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By K. C. Ten Brink, Allen D. Garrison, P. B. Elkin

It is the purpose of this article to present the results of an investigation of certain clay and shale suspensions having viscosities that are materially influenced by fluid motion, and to discuss the bearing of these results upon the choice of policy in the control of drilling fluids. A previous article described the design and the characteristics of an instrument adapted to measure the viscosity of plastic suspensions during continuous uniform motion and at a variety of speeds.' It has long been recognized that the viscosity of a clay suspension depends on the past history of the fluid motion. Since an abundance of literature is available on this phenomenon,2 it is not necessary to describe it in more than general terms. It is usually observed that rapid motion reduces the viscosity of a clay suspension, and that some time is required for the viscosity to fall to its equilibrium value after the steady motion is started. On reducing the speed of motion to some lower value, the viscosity again rises, but it also requires some time to attain a steady viscosity value at the slower rate of motion. Thus clay suspensions are usually observed to be increasing in viscosity as time passes when the measurement has been immediately preceded by fluid motion that was more rapid than that employed in the measurement. And it is usually observed that the viscosity falls as time passes when the measurement has been preceded by more quiescent conditions. Reed,3 and Broughton and Hand4 have reported a condition of observation of clay suspensions in which the viscosity was observed to fall during the first few moments of steady motion, and rise thereafter. The characteristics of the new instrument are particularly well adapted to studies of this kind. With it we have been able to observe all of the phenomena described above, and it is important to understand their nature because they all occur at some time during normal drill-

Jan 1, 1940

By Allen Garrison

IT is the purpose of this article to present. the results of an investiga-tion of certain clay and shale suspensions having viscosities that are materially influenced by fluid motion, and to discuss the bearing of these results, upon the choice of policy in the control of drilling fluids. A previous article described the design and the characteristics of an instru-ment adapted to measure the viscosity of plastic suspensions during continuous uniform motion and at a variety of speeds.1 It has long been recognized that the viscosity of a clay suspension depends on the past history of the fluid motion. Since an abundance of literature is available on this phenomenon,2 it is not necessary to describe it in more than general terms. It is usually observed that rapid motion reduces the viscosity of a clay suspension, and that some time is required for the viscosity to fall to its equilibrium value after the steady motion is started. On reducing the speed of motion to some lower value, the viscosity again rises, but it also requires some time to attain a steady viscosity value at the slower rate of motion. Thus clay suspensions are usually observed to be increasing in viscosity as time passes when the measurement has been immediately preceded by fluid motion that was more rapid than that employed in the measurement. And it is usually observed that the viscosity falls as time passes when the measurement has been preceded by more quiescent conditions. Reed,3 and Broughton and Hand4 have reported a condition of observa-tion of clay suspensions in which the viscosity was observed to fall during the first few moments of steady motion, and rise thereafter. The characteristics of the new instrument are particularly well adapted to studies of this kind. With it we have been able to observe all of the phenomena described above, and it is important to understand their nature because they all occur at some time during normal drill-

Jan 1, 1939

By E. Robert Ruhlman

The term potash refers to potassium oxide (K2O), a compound not found in nature or produced by man but used as a basis for comparison of all potassium compounds and now is applied generally to various compounds of potassium used by agriculture and industry. Potassium, the last of the three major plant foods to be used in appreciable quantities by agriculture, was originally produced only from organic materials for chemical uses. The first recorded identification of a mineral source of potassium was in 1797; but, until the discovery in 1839 of the large deposits of soluble potassium salts in Germany and their development in 1860-61, nearly all potassium compounds continued to come from organic sources. With the importance of potash to plant life discovered in 1840 by von Liebig and the production of potash in Germany after 1861, agriculture soon became the major consumer of potash. In 1958 agriculture accounted for about 95 pct of the total potash consumption; the chemical industry used the remaining 5 pct. Mineralogy and Geology Potassium, an important constituent of the earth's crust, occurs in many forms in numerous rocks and minerals, including water solutions, but is not found in its native state. Twenty-five of the more important potash minerals are listed in Table 1. The properties of the five potash minerals most common in Permian salt formations follow: Sylvite is isometric; has a hardness of 2, a specific gravity of 1.98, vitreous luster, and cubic cleavage; and ranges in color from clear to brick red. In taste it is similar to halite but has a sharper taste and a cooling effect on the tongue. It is very plastic under pressure. Langbeinite is isometric; has a hardness of 4, a specific gravity of 2.82, vitreous luster, conchoidal fracture, and no cleavage; and ranges in color from clear to gray. It is taste- [ ] less, somewhat granular, and slowly soluble in water. Polyhalite is triclinic; has a hardness of 3, a specific gravity of 2.77, and dull luster; and

