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By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18. 19. 21, 22, 23, 24, 30, 34). concluded that a foundation lor the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.I One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur 0. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 232,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. Stadler's Hypothesis Worthless It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left—the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things. that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in finc crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1943

By J. S. Kennedy, G. L. Simard, A. A. Lefrew, C. M. Judson, R. B. Booth

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By J. S. Kennedy, A. A. Lefrew, C. M. Judson, R. B. Booth, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By G. W. Lester, T. J. Nowak

The paper presents a practical method of utilizing pressure fall-off data obtained when a water injection well is shut in for determination of: (I) the static reservoir pressure, (2) the potential water injective capacity (md-ft) of the formation, and (3) the formation damage (skin effect) surrounding the wellbore. In the development of the method, equations are presented which give The theoretical background for predicting the behavior of water injection wells. Certain physical factors which limit the application of the method are discussed. The procedure and the relevant precautions in obtaining the data are discussed. A sample analysis and computation from an actual pressure fall-off curve is illustrated. Fintrlly, general characteristics of pressure fall-off curve! obtained in several reservoirs are presented. INTRODUCTIO N Theoretically, in an injection well the flow of water into the formation will continue as long as the sand-face pressure is greater than the reservoir pressure. However, in practice, engineers have observed that upon stopping injection and opening the wellhead to atmospheric pressure, some wells backflow water for time intervals ranging from several seconds to several hours although the sand-face pressure, as calculated from the hydrostatic head, is considerably greater than the static reservoir pressure. Further, field observations indicated that upon shutting in a water input well, the wellhead pressure does not drop off immediately, but a pressure decline occurs lasting from several seconds to several days. These observations make it evident that when an input well is shut in, a residual pressure lingers in the vicinity of the wellbore which is greater than the average reservoir pressure. This residual pressure declines first rapidly, then more slowly, to the static reservoir pressure: therefore, it is called transient back-pressure or pressure fall-off. The first step in investigating the mechanism of pressure fall-off is to establish what general conditions are necessary for its occurrence, and to this end, Dickey and Andresen1 have presented a qualitative explanation describing the mechanism. They point out that the formation pressure gradient in the vicinity of the well does not disappear immediately when the input well is shut in, as if the system were filled with a totally incompressible fluid, but it is maintained by the expansion of the compressible fluids and by the elasticity of the formation. In such a compressible system the decrease in pressure is possible only to the extent that the water front continues to advance until the pressure is equalized. The principal aim of this paper is three-fold; namely. (1) to present a theoretical quantitative analysis of pressure fall-off data, (2) to present an application of the developed theory to field data, and (3) to discuss the general characteristics of actual pressure fall-off curves. Under (I), theoretical equations dealing with such factors as compressibility of the fluid-reservoir system, mobility of the fluids and certain physical restrictions that

Jan 1, 1956

By J. C. Cordell, C. F. Weinaug

A study of the behavior of retrograde condensation from gas mixtures was made in the presence and absence of sand in order to determine if the condensed liquid would re-vaporize in the Presence of sand. Methane-butane and methane-pentane mixtures that would form liquids by retrograde condensation when produced from a constant volume cell were used. The methane-butane mixtures of similar composition were produced by three different methods. The first two were charged into an empty cell and were produced in one case within a period of 9 hr and in the other within a period of 3 days. The third mixture was charged to a sand-packed cell and produced within a period of 9 hr. The curves relating composition of the produced gas to pressure obtained from these experiments show that equilibrium was maintained as long as liquid was condensing. However, during the portion of the pressure decline where the condensed liquid should be revaporizing, equilibrium was maintained only when the mixture was produced from the sand-packed cell. The methane-pentane mixture is produced only in the presence of sand. The data obtained for this system also show that equilibrium is maintained at all times during the pressure decline. These results indicate that revaporization is aided rather than prevented by the fact that the condensate "wets the sand." The significance to the petroleum industry of the behavior of hydrocarbons in the retrograde region is becoming increasingly important because a large percentage of reservoirs being discovered today arc of the gas-condensate type. The important characteristic of a gas-condensate reservoir is the retrograde condensation of a liquid phase throughout the reservoir if the pressure is allowed to decline. In order to prevent the loss of this retrograde liquid in some of these reservoirs, they are "cycled"; that is, the material produced from the reservoir is processed to remove the heavier hydrocarbons and the light fractions are returned to the reservoir to maintain the reservoir pressure. Another method of producing these reservoirs is Pressure depletion. There are other methods but they are not in general use. Although a large number of factors are involved in determining the optimum method of producing a reservoir, only the problem of whether the retrograde condensate resulting from pressure depletion will revaporize from sand at equilibrium conditions is considered in this paper. Also the data are limited to the methane-n-butane and the methane-n-pentane systerns at loo°F and one type of sand. Three types of tests were run in order to compare the revaporization of retrograde liquid formed in a cell with that formed in a sand-packed cell, and to establish the effect of time. The results of tests presented in this paper indicate that both time and the presence of sand promote the revaporization of

