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By Donald F. Smith

This report describes the construction and calibration of two ice calorimeters and includes results of high-temperature heat-content measurements, made by the Federal Bureau of Mines, on rubidium fluoride, hafnium tetrafluoride, cesium chloride, and cesium iodide. The heats and entropies of fusion of rubidium fluoride, cesium chloride, and cesium iodide have been calculated at their respective melting points using equations derived from the experimental heat-content data. Hafnium tetrafluoride did not melt within the range of temperatures investigated. Heat and entropy of transition of cesium chloride from the alpha to the beta form were also determined. INTRODUCTION Free-energy data usually afford the cheapest and quickest means of determining the feasibility of experimentally untested reactions. For known reactions, free-energy data show the variation of the equilibrium constant with temperature and make it possible to calculate, without experiment, the maximum ratio of product to raw material for a given chemical process.

Jan 1, 1961

By H. F. Feldmann

This Bureau of Mines report presents a method for the computer solution of the equilibrium compositions of any complex, multiphase, chemical system for which appropriate thermodynamic data are available. The method describes in detail the computation of systems in which solid or liquid species can form by heterogeneous chemical reactions where these species do not occur in any equilibrium equations. Also described are the calculation of phases formed by condensation (pure or solutions) and the inclusion of other system restrictions such as electroneutrality. The method is being used to compute the equilibrium composition of mixtures of an electrically conductive plasma and a liquid slag phase arising from the high-temperature combustion of coal for magnetohydrodynamic power generation. These mixtures can contain up to 65 species including gases, liquids, free electrons, and ions.

Jan 1, 1969

The Geophysics Education Committee has devoted several years to a consideration of the problem of training geophysi-cists. Past reports have dealt largely with fact finding and with the discussion of particular aspects of geophysical education. In the present report it is proposed to review the subject more comprehensively. This involves the question of what educational qualifications the geophysicist of the highest professional standards should possess, and the related question of what changes must be effected in existing educational institutions in order that prospective professional geophysicists may obtain instruction of the desired quality. The type of geophysicist here contemplated is one familiar with what is known already in the several branches of earth physics, and capable not only of following contemporary progress in any of these branches, but of contributing to that progress in a research capacity. Geophysics in its broadest sense, as has been emphasized repeatedly by this Committee, is the study of the physics of the earth and of terrestrial processes. This includes both the static and the dynamic characteristics of the gaseous, the liquid, and the solid portions of the earth, as well as its gravitational, thermal, and magnetic and electrical manifestations. Some branches of earth physics have been cultivated but slightly; others have reached an advanced state of development. Those branches whose development is sufficient to warrant explicit recognition in the form of organized Sections of the American Geophysical Union are: geodesy, seismology, tectonophysics, and volcanology, dealing with the rock constituents of the earth; oceanography and hydrology with the aqueous constituents; meteorology with the atmospheric constituents; and terrestrial electricity and magnetism with the electromagnetic manifestations. At present, instruction on the professional level in any of these branches of earth physics can be obtained in but few universities in North America. In most institutions where such instruction is undertaken different subjects are given in different and independent departments. Geodesy and hydrology are taught, if at all, as a part of civil engineering. The nearest approach to volcanology and tectonophysics ordinarily is represented by petrology and structural geology given

Jan 1, 1946

The Geophysics Education Committee has devoted several years to a consideration of the problem of training geophysi-cists. Past reports have dealt largely with fact finding and with the discussion of particular aspects of geophysical education. In the present report it is proposed to review the subject more comprehensively. This involves the question of what educational qualifications the geophysicist of the highest professional standards should possess, and the related question of what changes must be effected in existing educational institutions in order that prospective professional geophysicists may obtain instruction of the desired quality. The type of geophysicist here contemplated is one familiar with what is known already in the several branches of earth physics, and capable not only of following contemporary progress in any of these branches, but of contributing to that progress in a research capacity. Geophysics in its broadest sense, as has been emphasized repeatedly by this Committee, is the study of the physics of the earth and of terrestrial processes. This includes both the static and the dynamic characteristics of the gaseous, the liquid, and the solid portions of the earth, as well as its gravitational, thermal, and magnetic and electrical manifestations. Some branches of earth physics have been cultivated but slightly; others have reached an advanced state of development. Those branches whose development is sufficient to warrant explicit recognition in the form of organized Sections of the American Geophysical Union are: geodesy, seismology, tectonophysics, and volcanology, dealing with the rock constituents of the earth; oceanography and hydrology with the aqueous constituents; meteorology with the atmospheric constituents; and terrestrial electricity and magnetism with the electromagnetic manifestations. At present, instruction on the professional level in any of these branches of earth physics can be obtained in but few universities in North America. In most institutions where such instruction is undertaken different subjects are given in different and independent departments. Geodesy and hydrology are taught, if at all, as a part of civil engineering. The nearest approach to volcanology and tectonophysics ordinarily is represented by petrology and structural geology given