Jan 1, 1960

By J. A. Danko, C. D. Pears, L. D. Schmidt, J. P. McGee

This paper describes a pilot plant built on the campus of West Virginia University by the Federal Bureau of Mines station at Morgantown, West Virginia, for gasifying pulverized coal in a mixture of oxygen and steam at pressures in the gasifier up to 450 psig. The work upon which this report is based was done under a cooperative agreement between the Bureau of Mines and the West Virginia University. The goal of Bureau of Mines work at Morgantown is development of a low-cost process for producing mixtures of carbon monoxide and hydrogen for the modified Fischer-Tropsch synthetic-fuel plants, which may be shifted to produce hydrogen for coal-hydrogenation plants. Gasification with oxygen offers the inducement that the gas may be generated at the pressure at which the gas will be utilized in a gas-synthesis plant. Since the optimum pressure for the synthesis appears to be about 400 psig, the gas should be produced at approximately 450 psig to take care of pressure drops in the purification train and control valves. If the gas is generated at the pressure of utilization, only the oxygen need be compressed, not the raw synthesis gas. This means a saving in power of 5 hp per hour per 1000 cu ft (CO + H2), which is approximately a saving of 4 cents per gallon of gasoline. For example, consider a commercial plant generating 18,000,000 standard cubic feet per hour of raw gas that would produce approximately 10,000bbl of liquid product per stream-day. Assume that this gas would be 85 pd CO + H2 and that the oxygen required would be 320 cu ft per 1000 cu ft of CO + H2. The following estimate is based on a commercial centrifugal compressor. If the 18,000,000 std cu ft per hour of synthesis gas is compressed to 450 psig with 74 pd efficiency, 107,000 hp is required for compression. If the synthesis gas is generated at 450 psig pressure, only

Jan 1, 1953

By S. Skowronski

The melting of cathode copper, ususally containing 95.98+ per cent. • Cu, would appear to be a simple matter. Owing to the well known affinity of copper for sulfur, however, so much sulfur is absorbed by the copper during the operation that a long and expensive refining process is required to remove it, and the final product is inferior in purity and lower in electrical conductivity than the original cathode copper. The furnace operation, as now conducted, includes the following stages: 1. Charging the cathodes into the furnace. 2. Melting the cathodes. 3. Oxidizing period—saturating the copper with cuprous sub-oxide and bringing the metal to the condition known as "set copper;'' this is now done by blowing air into the molten bath of metal. 4. Reduction period, otherwise known as "poling," whereby the oxygen previously added is removed by covering the molten bath completely with coke or charcoal and introducing large poles of green wood; this reduces the cuprous sub-oxide, bringing the copper to the "tough pitch" stage ready for casting. 5. Casting Period. Many experiments have been made to obviate the long periods of oxidation and subsequent reduction, with no success. While the copper first cast will be good, as indicated by the set surface of the bars, it is impossible to hold it to the "tough pitch" condition, and long before the whole charge has been poured the copper will become "overpoled," entailing numerous difficulties. Sulfur has always been blamed by the furnace men as the reason why this refining process is necessary, yet the literature on the subject does not sufficiently emphasize how small a proportion of sulfur will ruin copper for practical purposes. The sulfur absorbed by copper during the melting period comes from two sources: (1) the sulfate left on the cathode sheets in the tank houses; (2) the fuel. The percentage of sulfates on the cathodes is variable, and depends on the care taken in washing the cathodes after removing