Jan 1, 1949

By J. D. Milburn, H. J. Hill

In quantitative interpretation of electrical logs the presence of clay minerals introduces an additional variable which further complicates an already complex problern. Although recognizing the difficulties introduced as a result of the heterogeneity of natural sediments and despite the present incomplete state of knowledge regarding electrochemical behavior of shales, dissemirzated clay minerals and concentrated electrolytes, it was felt that useful empirical correlations might be obtained from experimental investigation. Six typical sandstone formations, having a wide variety of petrophysical properties, were selected for the study. Approximately 45 samples from each formation were selected to satisfactorily represent the range of pore size distribution within the particular formation, As a matter of general interest, four limestone formations were also included in the investigation. Previously proposed equations relating to resistivity, SP and interrelationship of the two phenomena have, where possible, been tested with data obtained in this investigation. These equations do not satisfactorily describe experimental behavior of samples through all degrees of shaliness or throughout the range of brine solution resistivities normally encountered in logging practice. An empirical equation has been developed which quantitatively relates formation resistivity factor to satirrnting solution resistivity, porosity, and "effective clay content." This relation is indicated to be uniformly applicable to clean or shaly reservoir rocks. It is shown that both the SP and resistivity phenomena of shaly samples are related to the sample cation exchange capacity per unit pore volume. The independent chemical determination of this parameter is thus a means of determining the "effective clay content" of samples. Some implications regarding theory and electric log interpretation of shaly sands are discussed. INTRODUCTION The use of electrical resistivity logs as a means for estimating formation porosity is based upon the original work of Archie1. It was shown by empirical methods that the resistivity of a rock, when 100 per cent saturated with brine solution, could be related to rock porosity through the equation, F = Ro/ RW = f-m.......(1) where F, the formation resistivity factor, is defined as the ratio of the resistivity of the 100 per cent water saturated rock, Ro, to the saturating solution resistivity, Rw; f is the ratio of pore volume to bulk volume; and m is the slope of the average line when the data are plotted on log-log paper. This relation was established for relatively shale-free formations containing water having high salt concentrations, and under these conditions F may be considered constant for a given rock sample. Applications of Eq. 1 to interpretation of logs of shale-free formations has been quite successful when satisfactory formation water resistivity data could be obtained. The most readily available means of estimating formation water resistivity is the self-potential log. Conventional methods of SP log interpretation involve correct.

Jan 1, 1957

By H. L. B. Gould, Jr. Wenny D. H.

TO date there has been but limited interest in alloys of 80 to 95 pct Co and Fe with or without other additions. In 1932, S. R. Williams' reported practically zero magnetostriction for the 90 pct Co-10 pct Fe alloy. This same composition was used for pole pieces to control the magnetic field in magnetrons operating at high temperatures.' In 1947, a 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn composition was investigated3 for use in ballast lamps because of its high temperature coefficient of resistance. Recently, as part of a survey of ductile and malleable magnetic alloys capable of being processed to thin gages for possible applications in memory devices, the high Co-Fe alloys have been re-examined to determine their fabricating and magnetic characteristics. Alloys from 80 up to 95 pct Co and Fe with and without additions such as vanadium were prepared. In general these all had excellent ductility and malleability. Wire was drawn to thin gages without difficulty and fine hard-drawn wires flattened to 2) The phenomenon may have potential in estimating the carbon content of molybdenum. A given solution-treating temperature and cooling rate could perhaps be calibrated so that the area fraction of surface covered by carbide could be interpreted in terms of carbon concentration. By segregating to the surface, a big "magnification" of the carbon content is obtained, which should make the method cheap, direct, and sensitive and, therefore, perhaps of interest to the molybdenum industry. This work was conducted at Battelle Memorial Institute. Financial support by the Aeronautical Systems Division, United States Air Force, under Contract No. AF 33(657)-7376, is gratefully acknowledged, and the writer is thankful for the experimental assistance of Miss Marjorie Cantin. ribbon without splitting. Similarly, strip was cold-rolled as much as 99.75 pct reduction to a 0.25 mil thickness without intermediate anneals. Samples of round and flat wire and foil, in the severely cold-worked and annealed states, were checked for magnetic characteristics. The alloys exhibited widely divergent magnetic characteristics depending on the processing and heat-treating procedures used in preparing the samples. Direct-current hysteresis loops showing the different magnetic characteristics of 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn alloys are shown in Figs. 1 to 8 inclusive, while Figs. 9 and 10 show the loops for an alloy of 82 pct Co, 11.75 pct Fe, 5.6 pct V, and 0.65 pct Mn. Figs. 1 and 2 show the high remanence and exceedingly square-loop characteristics of the hard-drawn wire and ribbon roll flattened therefrom. With the change in processing from roll flattening to flattening by drawing through flat diamond dies the resultant change in texture is accompanied by the drastic change in the shape of the loop as shown in Fig. 3. This skewed loop on annealing reverts to a more normal loop as shown in Fig. 8. The most unique loops are obtained with flat rolled strip. These are shown in Figs. 4 and 5. In the case of the hard-rolled material, Fig. 4, there is little change in induction until the magnetizing force reaches 50 oe. From 50 to 60 oe there is a sharp increase in induction to over 15,000 gauss, which for all practical purposes is saturation. The induction remains at a constant value while the magnetizing force decreases to 40 oe. At this point the

