if organic matter exercises any influence on the determination, it would be plainly evident in the results obtained. But the accompanying table of results

Jan 1, 1885

By Paul D. Merica

One of the most useful, and at the same time least commonly used, methods of thermal analysis for the determination of transformations in metals and alloys consists in the recording of the time intervals required for successive increments of temperature change during heating or cooling, the temperature of the furnace containing the specimen being altered at a uniform rate. The curve obtained by plotting these time intervals as a function of the mean temperature of the specimen durnig the interval is called the inverse-rate curve. It is probably due to the fact that no simple and convenient method has apparently been available for the measurement of the successive time intervals that this method has not been so generally used as, for example, the differential method, for which several types of automatic or semi-automatic apparatus have been designed. Whenever this method has been used, the intervals have usually been measured with the use of a chronograph; its operation as practised at the Bureau of Standards1 is as follows: The temperature of the specimen is measured by a thermocouple and a dial potentiometer. The operator sets the potentiometer at successive values of the electromotive force differing by equal increments, usually 0.02 millivolt, and records the exact instant on the chronograph, by pressing a contact key, at which the galvanometer coil passes through its null position. Two-second intervals are also recorded on the chronograph record, and the number of seconds elapsing between successive signals is afterward counted from the record and plotted as a function of the electromotive force or of the temperature. This is an admirable method and by it most minute thermal arrests may be detected, but it requires a good chronograph, which is generally difficult to obtain, and the time of one operator during the recording and, subsequently, to read the intervals from the record; the latter operation often takes from one to two hours. There is here suggested a simple, convenient, and, it is believed, equally accurate method of recording the successive time intervals, by which the

Jan 1, 1921

By L. T. Larson

The spectral reflectivity of zirconium in light of 441 to 668 nanometers (nm) wavelengths and air immersion has been determined. Bireflectance and apparent-angle -of-rotation measurements show zirconium to be optically isotropic when examined in light of approximately 484 nm wavelength. There is a direct relationship between bireflectance and the tilt of the basal pole of zirconium from the surface normal. This relationship allows the determination of the spatial orientation of the basal pole of an individual single crystal within a coarse-grained poly crystalline section to within± 2 to 3 deg for angles of basal pole tilt from 0 to 90 deg. In recent years considerable attention has been given to the quantitative determination of optical properties of opaque minerals by use of vertically incident, plane-polarized light. In particular, Cameron' and Cameron et a1.2 have developed criteria for the identification of a large number of anisotropic ore minerals based upon measurement of the apparent angle of rotation and the ellipticity or phase difference of the reflected light. It was shown by Larson and Pickle-simer3 that apparent-angle-of-rotation measurements may also be used to determine crystallographic orientations of grains of noncubic metals. In particular, it was shown that the basa.1 pole orientation in space of zirconium grains can be determined to ±3 deg for those grains with basal pole tilts of 10 to 90 deg from the plane of the section. Another, even more widely studied, optical property is reflectivity. cameron4 has commented upon measurement of the reflectance of plane-polarized, vertically incident light and Bowie and Taylor5 have made such measurements an integral part of their system of ore-mineral identification. Leow6 has reported on the spectral reflectivity of molybdenite and has used reflectivity values to calculate refractive indices and absorption coefficients. Cameron7 has made use of reflectivity values to ascertain aniso-tropic ore mineral symmetry and Piller and v. Gehlen8 have evaluated sources and importance of errors in reflectivity measurements as applied to calculation of optical constants. cambon9 has shown that reflectivity measurements using vertically incident, plane-polarized light are useful in the investigation of metals and in the identification of phases present in alloys. Bronson10 has made preliminary measurements on the optical anisotropy of beryIlium and Mott and Haines11 have published qualitative data on the intensity of light reflected from sections of bismuth, tin, and aluminum when these metals are microscopically examined under crossed polarizing plates. Koritnig12 has correlated the reflectivity of homogeneous solid solutions with their chemical compositions. From the above work and investigations in progress by this author, it is apparent that accurately determined values for the reflectance of vertically incident, plane-polarized monochromatic light from carefully polished surfaces of noncubic metals can prove useful in identification, composition determinations, and crystallographic orientation applications. Finally, reflectivity values, when measured in two media of differing refraction index and related to standards whose spectral reflectivities in these media are known, can be used to calculate optical constants such as refractive index and absorption coefficient. These constants may prove of use to those concerned with problems of electron band configuration. This paper reports the spectral reflectivity of zirconium measured in light of 441 to 668 nanometers (nm) wavelengths and air immersion. It also gives maximum bireflectance values for a prism section of zirconium in these wavelengths and shows how bire-flectance may be used to determine the crystallographic orientation of zirconium single crystals. Because of the lack of information on the reflectivities of the standards in oil immersion, no attempt is made to calculate the refractive indices or absorption coefficients although it is recognized that such values may be of fundamental importance. METHOD Single crystals of zirconium were cut by electro-discharge machining from a single-crystal rod grown from iodide bar by an electron-beam zone-melting process.13 The crystal sections were mounted in cold-setting epoxy resin and mechanically polished to a plane, uniform, bright surface. Each crystal was then chemically polished in a 26/26/43/5 mixture (by vol) of water, nitric, lactic, and hydrofluoric acids to remove the mechanically damaged and smeared surface layer. Final polish was obtained by electropolishing at 30 v in a bath of methyl alcohol and perchloric acid (98/2 by vol) at -70oc.14 Reflectivity measurements were made using a photometer system designed and developed at Oak Ridge National Laboratory and described in detail by Larson.15 Briefly, the reflectivity measuring system consists of a reflecting microscope; a double-beam, null-balancing photometer array; a mechanically driven microscope stage; and a direct X-Y readout of the reflectivity of the specimen relative to its orientation on the microscope stage. The measuring photometer receives its signal from the specimen through a slotted Wright occular placed on top of the photovisual head of the microscope. The reference photometer receives light through a flexible glass "light pipe" from a mirror in the reflecting system of the microscope. Monochromatic light is attained through use of interference filters (15-nm half-peak width pass bands) placed in front of a stabilized Vickers 12 v, 100 w, tungsten-filament, quartz-iodide lamp.