Jan 1, 1919

By Clemens Jones

The peculiar property of the lode-stone has been known for many centuries. It was very early observed that, by contact with it, iron is magnetized; and it is needless to dwell here upon the history allied to this discovery, now constituting the wonderful science of magnetism. Deposits of magnetic ore are distributed all over the world. The ore is sometimes very rich and comparatively free from gangue, sometimes sparsely disseminated in the native rock. These bodies of lean ore often cover large areas. Modern ingenuity has utilized the principle of the magrtet, originally derived from the ore itself, and really belonging to the time of Plato and Theophrastus, to separate the magnetic ore-particles from the rock which has previously been crushed. This process recovers the ore in the state of a concentrate very rich in iron and, in some cases, desirable for Bessemer purposes. The magnetic separator is no longer a novelty. It was only at the last meeting of the Institute in New York, that Messrs. Birkinbine and Edison (Trans., xvii., 728) and Mr. Robert Cook (Ib., 599) described some of' the principal designs of apparatus in use. E. S. Dana classifies the natural magnetic minerals in the following order: magnetite, pyrrhotite, franklinite, almandite and minerals " containing considerable FeO." Of these, ferroso-ferric oxide, or magnetite, is the type. The proportionate amount of ferrous oxide essential to magnetize the compound, is not established. Ferrous oxide appears to be the only magnetic oxide of iron. Tissandier (Compt. Rend., lxxiv., 531) produced ferrous oxide in the anhydrous state, by the action of carbon dioxide on pure iron at a red heat, according to the equation : Fe + CO2 = FeO + CO. This is black, crystalline and magnetic. Heated to redness in the air, it is converted into Fe3O4. Sidot (Compt. Rend., lxvii., 175) has also produced an oxide exhibiting magnetic polarity, by heating ferric oxide to a temperature

Jan 1, 1891

By L. C. McCabe

This paper is a progress report on a study of the distribution of the banded ingredients (Figs. 1 and 2) in Illinois screenings and the method of determining their distribution. Proximate analyses and screen tests1 have been reported and a further report on the washability characteristics of the screenings is in preparation. The microscopic study of the screenings is not yet far enough advanced to permit a conclusive report on the effect of mining, screening and washing on the distribution of the banded ingredients in the coals of Illinois. However, considerable fundamental data have been collected as a background for the screenings investigation and for a proposed study of fuels composed of known quantities of vitrain, clarain and fusain, the three common banded ingredients of Illinois coals. These fundamental data and the preliminary information now available from the microscopic study of screenings are broadly indicative of the reaction of the coals to the physical processes affecting them in mining and preparation. Proximate analyses of samples of vitrain, clarain, and fusain from several Illinois mines have been published2, but those given in Table 1 serve to show the differences that are apparent in proximate analyses. The vitrain samples are consistently low in ash, and the unit-coal value is uniformly lower than in clarain. The average fuel ratio (F.C./V.M.) of the vitrain samples in the table is 1.57 whereas the clarain average is 1.42. The fusain analyses vary considerably in ash and moisture. In the two samples from this mine the moisture values range from 8.99 to 22.80 and the ash from 4.86 to 16.91 per cent. Fusain has higher fixed carbon than either vitrain or clarain but the percentage is erratic from sample to sample. The relative proportions of the banded ingredients in the Herrin (No. 6) coal in Illinois is reasonably well known but detailed information

Jan 1, 1936

By L. C. McCabe

This paper is a progress report on a study of the distribution of the banded ingredients (Figs. 1 and 2) in Illinois screenings and the method of determining their distribution. Proximate analyses and screen tests1 have been reported and a further report on the washability characteristics of the screenings is in preparation. The microscopic study of the screenings is not yet far enough advanced to permit a conclusive report on the effect of mining, screening and washing on the distribution of the banded ingredients in the coals of Illinois. However, considerable fundamental data have been collected as a background for the screenings investigation and for a proposed study of fuels composed of known quantities of vitrain, clarain and fusain, the three common banded ingredients of Illinois coals. These fundamental data and the preliminary information now available from the microscopic study of screenings are broadly indicative of the reaction of the coals to the physical processes affecting them in mining and preparation. Proximate analyses of samples of vitrain, clarain, and fusain from several Illinois mines have been published2, but those given in Table 1 serve to show the differences that are apparent in proximate analyses. The vitrain samples are consistently low in ash, and the unit-coal value is uniformly lower than in clarain. The average fuel ratio (F.C./V.M.) of the vitrain samples in the table is 1.57 whereas the clarain average is 1.42. The fusain analyses vary considerably in ash and moisture. In the two samples from this mine the moisture values range from 8.99 to 22.80 and the ash from 4.86 to 16.91 per cent. Fusain has higher fixed carbon than either vitrain or clarain but the percentage is erratic from sample to sample. The relative proportions of the banded ingredients in the Herrin (No. 6) coal in Illinois is reasonably well known but detailed information