Jan 1, 1965

By S. C. Schaeker, A. W. Schlechten, A. H. Larson

PARRAVANO and Malquori' studied the equilibrium of H2S-Hz with molybdenum and its lowest sulfide which they believed to be MoS2. Mc Cabe' has shown that its composition is actually Mo2S3 and determined its dissociation pressure by means of Knud-sen effusion measurements. Stubbles and Richard- son3 have recently studied the equilibrium of gas mixtures of H2S-HZ with the two-phase solid mixtures of Mo-MozS3 and Mo2S3-MoS2. The latter investigators found that M02s3 deviated slightly from the stoichiometric composition, but they did not determine the homogeneous region of the disulfide phase. Morimoto and Kullerud, studied the Mo-S system by quenching, microscope, and X-ray methods and concluded that the disulfide is stoichiometric. The present investigation was concerned with the measurement of the sulfur vapor pressure variation with composition at 1100°C in the homogeneous region of "MoS2". These measurements were made by reacting: 1) molybdenum powder (99.97 pct Moj with sulfur vapor, and 2) MoS1.g9 (formed by reaction of Mo + H2S) with sulfur vapor in a quartz capsule. Conditions were controlled to form an equilibrated phase within the homogeneous region of the disulfide. The quartz capsule was sealed off initially under a vacuum and the residual gases were gettered by titanium powder contained in one end of the capsule. A mixture of Mo + S or MOS,., + S was in the other end. The section containing the titanium powder was heated for 24 hr at 700°C and then removed by flame sealing. The end of the capsule containing the charge was then heated to 1100°C. The other end of the capsule was maintained at a temperature which would produce the desired sulfur pressure in the capsule (liquid sulfur distilled from the charge mixture was retained in this end). After equilibration, the capsule was removed from the heating assembly and rapidly air-cooled. It is assumed that equality existed between the total sulfur pressures (PT) in the two ends of the capsule and not between the partial pressures of the different molecular species (S, SZ, Three separately controlled heating elements were used to maintain the proper temperature gradient over the length (approximately 12 in.) of the capsule. A thermocouple-Wheelco "Capacitrol" system was used for temperature control of the two end heating elements within 2"C. The center heating element was controlled directly by a " Power -stat". Separate controlling and measuring thermocouples were used for both end heating elements. Pt-Pt(l0 pct Rh) thermocouples were used for 1100°C and Chromel-Alumel thermocouples were used for lower-temperature control and measurement of the assembly. Silver foil was wrapped around the end of the capsule containing the liquid sulfur to insure a constant temperature zone. The thermal gradient over the entire length of the capsule was measured to: 1) ascertain that the length of the constant temperature zone of the liquid-sulfur end and the sulfide end was sufficient, and 2) ascertain that the liquid-sulfur zone was the zone of lowest temperature. The data obtained in this investigation are shown in Fig. 1 and Table I. The total sulfur pressure (PT) and p(S2) were calculated from the data of Braune et UZ.~ The compositions of the equilibrated disul-

Jan 1, 1964

By Wm. D. Owsley, R. E. Moeller

In the petroleum industry, the process known as oil well cementing is the equivalent of pressure grouting in the mining and construction industries. The science of oil well cementing has been known and practiced for many years. At the present time it has been brought to a high degree of perfection in the handling of many different types of jobs, all of which are known as oil well cementing. In order to understand more easily these processes, we will discuss briefly several different types of oil well cementing jobs, the purposes for which they are performed, and the methods of their accomplishment. It is believed that some of .these procedures, in a modified form, can be applied to pressure grouting projects in general. Originally, oil well cementing consisted of placing a neat cement slurry about a steel casing set in a bore hole. Cement is used about these casings to protect them from the corrosive effects of ground waters, to protect the oil and gas zones from encroachment of undesired water from other levels, to prevent the blowing out of high pressure oil and gas zones from shallow levels, and to strengthen generally and support the casing being placed in the bore hole. After the bore hole is completed to the desired depth, casing is run into the well, pumps are attached to this casing and circulation of the mud fluid in the hole is established; this circulation being from the inside of the casing into the annulus about the casing, and thence back to the surface. Next, a cement slurry is mixed and pumped into the inside of the casing string, A plug, which acts as a piston within the casing, is placed above the cement slurry. This is to separate the top of the cement slurry from mud or water which is used to shove the cement down through the casing and out into the annulus. This plug further serves the purpose of shutting off against a baffle in the bottom end of the casing string, thus stopping the flow of cement out of the casing and leaving the shoe, or lower end of the casing, surrounded by cement and also filling the annulus there above. Casing strings cemented in the above described manner may vary in length from a few feet of large diameter pipe to very long lengths of smaller pipe. As of the present date the longest string of casing which has yet been cemented is some 16,600 ft deep. As a general rule, the deeper the well and the more cement slurry used, the higher the pressures which are required to place the slurry. In parts of West Texas, it is not uncommon to use 4000 sacks to cement a single string of casing in place. Machinery used to mix the cement and place it into the casing is mounted on heavy duty, powerfully equipped trucks which are capable of negotiating any type of highway or country roads. These trucks