Jan 1, 1946

By Jamal Rostami, Omid Frough, Wei Hu

Characterizing the abrasiveness of soil/rock and the allowable wear of hard-facing products in various conditions is a critical factor in selection of the best material for certain applications related to drilling and excavation in mining and construction industries. The Soil Abrasion Index test machine at Colorado School of Mines (CSM) is one of the recently developed unique systems capable of testing soil/crushed rock abrasion under various conditions, such as dry, wet, and saturated settings. It is also capable of testing the performance of various types of hard-facing materials in a given geo-material. This paper studies the wear properties of different hard-facing materials in various crushed rocks from a surface mining operation in the iron range region of the USA. The hard-facing materials include regular and hardened steels and six different specialized hard facings, based on chromium carbide. The soil/rock include a standard sand and two rock samples from the surface mine. Fourteen abrasion tests were conducted, where the weight loss of each hard-facing material was measured over timespans up to 1 h of testing. The results show the distinct performance differences between the steels with 17 HRC and 43 HRC hardness and the hard-facing products for this application. The results show the possibility to evaluate the abrasiveness of different rocks at a mine or construction site and the performance of various hard facings in similar working conditions. This is a practical solution for selection of the cutting tool or reinforcement of bucket lips and truck beds for comparison of relative wear life between different wear-resistant materials.

By James P. Bowersox

Modem mineral processing plants handle large amounts of ore and produce large tailing streams. Plant performance can be optimized when the water is quickly recovered with a thickener. The caisson thickener was developed to overcome process and mechanical problems with the conventional traction and center column units. The caisson is a hollow center column that serves as a pump house. The rake arm structure is supported by a hydrostatic bearing which sits on top of the caisson. The caisson thickener with a hydrostatic bearing has operated for many years in several mineral processing applications.

Jan 1, 1981

By Thomas T. Read

Jan 1, 1913

By Walter Wood

The specifications for locomotive-cylinders, which are given in a separate paper at this meeting, have been prepared so that castings (upon the successful use of which so much depends) shall be made to conform to standards that will yield good results. After the essentials, which go with a sound and perfect cauting, the requirements to be borne in mind are those concerning the quality of the material. These have been determined from the actual practice of the largest users,—representatives of the American Locomotive Company, the Baldwin shops, and the Pennsylvania Railroad being upon the Committee. The results called for by the test-bar have been carefully checked by actual experiment upon metal that has given satisfactory service in cylinders.