Jan 1, 1936

This report presents the comments of members of the Institute's Sub-committee on Physics of Mine Ventilation on the proposals of a special committee of the Institute of Mining Engineers (London). This report is as follows: THEORY OF MINE VENTILATION Abstract of a report submitted June 16, 1925, to the Council of The Institution of Mining Engineers by a Special Committee Laws of Flow of Aib The law of flow of air in mine galleries is, at present, expressed by two formulas differing slightly in shape but both derived from the original hydraulic formulas of Chezy and others. These formulas are: The Atlcinson Formula.—Pa = KsV2, which in transformation becomes a3 where P = pressure producing flow; K = coefficient of friction; s = surface of the mine galleries; V = velocity of flow; Q = rate of flow; a = area of mine galleries. This formula is especially applicable to mine galleries, but is unwieldy in application, as in many problems we are dealing with changes produced in the same set of airways when K, s, and a are assumed not to change, and the only variables are P and Q. Great uncertainty prevails as to the exact values to be assigned to the coefficient K in different types of airway, as different workers have given widely differing values. This formula assumes: (I) That resistance to flow is independent of the pressure within the gallery. (2) That changes in volume within the limits of pressure ordinarily met with may be neglected. (3) That changes in density and viscosity and mode of flow of the air may be neglected. (4) That the coefficient K is a constant. (5) That P is proportional to the square of the velocity. We cannot find any reliable experimental work leading us to conclude how far these assumptions are justifiable in mining practice. Equivalent Orifice Formula.—The fundamental form of this formula is Q = ~nA.\/2~11

Jan 1, 1927

By Walter J. Karplus, Otto J. M. Smith

The transient response of earth formations may be tlcter.171ined by means of four electrodes mounted coli-rienrly on n sonde. Exponentially decaying current pules are applied to one pair of electrodes and the re.rrrlting voltage transient at the other pair is recorded. It is shown by theoreticol analysis and verified by laboratory experiments that this arrangement readily yields the direct resistivity of the formation and provides valrrable additional information as well. INTRODUCTION Although electrical transients have been employed with moderate success in geophysical prospecting, their application to well logging has received virtually no attention in technical literature. In the conventional direct resistivity logging methods only the zero frequency impedance of the formation under study is measured, and no information is obtained regarding its reactive characteristics. Since the use of certain transients appears to offer some advantages in this respect, experiments were performed on a laboratory scale to investigate this possibility. This investigation was limited to a study of a four-electrode array where both the receiving and transmitting electrode pairs are mounted on a logging sonde, and decaying exponential pulses are applied to the transmitting electrodes. THEORY Given an electrode configuration as shown in Fig. I, located in a homogenous medium of resistivity p, if each electrode has an effective radius, r, which is small compared to the spacing, s and a, it is easy to show by integrating the volume resistivity that the input resistance, Rrw, of the transmitting electrodes is Rxw=p/2pr If a capacitor of capacity C, charged to a voltage Em, is suddenly connected to these electrodes, the resulting current, I(t), will then be The voltage transient, E(t), at the receiving electrodes may then be found by substracting the resulting potential at electrode Y from that appearing at electrode Z. and by inserting Eqs. 1 and 2 Integrating Eq. 4 with respect to tim

Jan 1, 1957

By F. E. Wood

This paper is written primarily as a discussion of Dr. W. P. Hase-man's paper on "A Theory of Well Spacing"' and presents briefly the production records, and intensity and rate of development in a large portion of the two principal producing sands in the Salt Creek field, Wyoming. The study includes 1350 wells, 160,000,000 bbl. production, well spacings varying from two to seven wells per 40 acres and early and late development. The general conclusions to be derived from this study are: 1. It is impossible to formulate a mathematical rule to apply to well spacing in the Salt Creek field. 2. Each tract is a separate problem. 3. Tracts first drilled produce the most oil, with many exceptions. 4. Initial production is not a reliable index to the relationship between past, current, or future production. 5. Wells which have produced the most oil in the past are not necessarily yielding the greatest current production nor will they yield the greatest future production. In fact, wells which have yielded the greatest past production will, in at least one-half the cases, make less oil currently or in the future than wells which have produced a smaller quantity of oil in the past. 6. The following is a safe rule to apply in well spacing in the Salt Creek field: (a) If the drilling of an additional well on a tract results in a sustained increased production, with prospects of making a profit, the tract is not overdeveloped and additional wells might be drilled. (b) If the drilling of an additional well does not effect a sustained increase in the production of a tract, the tract is fully developed. Second Wall Creek Sand The Second Wall Creek sand, covering 20,000 producing acres, is the principal producing horizon in the Salt Creek field; 1610 wells are producing at this time from this sand. This paper deals with hut a portion of the entire field including 10,680 of the more productive acres,