Jan 1, 1949

By E. A. Gulbransen, W. S. Wysong, K. Andrew

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of '3 pct chrome-iron in vacua of the order of 5 X lo' mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a 'low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600' C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,' and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By Don M. Jackson

The techniques for the growth and controlled, graded doping of silicon epitaxial overgrowth layers were established. Grading of- impurities such as arsenic or boron in arbitrarily chosen profiles oiler four orders of magnitude (from I X 10Lg to 1 X 10L5 cm) was accomplished. The graded structures were grown in a stepwise manner where in the profiles were approximated by growing many separate layers with small doping-level changes between layers. Masked-area growth of silicon through windows in a SiO2 masking film was acconiplished through the simultaneous injection of HCl gas 102th Sic14 in the epitaxial reactor. The HCl served to inhihit the growth of silicon on the Sz02 surface, and also to control the cross-sectional profile of the silicon mesas. silicon from the substrate was etched out through the windows, and then epitaxial material was used to fill the holes hack in to form planar diodes. Simullaneous HCl injection was adapted to control the cross-section profile of the hack-filled regions. Arsenic-huried regions beneath in te- In recent months, the epitaxial growth process in semiconductor materials technology has evolved into a complex system directed at both material improvement for better monolithic integrated-circuit characteristics and the development of new silicon structures for future integrated-circuit needs. The advent of high-temperature HC1 gas etching1 grated-circuit transistors reduced V(SAT) by slightly more than one third, bringing this parame-ter to that of an isolated component transistor. When arsenic was diffused into the starting sub-stvate, it was necessary to remove any excess arsenic in order to avoid excessive audodoping of the subsequent epitaxial layer. Oxide isolation of single-crystal regions in a substrate provided complete electrical isolation of integrated-circuit components, thereby eliminating parasitic capacitance which is inherent in standard integrated-circuit processing. The process involved the etching of deep mesas on silicon Wafers, the formation of an oxide over the mesa surface, and then the deposition of several mils of polycrystalline silicon over the oxide. The original substrate was lapped and polished allay until the mesas were left isolated in the polycrys-talline matrix. The Final components were fabri-cated in the single-crystal islands. Speed and power-handling capabilities of standard circuits were improved through the process. wherein work-damaged material is removed from the surface of the silicon wafer just prior to the silicon deposition step has made it possible to grow silicon films with structural quality that approaches that of the substrate. HBr used in the same volume ratio as HC1 etches silicon at the same rate and with the same results as HC1. Recent developments in epitaxial materials technology have occurred in the areas of precise doping control, buried prediffused regions between over-

Jan 1, 1965

By Seymour Fiekowsky, Alvin Kaufman

Taxes are compulsory charges levied by a government for its support. They are usually paid to support the general services provided by government rather than special services (such as safety inspection). The latter are normally supported by user charges often called license fees. Taxes are used by national governments not only to raise money but also as a part of fiscal policy. As such, taxes are used to stimulate or deflate the economy, as an incentive to save or invest, as a means of allocating national resources, and as a means of redistributing income. In our discussion, we will deal only with those facets of the subject that relate specifically to the mineral industry. In doing so we will deal with taxes levied on all industry in a generalized way and only insofar as it affects our industry, but at some length on those portions of the tax system related directly to the mineral industry. It is not our intent to provide a "cookbook" for computing taxes, but rather to present some of the policy issues that bedevil those who must develop our tax policies. MINERAL TAXES The mineral industry is subject to the full range of taxes levied by governments. These include taxes on income, property, and sales, as well as excise and severance taxes. The latter are somewhat similar to a royalty in , that such taxes are levied either ad valorem or per unit of output. Severance taxes most commonly are charged to oil and gas output, although coal, salt, sulfur, and iron ore production also have been taxed in this manner. The major governmental advantage of the severance tax is the administrative ease of collection. On the other hand, it poses an addition to cost independent of profitability. As a consequence, the severance tax can cause premature abandonment if mineral product prices do not rise sufficiently to cover it. Such a rise may not occur if differential tax rates are levied by the various states. Property taxes normally are levied on all property owners, including mineral owners. The major difficulties in this kind of tax, in so far as mining is concerned, are erratic valuation coupled to the inherent problems involved in assessing a property where the extent and richness is chiefly unknown. The impact of these taxes, including state income taxes, is reduced somewhat, as they are usually deductible from gross income as a business expense with a consequent lowering of national income taxes. The net cost of severance, property, sales, and state or local