Jan 1, 1905

By G. N. Goldberg, Robert A. Rapp

The steady-state kinetics and microstructures of simultaneous internal oxidation and external scale formation were investigated for the oxidation of Cb-Zr and Ch-Zr-Re alloys in pure oxygen at 1000°C. For each binary alloy, a constant rate of scale formation was observed at steady state; the internal oxidatton zone reached a steady-state, time-independent thickness. The dependence of the scaling rate on zirconium content exhibited a maximum at a low zirconium colttent; more concentrated alloys oxidized at a slower rate than pure columbium. This composition dependence of the scaling rate may be partially attributed to the effect of the internal oxidation process as an intenla1 sink for oxygen, with the formation of voluminous, and relatively impermeable ZrO2 precipitates. However, the morphologies of the ZrO2 internal oxide precipitates also affected the scaling rate. The internal oxide precipitates were distributed uniformly in the external scale. The steady-state thicknesses of the internal oxidation zones were not in agreement with those predicted theoretically from an idealized simple model. However, in this particular alloy systen1 the ideal model is not satisfied experitmentally. For ternary Cb- Zr - Re alloys with Nr10e = 0.02 or 0.05, the steady-state thicknesses of the internal oxidation zones were less than those for the corresponding binary Cb-Zr alloys. For ternary alloys with NRe(0) - 0.05, a more adherent and much less porous external scale was formed, and a reduction in the kinetics of scale formation was observed. A number of authors'-7 have reported linear oxidation kinetics for the reaction of pure columbium at 1000°C in air or in oxygen of about 1 atm pressure. A thin and tightly adherent oxide layer is found at the metal/oxide interface beneath a porous external layer of scale. Although the suboxides CbO and CbO2 represent thermodynamically stable phases at 100O°C, generally only Cb2O5* is identified as a reaction product in quenched specimens. Studies at 1000°C at lower oxygen pressures8,10 (Po2 - 10-4 Torr) show that both CbO and CbO2 do form and that CbO2 is a protective oxide. The growth of CbO2 results in parabolic kinetics until Cb2O5 is nucleated and grows. Apparently because of the large volume change associated with its formation, Cb2O5 is porous and does not serve as a diffusion barrier; linear kinetics prevail after the surface is covered with Cb2o5. On the basis of these observations, several authors5,9,10 have suggested that the linear oxidation of pure columbium at 1000°C in air or oxygen of 1 atm is limited by a Loriers-type mechanism,11 whereby the total rate or reaction is controlled by ionic diffusion through a thin layer of CbO2 which is maintained at a constant thickness throughout the linear oxidation. However, the concept of a Loriers model for a three-phase CbOlCbO2 Cb2O5 scale, with the only oxygen activity gradient across the NbO2 phase, is not self-consistent. Further, the suboxides CbO and CbO2 were not observed in the high-temperature X-ray diffraction study of columbium oxidation by Goldschmidt.8 From investigations in which the large PO2, dependence of the linear scaling rate was demonstrated, the importance of an oxygen adsorption or dissolution step has been suggested.4,5,7,10,12 Thus the mechanism for the linear oxidation of pure columbium remains quite controversial. Since further insight into the oxidation mechanism of pure columbium is not provided by this investigation, the authors wish to emphasize at the outset that their experimental results are not interpreted in terms of a particular rate controlling step for the oxidation of pure columbium. Previous investigations13-18 of the oxidation of Cb-Zr solid-solution alloys in air or oxygen at 1000°C suggest a remarkable dependence upon zirconium content. For an alloy of bulk zirconium mole fraction, N2r(0) equal to 0.05 or 0.10, the oxygen uptake is reported to be as high as four times greater than that for pure columbium;13,14 for alloys with NZr(0) 0.05 or 0.10 the oxygen uptake is reported to decrease with increasing NZr(0); to a minimum uptake of about one quarter that for pure columbium at NZr(0): = 0.50.13-15Since zirconium forms a more stable oxide (ZrO2) than the lowest columbium oxide (CbO), and since columbium exhibits a high solubility19,20 and diffusivity21,23 for oxygen, the internal oxidation of the zirconium component to ZrO2 is expected at a reaction front ahead of the advancing metal/scale interface. The external scale is then formed at the metal/scale interface by the inward migration of oxygen through the scale, probably through a series combination of molecular and ionic diffusion. Internal oxidation in conjunction with external scale formation has been investigated by Maak24 for the oxidation of dilute Cu-Be alloys in pure oxygen at 850°C. For cu-Be and many other binary alloys,24-27 very small, essentially uniaxial internal oxide particles are formed in the most dilute compositions; for somewhat more concentrated alloys. the internal oxide particles precipitate as platelets or needles. From pertinent solutions to the diffusion equation, Maak28