Jan 1, 1930

By D. T. MacRoberts

A simple disturbance in a gas reservoir travels with a finite velocity which is nearly independent of the amplitude of the disturbance. As a result very complex transients may be set up which seriously affect observation at a well. The time of transient is much longer than commonly supposed. INTRODUCTION A change in pressure at a gas well is not propagated through the reservoir instantaneously but with a definite fin- ite velocity. Knowledge of the period ! of this transient is of value because: 1. Observations of pressure and flow-rate during the transient may affect interpretation of back-pressure tests. 2. Interference effects between wells may be used to determine continuity of formation. 3. Additional information concerning the physical characteris- tics may possibly be deduced from the behavior of a well during the transient. MATHEMATICAL DEVELOPMENT It will be assumed that the well is initially closed in and that the pressure is constant throlughout the reservoir. As the initial disturbance passes outward from the well it is further assumed that a logarithmic pressure distribution is established between the most distant point reached and the well, so that: <l> = ((/)r-<t>w) I ------------ + (/) . (1) Manuscript received at office of the Branch September 15. 1948. Paper presented at Branch Fall Meeting, Dallas. Texas. Oct. 4-6, 1948. r. = distance to any point between r and rw r = radius of drainge iw= radius of well (/) = potential (P for incompressible fluids, P2 for perfect gases) Up to the time the effect reaches the point r the production from the well will be: W= (Pr-P,,,) . (2) i b W = volume produced t = sand thickness F = fractional porosity Pr = reservoir pressure Pm = average pressure between r and rw Pb = atmospheric Pressure All pressures will subsequently be stated in atmospheres and the constant Pb will be omitted. This will be produced at a rate: dw t k (Pr³-PW2) do d 0 - . (3) log — Pw = pressure at the well k = permeability 0 = time = viscosity

Jan 1, 1949

By D. T. MacRoberts

A simple disturbance in a gas reservoir travels with a finite velocity which is nearly independent of the amplitude of the disturbance. As a result very complex transients may be set up which seriously affect observation at a well. The time of transient is much longer than commonly supposed. INTRODUCTION A change in pressure at a gas well is not propagated through the reservoir instantaneously but with a definite fin- ite velocity. Knowledge of the period ! of this transient is of value because: 1. Observations of pressure and flow-rate during the transient may affect interpretation of back-pressure tests. 2. Interference effects between wells may be used to determine continuity of formation. 3. Additional information concerning the physical characteris- tics may possibly be deduced from the behavior of a well during the transient. MATHEMATICAL DEVELOPMENT It will be assumed that the well is initially closed in and that the pressure is constant throlughout the reservoir. As the initial disturbance passes outward from the well it is further assumed that a logarithmic pressure distribution is established between the most distant point reached and the well, so that: <l> = ((/)r-<t>w) I ------------ + (/) . (1) Manuscript received at office of the Branch September 15. 1948. Paper presented at Branch Fall Meeting, Dallas. Texas. Oct. 4-6, 1948. r. = distance to any point between r and rw r = radius of drainge iw= radius of well (/) = potential (P for incompressible fluids, P2 for perfect gases) Up to the time the effect reaches the point r the production from the well will be: W= (Pr-P,,,) . (2) i b W = volume produced t = sand thickness F = fractional porosity Pr = reservoir pressure Pm = average pressure between r and rw Pb = atmospheric Pressure All pressures will subsequently be stated in atmospheres and the constant Pb will be omitted. This will be produced at a rate: dw t k (Pr³-PW2) do d 0 - . (3) log — Pw = pressure at the well k = permeability 0 = time = viscosity