Jan 1, 1976

By R. N. Orava, L. A. Rice

One of the difficulties encountered in the preparation of titanium specimens for transmission electron microscopy is the formation of a surface hydride phase during the thinning operation at ambient temperatures. This necessarily destroys contrast, obscures features of interest, and often leads to misleading results. By cooling the polishing solution to temperatures below 0°C this problem has been overcome in the past.' However, since the cooling procedure is somewhat inconvenient, a technique was developed at this laboratory for thinning titanium at room temperature. The material examined was A-70 grade commercial-purity titanium purchased from the Crucible Steel Co. of America. The mechanical and thermal treatments, described elsewhere,* yielded a recrystallized grain size of 4 to 5 p. A slice, 0.5 mm thick and 1.5 mm wide, was cut from a bulk specimen2 using a diamond cut-off wheel. The sample was then coated with paraffin wax. Two concentric holes, about 0.03 in. in diam, one at each broad face, were scribed through the wax to the surface of the metal. Subsequent polishing for several minutes resulted in a preferentially thinned or "dimpled" region. Thereafter, the wax was removed and the entire specimen polished to the point of breakthrough at the base of the dimple. Polishing was effected chemically in a solution comprised of 30 pct HF and 70 pct HN03 by volume, kept at room temperature (20" to 25OC). The specimens were mounted in a stereo holder and examined at 100 kv in a Philips l00 B Electron Microscope. A micrograph from a foil prepared in this way is shown in Fig. 1. Several points are noteworthy. This electron micrograph shows neither evidence for the formation of a hydride phase due to specimen preparation nor, moreover, any obvious surface contamination in electron-transparent areas of a freshly prepared foil. Localized variations in foil thickness observed in some specimens seem to be a characteristic of this chemical polish but do not seriously detract from foil quality. With care, the lifetime of a good specimen exceeded 2 hr in the beam. On the other hand, the exposure of a sample to air at atmospheric pressure, when still warm from the beam, clearly resulted in the deterioration of a formerly clean area just previously in the field of view. An example in Fig. 2 of a contaminated region reveals features, and "spots", not unlike those observed in much purer material by Yamane and Ueda. Consequently, one can conclude that: 1) titanium can be thinned satisfactorily in a solution at room temperature for transmission electron microscopy; 2) large-scale precipitates, >50A in diam, are absent in commercial-purity, recrystallized, furnace-cooled, A-70 titanium containing about 3800 wt ppm interstitials and the same amount of iron; 3) care must be taken not to attribute surface contaminants to precipitates. The authors are grateful to the Franklin Institute for financial support and permission to publish.

Jan 1, 1967

By John W. Bell

In the introduction to an excellent pamphlet, John Gross' makes the following statements: Although marked progress has been made along mechanical lines, the theory and conception of underlying principles have not advanced so rapidly. This lack of advance in theory may be attributed to the unfortunate situation resulting from the controversy as to whether the Rittinger or Kick law is applicable to crushing. Many pages of the technical literature are burdened with theoretical discussions in favor of one or the other of these laws, which have tended to cloud rather than to clear the atmosphere. Realizing the situation, the Milling Committee of the American Institute of Mining and Metallurgical Engineers, through its secretary, E. A. Hersam, studied the milling industry and, because of the apparently hopeless lack of agreement in the Kick versus Rittinger dispute (5, 13, 14, 16, 18. 19. 21, 22, 23, 24, 30, 34). concluded that a foundation lor the theory of crushing was of primary importance. The numbers in the paragraph quoted refer to papers listed by Mr. Gross in his Bibliography on Crushing and Grinding.I One is obliged to infer that these papers show "hopeless lack of agreement in the Kick versus Rittinger dispute." No. 22 is a paper by Arthur 0. Gates2 and No. 23 is one by the writer.3 Employing the subject matter contained in papers Nos. 22 and 232,3 the writer will show that their authors formulated identical conclusions, based solely on experimental evidence. Exactly the same defect in the Stadler hypothesis was described in each of the two papers, although entirely different experimental methods were employed in uncovering it. Both of the authors, independently, formulated the conclusion that Rittinger's was a true hypothesis and Stadler's false. The evidence in a third paper4 will be employed to prove that Stadler's hypothesis, when examined experimentally, is worthless. Stadler's Hypothesis Worthless It is the writer's opinion that the evidence available in 1915 and the corroborating evidence in 1916 was amply sufficient to eliminate the need for any further consideration of Stadler's hypothesis. Certainly the evidence produced in 1918 dealt this hypothesis its coup de grace. It follows, therefore, that in the year 1918 there was only one credible hypothesis left—the Rittinger hypothesis. Gates' Opinion What information is available in Mr. Gates' paper?2 His conclusions are not consecutively summarized, none the less they are perfectly clear. On page 876, Gates says, and it is a very significant utterance: But my results show, among other things. that many more of Stadler's energy units are obtained per foot-pound-applied in coarse than in finc crushing. This suggests a doubt as to the correctness of his unit, since one would expect a foot-pound-applied to produce the same number of "energy units," whether the feed and resulting product were coarse or fine. When Rittinger's theory is applied, the number of mesh-tons (my unit of surface produced) is