Jan 1, 1967

By J. R. Hornaday, A. E. Morris, N. A. Parlee, D. C. Carmichael

Rates of absorption and effusion of hydrogen in solid iron were measurede by a Sieverts type of apparatus. With clean a iron these rates are diffusion controlled down to 420°C and are represented by the equation D = 6.70 x e-'100' crn2 sec-I Certain surface impurities can affect these rates at all temper-atuves. Thin oxide films lower, the apparent diffusivity of annealed iron markedly. Cold-worked iron (75 pct) annealed at 430°C has practically the same solubility and diffusivity as anealed iron. THE mechanism of absorption and evolution of hydrogen in solid iron alloys is not fully understood despite the large number of investigations on the subject. While there appear to be many instances of simple solid-state diffusion control of rate, there are many cases where investigators have either concluded that surface reactions are rate controlling or that some "nondiffusible" hydrogen resides in discontinuities. The purposes of this research were 1) to develop a sound method for studying this absorption and evolution behavior, 2) to examine it in pure annealed iron, and 3) to determine the effects of important variables, such as cold work, surface condition, and composition. This paper relates the progress toward these objectives. Much of the present knowledge of the movement of hydrogen through iron alloys comes from permeability studies which involve the measurement of the rate of passage (under steady state conditions) through membranes of the order of 1 mm in thickness. This method is open to question on various grounds. If surface reactions are involved, two different surfaces operating under two different conditions must be considered. The presence of defects in the membrane even of microscopic dimensions may lead to erroneous results. A few people have studied evolution of hydrogen into vacuum, under carefully controlled (unsteady state) conditions, and some of the best diffusivity data come from these sources. Most of these methods measure rates of evolution only and thus do not make a rigorous test for reversibility of behavior. It appeared that an "unsteady state" method that would permit the measurement of both rates of evolution and absorption under controlled temperature, pressure, and other conditions would offer several advantages. Accordingly the modified Sieverts apparatus described below was designed and built. APPARATUS This apparatus is shown in Fig. 1. The sample bulb is detailed in Fig. 2. Hydrogen of 99.5 pct purity and argon of 99.99 pct purity were used. The hydrogen was deoxidized and dried by means of a Deoxo unit followed by a "Dri-erite" tower. The argon was only dried. The gas burette was graduated in tenths of a cubic centimeter, and, with the aid of a travelling magnifier, readings could be estimated to the nearest 0.01 cc. The level of mercury in the burette was adjusted by means of a leveling bulb operated by a fine screw adjustment. An electrical system, consisting of two slightly separated platinum electrodes inserted in one leg of the manometer and a small light bulb was used to obtain rapid accurate adjustment of the pressure. The capillary tubing of the Vycor sample bulb was 3 mm bore as was all tubing back to the gas burette. The samples were discs made from vacuum-melted Ferrovac-E iron of greater than

Jan 1, 1961

Jan 1, 1953

By Joseph Cervik, Gerald L. Finfinger

This Bureau of Mines publication reviews underground methane drainage pro- grams being conducted in various coalbeds. Equipment used in drainage programs such as drills, underground pipelines, and methane monitoring systems is described.

Jan 1, 1980

By Norman B. Davis

Introductory Feldspar is one of the most important mineral products consumed by the various branches of the ceramic industry. In the manufacture of table ware, electric porcelain, floor tile, and enamels, it supplies the chief fluxing ingredients necessary to bond the other more or less inert materials together when moulded into desired shape and fired in a kiln. Feldspar is used in the manufacture of bottle glass as a means of introducing alumina in a form easily assimilated. It is also used in certain scouring soaps particularly designed for cleaning enamel and glass surfaces. Feldspar, as it finds its way to the trade, is not a single mineral but is rather a mixture of various proportions of the feldspar silicate series, either in natural intergrowth or blended in the milling process, to produce a desired result. It is often further modified by the presence of quartz in amounts up to 30 per cent. The table on the next page gives typical commercial analyses of feldspar from various sources. Canadian feldspar produced to date has consisted mainly of the high-potash, relatively low-soda, variety, and has enjoyed a good market in the United States for the manufacture of enamels, electric porcelain, and vitrified table-ware. About eighty per cent of the output has been exported to the United States, but, with increased milling facilities in Canada and changes taking place in domestic United States sources of supply, the proportion exported will be reduced next year.

Jan 1, 1931

By R. Minto, W. G. Davenport

The slag removed from the reverberatory furnaces of copper smelters contains significant copper values. A serious financial loss is involved, as further recovery operations are not normally carried out. This paper describes the factors affecting physical transport of matte into slag by gas bubbles, and the subsequent entrapment and flotation of matte drops. Three distinct patterns of transport behaviour have been identified from studies of a number of liquid/liquid systems, including liquid metal and liquid matte systems. A theoretical approach is proposed to explain these behaviour patterns, and to predict transport and entrapment behaviour in matte/slag systems. The concepts of "Film Coefficient" (ø) and "Flotation Coefficient" (?) are introduced. The effects of smelting process variables on the physical loss of copper matte in slag are also discussed.