Jan 1, 1949

By C. Altstetter

THE work herein reported is restricted to the carbides which occur in quenched and tempered AISI 43XX steels with carbon contents up to 0.40 pct and silicon additions of up to 3 pct. In view of the instability and extremely small size of the carbides formed at low tempering temperatures, the technique for successfully preparing specimens for X-ray diffraction will be outlined. The alloys listed in Table I were obtained through the courtesy of the United States Steel Corp. in the form of 1/2-in. rounds forged from 100 lb. induction furnace heats (except for 4337 which was a commercial heat). The stock was normalized and then swaged and drawn to 15 mil wire with anneals at 1200F between passes. The wire was austenitized for 45 min in evacuated vycor capsules and quenched into iced brine with simultaneous smashing of the capsule. Tempering was done in air with a water quench after tempering. The carbides were extracted in a simple cell using a solution of 1M KC1 and 0.5 pct citric acid with an initial current density of 0.1 amp per sq cm. One end of a short length of wire was immersed in the solution, and the current at constant voltage was noted as a function of time. After about an hour the current dropped sharply because of the decrease in specimen cross-section. At this point it was found that the dissolution could be stopped and that the very fine wire which then resulted was just large enough to permit handling of the extracted precipitate still clinging to it, yet so small that it diffracted and absorbed only a negligible amount of the X-radiation. This rod of residue with a convenient handle of undissolved wire was rinsed in distilled water. alcohol, and acetone. Then it was dipped in a thin solution of cellulose-acetate cement and dried in vacuum. The resulting specimen was straight, uniform in density, easily handled, but most important, was completely sealed and never exposed to air. Furthermore, the residue had never been subjected to strong acids or rough handling such as in the extraction-replica technique or in the complete extraction to a powdered residue. It was found that improperly coated specimens were pyrophoric, turning to oxide with a dull red glow as they were exposed to air and yielding patterns of Fe2O3 and Fe3O4. The steels containing 3 pct Si were especially difficult to prepare for this reason. The specimens were put in a 57 mm Straumanis camera with double pinholes or slits and irradiated with filtered-chromium radiation. Readable patterns were obtained in less than an hour. A preliminary finding of some note was that for both tempered and as-quenched specimens of steels 4337 and 4337 (1.5 Si). M23C6 patterns were found along with the patterns of other constituents of the residues. This result was somewhat surprising in that previous investigators had reported that this carbide did not appear in a 0.38 pct C, 0.48 pct Mo steel1 or in chromium steels of less than about 10 pct Cr.2 Although the total amount of carbide-forming alloying elements is less than 2 pct, due to their mutual interaction and the action of the plastic deformation in promoting equilibrium, this carbide was able to form even in the steel containing 1.5 pct Si. M23C6 was not detected in the 4337 (3.0 Si) steel and the lower-carbon steels were not investigated in this condition. It is very likely then that the steels studied herein underwent a fourth stage of tempering during the anneals at 1200°F. This result has significance in that even a small amount of undissolved M23C6 in a low-carbon, low-alloy steel would exert a large effect on its hardenability. Its presence would also influence the mechanical properties by decreasing the carbon content of the matrix. Annealing in vacuum for 1 to 4 hr in the austenite field removed all traces of MZ3C+ The results on carbide precipitation during tempering, summarized in Table I, are in agreement with those of Klingler et al.3 for the higher carbon steels. For the AISI 4337 steels it is noteworthy that in the steels with added silicon the E carbide persists to longer times and higher temperatures and that silicon delays the formation of cementite. The results for the lowzr-carbon steels parallel those of the higher-carbon grade. The appearance of E carbide in the AISI 4315 is significant. There is considerable disagreem-nt in the literature as to whether this carbide forms in the tempering of steels containing less than about 0.2 pct C. Following the detection of E carbide in a 0.18 pct C plain-carbon steel,4 its occurrence in a steel containing chromium and molybdenum should be expected. The fact that the low-carbon steels have the same carbide-precipitation sequence as the high-carbon steels has bearing on the larger problem of the exact tempering reactions in all steels. Following the suggestion of Roberts et al.,&apos; the first stage has been generally assumed to result in a metastable equilibrium of c carbide and martensite of about 0.25 pct C. From this it was concluded that a steel having less than 0.25 pct C should then be under-saturated with respect to c carbide and should not precipitate this carbide upon tempering. In view of the experimental findings of c carbide in steels hav-