Jan 1, 1943

By Wallace W. Key

Chalk is a natural calcium carbonate occurring as the remains of soft, friable, minute marine organisms. Whiting can be either finely ground calcium carbonate prepared from chalk, marble, or limestone or the product obtained by chemical precipitation from a solution or suspension containing lime. Until relatively recently, whiting made from limestone was termed "whiting substitute," but it is now usually designated as limestone whiting. Precipitated calcium carbonate, sometimes called "precipitated whiting" or "precipitated chalk," is a finely divided calcium carbonate product obtained by chemical precipitation from a solution or suspension containing lime. Considerable quantities of precipitated calcium carbonates are produced from many chemical processes. Naturally occurring calcium carbonate in a variety of crystalline forms and in all degrees of chemical purity forms a substantial part of the earth's crust. Exactly where a chalk grades into a marl or calcareous shale through increase of clay or silt or into a hard limestone through consolidation and crystallization is difficult to determine because no rigid specifications have been promulgated for classifying them. Composition and Properties Once considered to be amorphous, chalk was later found to be cryptocrystalline. In the pure state it consists entirely of CaCO3, but many deposits are impure. When impurities are removed and the material is reduced to a finely divided state, it is known as chalk whiting. Much confusion attends the use of the term "chalk" as well as the classification of whiting materials. For instance, blackboard chalk is not necessarily chalk but is sometimes plaster of paris or a form of talc. Colored "chalks" may be true chalk colored and compressed with a binder but are probably such materials as hematite, clays, or carbonaceous matter. The term whiting was applied exclusively to the product derived from true chalk before World War I. Chalk imports were difficult to acquire during World War I, and whiting substitutes, a term applied to the products derived from natural rock deposits and precipitated calcium carbonate, were introduced. Substitute whitings were not acceptable at first, but it was found that blending true chalk with substitutes often created an improved product; eventually by selection of limestone and finer grinding, products not only acceptable, but for some uses superior to chalk whiting, were developed. Gradually the term "substitute" was dropped because chalk whiting had lost its importance, being largely supplanted in the United States by other whiting materials. Whiting is now made in ever-increasing quantities from limestone, marble, dolomite, marls, vein calcite, oyster-shell, as well as primary and byproduct precipitated calcium carbonates. Distribution of Chalk Europe-In England, France, Belgium, Denmark, and other European countries highpurity chalk occurs in extensive beds. The Cretaceous period, or the "age of chalk," in geologic history receives its name from the great deposits of chalk exposed on either side of the English Channel. It has been estimated that oceans in which chalk and allied deposits were formed covered more than 500,000 square

Jan 1, 1960

By N. E. Grosvenor

Several methods have been proposed for determining the tensile strength of rock. These have been tried out over the past several years, but the results have been erratic and of doubtful value. The tensile strength of rock is its weakest property, and this property apparently enters into all failure phenomena, whether underground or on the slope of an open pit. Therefore, it is essential that detailed quantitative information is known about the tensile strength of rock if the design engineer is going to select the proper pit slope, pit orientation, or orientation of underground workings so as to give the most economical and safest mining condition. This quantitative information may be used to orient the pit in such a manner as to allow steep slopes along two sides. This information possibly may be used to orient the direction of either underground workings or open pits so as to decrease powder consumption and to increase blasting efficiency. Hence it is of prime importance that a method of determining accurately the tensile strength of rocks be developed. The U. S. Bureau of Mines states' that no standard methods have been proposed by the ASTM for testing the tensile strength of rock. The method described in the Bureau publication is said by them to be unsatisfactory. A similar test that has been used in our laboratory in place of the USBM test is shown in Figs. 1 and 2. h this test the core is placed in a set of grips that has been designed for one particular size core. The grips are designed to distribute the stress around the core if they are tightened correctly. A universal joint or a flexible cable may be used in conjunction with the apparatus to prevent bending or twisting of the specimen. The main difficulty encountered with the system shown is the failure of the specimen within the grips. The possible cause of the failure within the grips may be due to a stress concentration set up by the uneven tightening of the grips. This method can be used only for tests on cores, and even then has been found to be totally unsatisfactory because of the failure within the grips. The U. S. Bureau of Reclamation has been using a test similar to the sketch shown in Fig. 3. Sulfur is cast around each end of the specimen to form a bearing surface and then a ring grip is used to apply a tensile stress. The grips are in contact with the sulfur cast and do not touch the specimen. This method is unsatisfactory, apparently because a large number of the specimens appear to break within the sulfur cast. Professor Wuerker of the University of Illinois uses the test shown in Fig. 4.' Professor Wuerker states2 that this method has given definite and reproducible results with the weakest as well as with the strongest rocks. The test is a supplement in all cases where cores cannot be obtained. The principle and equipment are the same as for the test for tensile strength of hydraulic-cement mortar. Soft