Jan 1, 1972

By R. V. Subramanian

This project financed by the Bureau of Mines investigated the use of polymers to achieve rock bonding and reinforce coal mine structures for better or permanent ground support. Support was achieved by pumping the polymers into the rock interstices to bond the mass together for increased structural competence. Holes were drilled in the mine roof, after which the polymers were injected at about 100 psi to permeate the cracks. Initial laboratory work indicated that of all the resin systems tested, the epoxy resins could most likely be modified to be suitable for rock injection. This was confirmed when several potentially suitable resin systems underwent intensive evaluation. In a series of three field tests, two conducted in a copper mine with coal mine-type shale and the third in a coal mine, it was shown that the polymers penetrated cracks less than 0.005 inch wide. The fast-setting epoxy systems, cured out in thin films under mine conditions, produced a bond exceeding the strength of the uncracked virgin rock.

Jan 1, 1974

Jan 1, 1927

By C. W. MacGregor

THE observation of the flow layers, or Lüders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-steel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are in reality traces of wedge-shaped flow layers and are formed by the intersection of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45° to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ner, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45° to the principal stress direc-tions at the point. As examples of the latter may be mentioned the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subjected to internal pressure only, etc. Hence if the flow layers are observed from an experiment, the shear-stress trajectories -the curves indicating the directions of the maximum shearing stresses in the body-may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45° to the principal stress directions, the family of principal stress trajectories, or the curves indicating the directions of the principal stresses, may be thus obtained. Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowan;1 in duralumin and other aluminum alloys, by Dawidenkow,2 Elam,3 Fell, and others; in copper and copper-alloy crystals, by Elam;5 in brass by Elam;5 in brass wires by deForest;6 in higher carbon steels, tungsten steel, and

Jan 1, 1939

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper' a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

By M. R. J. Wyllie

Eight laboratory-prepared aqueous base drilling muds representing common mud types, and 15 aqueous base drilling muds sampled in the field, have been used in an experimental investigation of the relationship between the streaming potential developed across a mud filter cake and the differential pressure causing filtrate flow. It has been established that the relationship is of the form, ES = kPy, where Es is the streaming potential, P the differential pressure and k and y are constants for any particular mud system at constant temperature. Beyond a certain minimum thickness this relationship is independent of filter cake thickness. Experiment has shown that both k and y are temperature dependent parameters and that in certain mud systems there is a critical value of P above which the simple relationship Es = kPY ceases to hold. The constant k tends to be a function of the mud resistivity at 77ºF, but the exponent y has not been found to be related to any commonly measured mud property. Certain field experiments are described which serve to demonstrate that the total SP (self potential) developed opposite a formation may be quantitatively accounted for as the algebraic sum of an electrochemical potential and an electrokinetic potential. A chart to permit the simple use of mean solution activities in the interpretation of electrochemical SP data is given and its use described. Various field methods for computing the electrokinetic SP component of the total SP are considered and rejected as being unduly complicated and inaccurate. It is shown that the employment of low resistivity drilling muds is essential if optimum accuracy is desired in the use of the S.P. curve for the purpose of computing connate water salinities by the electrochemical SP method. The use of such low resistivity drilling muds is accordingly recommended. INTRODUCTION In a previous paper' a quantitative analysis of the electrochemical compovent of the SP (self potential) curve was made and it was shown that the electrochemical* emf, E, could be expressed as E = ZtRT/F In a,/a,, where t is the transference number of the chloride ion, R is the gas constant, T the absolute temperature of the formation water and mud, a, the mean activity of the connate water (assumed to be sodium chloride) and a, the mean activity of the mud (as sodium chloride). The essential accuracy of this expression was confirmed by an investigation 2 of the SP kicks opposite sands of known water salinity. The logs examined had been routine runs in oil wells in a number of Mid-Continent states. Further confirmation of the original analysis of the electrochemical SP is implicit in the paper by Tixier3 wherein a relationship between the SP and the ratio of connate water and mud resistivities, based only on field data, is given. Allowing for the fact that mud and connate water resistivities were used instead of activities, and that electrokinetic effects were ignored, the constant reported by Tixier is essentially 2tRT/F. The error involved in the universal substitution of resistivities for activities will receive further reference below. Possible reasons for the fact that the electrochemical properties of shales do not appear to be significantly dependent upon either the nature or the quantity of cation exchange materials, such as clays, they contain has been considered at some length by Wyllie and Patnode.4 In the same paper, the probable effects of shale thickness and compaction on electrochemical efficiency, and hence the inherent difficulty of obtaining reliable laboratory-scale data, were also pointed out. However, it is

Jan 1, 1951

Jan 1, 1961