Jan 1, 1970

By E. E. Donath

Application of the coal hydrogenation process for the production of chemicals is described. It has been estimated that a plant to produce 31,090 bbl per day of chemicals and fuels would cost $326,- 000,000. These products would consist of 6.1 pct by weight tar acids, 50.8 pct aroma tics, 16.4 pct LPG, and 26.7 pct gasoline. THE coal hydrogenation process is well known as a means for the production of liquid fuels from coal. In this paper the possibilities of the coal hydrogenation process as a source of chemical raw materials will be discussed. The recovery of chemicals from coal hydrogenation products necessitates some modifications and additions to the equipment used for the production of fuels. The conversion of coal into liquid fuels such as gasoline requires two steps: liquid phase and vapor phase hydrogenation. Intermediate oils obtained in the liquid phase contain oxygen and nitrogen compounds, especially aromatic compounds, since the coal itself is composed mainly of cyclic compounds. These oils are the raw material for the separation of high molecular weight aro-matics and of tar acids and tar bases. The relative amounts of heavy and middle oil—boiling above and below, e.g., 325°C—can be influenced by temperature, residence time, and catalyst of the liquid phase hydrogenation. In the vapor phase hydrogenation a solid bed catalyst is used to convert the intermediate oil from the liquid phase operation into hydrocarbons of the gasoline boiling range. Essentially pure hydrocarbons with a low content of sulphur, oxygen, nitrogen, and olefines are obtained. Depending mainly on the catalyst, the high ring compound content of the liquid phase oil can be preserved and gasoline rich in aromatics obtained. However, with other catalysts, these ring compounds can be split into gasoline with a high content of isoparaffins.' Again, depending on the operating conditions, products of varying boiling range can be obtained. Selection of catalyst and operating conditions therefore makes possible the production of different grades of motor fuel and also variations in the relative amounts of benzene, toluene, and xylene when aromatic hydrocarbons are produced. The schematic flowsheet, Fig. 1, shows the main steps of the coal hydrogenation process, and the product streams used for the recovery of chemicals are indicated. In the liquid phase hydrogenation stage, coal is made into a paste with recycle heavy oil. The coal paste is mixed with hydrogen and preheated at a pressure of 300 to 700 atm in heat exchangers and preheaters. The coal paste and hydrogen enter high pressure converters where the liquefaction of coal, conversion of the high boiling liquid materials initially obtained, into intermediate oils is performed at a temperature around 470°C. The reaction products enter the hot catchpot in which lower boiling oil vapors are separated from the residue containing unreacted coal, ash, and heavy oil. This residue, usually called H.O.L.D. (heavy oil let down), is processed to separate solid and liquid material. By thermal treatment of the residue, e.g., a coking process, distillate oil is obtained, which can be recycled as part of the pasting oil. This stream is rich in polynuclear aromatics and can be, and has been, used for the recovery of such material. The oil vapors and hydrogen from the hot catchpot are cooled in heat exchangers and a cooler, and the condensed oil is separated from the recycle hy-

Jan 1, 1953

By John P. Huger

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

Jan 1, 1963