Jan 1, 1961

By R. C. Allen

About four years ago the writer proposed a revision of the correlation of the Huronian formations in Michigan, and noted the bearing of the question on the correlations of the Huronian rocks in Wisconsin and Minnesota.1 Dr. C. K. Leith opposed this revision and argued for the retention of the correlations of the United States Geological Survey, published in 1911,2 for which he and Dr. Van Hise were mainly responsible. As late as June, 1917, Harder and Johnson, following Leith, thought it "premature to change radically a correlation based on years of careful field work."3 The work of Wolff on the Mesabi and Cuyuna Ranges, of Hotchkiss on the Gogebic Range (unpublished), and of the writer and assistants on the Michigan ranges, together with data developed by exploratory and mining operations, has introduced so many new facts not recognized in the scheme of the U. S. Geological Survey that the correlations of 1911 must be considered, in some important respects, obsolete. Indeed, new data are accumulating so rapidly that any classification, which for the moment may seem best to explain the facts, is almost immediately modified or refined by further observations. The problem of Huronian correlations is difficult, but interesting and important. With the aid of fossils, stratigraphers of the post-Algonkian formations have been able to show that slight disconformities mag separate strata of vastly different ages, and that within physically conformable strata may be concealed a hiatus of great magnitude. In the non-fossiliferous Huronian group, minor physical breaks in the strata are only beginning to attract attention, and it is too early to discuss what bearing these will have in correlating the formations of one area with those of another, but it is safe to say that the "lost intervals" which are not disclosed by physical relationships will remain forever lost; therefore we may not hope to discover the ultimate truth concerning the

Jan 1, 1920

By J. B. Macelwane

Historically whenever application of scientific results to a new problem required the special experimental background, the economic outlook and the practical knowledge characteristic of the engineer, a curriculum in that type of engineering based on the professional requirement grew up in the engineering colleges. This is precisely what is happening now in geophysical engineering. THE Mineral Industry Education Division of AIME has long been interested in geophysical education. Organized in 1938, a Committee on Geophysical Education presented a number of reports in succeeding years. The AIME is an engineering society; hence it might be expected that the interest of the Mineral Industry Education Division would have centered about the relation of courses in geophysics to engineering education. However, this was not the case. The burden of the discussion held under the auspices of the Committee on Geophysical Education bore on geophysics in general and particularly on its relation to geology. In the decade that has passed since those meetings much water has flowed under the bridge. Not only have the geophysical sciences developed at an extraordinarily rapid rate but the practical importance and the range of their applications have spread in ever widening circles and have even assumed a very prominent place in research programs of the military, the Army, the Navy and, particularly, the Geophysical Research Directorate of the Air Force at Cambridge, Mass. So enormously have the geophysical sciences as such grown in scope and in degree of specialization that no one man in a lifetime of study can hope to master the theoretical and experimental complexities or even to follow intelligently in the published literature all the varied accomplishments of basic research in these fields. As in the other sciences, most of the results of geophysical research have potential economic value and are being applied to a wider and wider range of human needs. Here we see a parallel with the older sciences and their relation to engineering. Whenever the applications of scientific results required the special experimental background, the economic outlook, and the practical knowledge characteristic of the engineer, a curriculum in that type of engineering grew up in the colleges and universities. In the words of the "Report of the Committee on Adequacy and Standards of Engineering Education" in the January 1952 number of the Journal of Engineering Education: "Engineering education in America was not developed after a preconceived plan. It evolved in parallel with the needs of a growing country, a country engaged in the development of a vast industrialization. From the first it filled a practical need, and its design emanated largely from an evaluation of the professional requirement." The advent of the railroad created a need for scientifically trained engineers and the response was the curriculum in civil engineering. The development of steam power created the demand for a curriculum in mechanical engineering. Neither of these types of engineers was trained to cope with the requirements of electrical power, and so there came to be a curriculum in electrical engineering. The advent of radio communication and of electronics during the first World War and in the years that followed resulted in the establishment of electronics engineering, sometimes within the curriculum in electrical engineering and sometimes independent of it. The complexities of industrial management have created an ever increasing demand for industrial engineers and the consequent building up of a curriculum in industrial engineering. The wide industrial application of chemical processes required a type of engineer whose background was training in chemistry but who was able to design processes and plants on an industrial scale; hence we have the curriculum in chemical engineering. The advent of the airplane created an entirely new set of problems which were solved by the training of aeronautical engineers. Many of these have called for more and more science and mathematics. Such was the history of the older engineer-

Jan 1, 1953

THE purpose of this chapter is to present a general outline of the basic open-hearth process for the benefit of students, practicing open-hearth operators, and metallurgists who wish to review the subject. The discussion is limited to a description of the sequence and purpose of the operations, illustrated by data and examples. Subsequent chapters deal with more detailed and fundamental studies of the subject. The function of the basic open-hearth furnace is to convert various types of ferrous material into finished steel of given composition and quality. In comparison with other steel-making methods, the basic open-hearth process is one of the most versatile, both from the stand- point of the raw materials that can be used and the types of steel that can be produced. The process can be considered as a sequence involving melting, refining, and deoxidation. In the case of some types of liquid-metal charges the melting stage is not present, but refining and deoxidation in varying degrees are fundamental features of the process. GENERAL DISCUSSION OF THE BASIC OPEN-HEARTH PROCESS The first consideration in open-hearth practice is the type of charge on which the operation is based. This consists of three components-fluxing, oxidizing, and metallic materials. Fluxes. In the basic process the fluxing material is primarily lime, added in the form of either limestone (CaC03) or burnt lime (CaO). This is supplemented by magnesia (MgO) and lime from the furnace bottom and banks. The function of these fluxes is to form a slag with the silica (SO2), manganese oxide (MnO), iron oxides (FeO and Fe203), and phosphorus oxide (P205) that are produced by the oxidation of varying amounts of the silicon, manganese, iron, and phosphorus in the charge during melting and refining. The slag, composed of the basic fluxes and the neutral and acid oxides, floats on top of the steel bath when the charge is melted. The composition of this slag depends on the amount of each slag-forming element present in the charge and on the extent of oxidation of these elements during the course of the

Jan 1, 1944

By Henry J. Welge

The approximate methods which are now in use for calculating oil displacement from reservoirs by gas-cycling or gravity-drainage at constant gas pressure, or by water flooding, make use of fundamental relationships derived by Leverett' and Buckley and Leverett.2 The mathematical equations needed are derived by applying Darcy's law to the flowing phases, and by material balance considerations. ln general, any treatment of this type gives. for any particular exploitation time considered, a plot of oil saturation against distance in the reser-voir. The oil recovery must then be obtained by integrating in some manner the area under the plot. A useful analytical method has been derived for computing the average saturation, and hence the oil recovery. Use of this method simplifies the calculations because it makes unnecessary any numerical integrations. and even the saturation distribution plots are not needed. A further advantage of the method is that knowledge of the relative permeabilities is required only for a limited and intermediate saturation range. In both the Buckley and Leverett method and the method discussed here, a linear sand section is assumed, and in the case of gas drive the gas pressure is assumed sufficiently constant both with respect to reservoir position and time so that changes in gas density. solubility, or reservoir volume factor are negligiklle. Thus, the exploitation contemplates oil displacement as by an immiscible phase. Examples are given to illustrate how the new method can be used. INTRODUCTION AND THEORETICAL BACKGROUND This paper treats a simplified method for computing oil recovery when the oil is displaced, from the reservoir sand by a fluid which, within the limits of accuracy desired, can be assumed to be incompressible and immiscible with the oil. The method makes use of two basic relations originally developed for the case of water displacing oil. However, the case of gas displacing oil saturated with gas at a constant (or nearly constant) pressure may also be considered a displacement by an immiscible fluid. This is possible for the reason that the concentration of the gas in the oil never changes if tile pressure is fixed. consequently, any additional free gas must remain undissolved in the oil, and so must act essentially as an immiscible phase. For convenience, the cape of gas drive will be considered first. Both of the two basic relations needed refer to a linear reservoir, or one which may be somewhat idealized so that a constant cross-section is exposed to fluid flow. Further, the displacing phase is injected at one end, or face; of the reservoir, while the produced fluids are understood to emerge at one point only. which is the opposite face of the reservoir. As indicated in Fig. 1, the reservoir may he inclined by some angle 8. The first of the required equations may be derived by applying Darcy's law to both displacing and displaced phases, and subtracting the two equations. The result for water drive has been given previously, as Equation (13) of the reference by

Jan 1, 1952