Jan 1, 1962

By R. C. Ferguson, Harlowe Hardinge

Oscar Johnson—In my opinion, the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. Comparing the entire groups of operators with those who have had the opportunity to make slow-speed mill studies, I think you will find the latter small in numbers. Most managers want the equipment worked to its maximum output. There are, however, some installations where plant and mill sizes are such that they can do the job with reduction of mill barrel speeds. The past and the present installations of the industry are laid out to get the most capacity for the least capital outlay. This is the case even with the plants of Chile Exploration, International Nickel, Morocco, and Anaconda, now under construction or being changed. The industry recognizes that most all equipment it buys today is good and can be depended upon for efficient performance. Under this scheme of things, I am doubtful that slow-speed ball mill operation will be generally applicable. With reference to the U. S. Bureau of Mines laboratory tests, I think table II could have been omitted. It is inconclusive as to maximum efficiency for the low-pulp level mill on hard ore. There should be no question about this point. However, data on mill speeds can be found to substantiate various theories as well as refute them. Gow, Guggenheim, Campbell and Coghill, in their paper on Ball Milling,&apos; believe their 2 x 2 ft laboratory mill reflects results that can be expected from large mills. If so, then referring to their table 11, they state, "The conclusion to be drawn from this second series is that high speed, not exceeding 72 pct of the critical, favors capacity, as before, but that with proper conditions of operation high speeds may give as good efficiency values as low speeds. In this case the efficiency values are nearly constant. A horizontal curve would indicate that the amount of grinding was directly proportional to the power expended, and these tests suggest that such a coildition can be made to exist in commercial operations." Table II (From Paper by Gow et a1)2 Speed. Pot Critical 32 42 52 62 72 82 Capacity: Surface tons per hr (65- mesh) 266 42.1 54.4 65.9 74.3 74.1 Surface tons per hr (200- mesh) 56.1 87.4 112.7 137.1 154.2 153.0 Efficiency: Surface tons per net hp hr (65-mesh) 35.7 36.3 36.3 35.4 34.3 32.3 Surface tons per net hp hr (200-mesh) 75.3 75.3 75.1 73.7 71.0 66.0 Ore in mill, 1.b. 98 100 100 113 122 165 The field performance data, table 111, represents much effort in its collection and preparation. But, one must realize that there are many variables that effect the efficiency of grinding mill operation, and too much must not be assumed as to the effect of some specific change. Possibly with changes in mill speed, the results might be more consistent by also a change in ball rationing, type of ball, volume of ball charge,. p.ulp level and amount of pulp in the mill, pulp consisting, design of liner, circulating load, etc. Also, changes in ore character must be reckoned with when evaluating grinding performance. At present the Climax Molybdenum Corp. is running at much reduced capacity. Mr. James Duggan informs me that at mill speeds of 17 rpm, they save a $0.025 per ton on liners and $0.025 per ton in power, but, if the demand for molybdenum increased, he would go back to higher speed to obtain maximum tonnage, as the values from the increased tonnage would far more than offset the one half saving at the slower speed. The Jnspiration ran a six months&apos; test between mills running 21 rpm and 23.5 rpm. The slower mills ground 10 pct less ore with a slight saving per ton, but when the reduced plant tonnage was checked back into the actual cost figures of concentration, the high-speed mills with their greater tonnage showed considerable advantage. To be convinced of possible practical results from the predictions in the conclusions, I think we would have to rely on the analysis of expert cost accountants to furnish the necessary proof figures. Hardinge and Ferguson are to be commended for the work in preparing this paper. I am convinced that our Massco engineers should go into higher speeds with our equipment. Harlowe Hardinge (authors&apos; reply)—For one, I heartily agree with Mr. Johnson&apos;s opening statement that the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. It was on this basis and for this reason the paper was written. Mr. Johnson, on the other hand, takes the position that, on the whole, low speeds are not justified from the economic standpoint, basing his principal reason on the fact that lower mill speeds cut mill capacities and hence reduce the gross income from the product produced. There is no denying this point. It is almost axiomatic. It is for this very reason that the overall advantage of lower mill speeds has been discounted and even overlooked. It was for this reason mainly that the paper was written in the first place. It is one thing to plan an efficient operation at the outset, basing one&apos;s figures on the tonnage requirements at the time, and it is quite another to be confronted with the problem of increasing the output of an existing installation at a minimum of capital expenditure. Economic consideration of a new installation is greatly influenced by referring to an old one. Too often, the analyst assumes that if this practice is followed in the new installation, one would not go wrong. It is just here that he may be wrong. Past practice and low capital expenditure are all too frequently given priority over the engineer&apos;s analysis of operating costs. When we are able to start fresh, we should give proper weight to other economic factors which do not exist in an old installation. It is these economic factors that make it possible to spend at the outset just a little more money and get it back in a matter of months and effect big savings for years to come. F. C. Bond—This paper is of considerable importance in that it emphasizes a modern trend to operate ball mills at somewhat slower speeds than formerly. We have checked the data in the paper with that obtained

Jan 1, 1951

By Harlowe Hardinge, R. C. Ferguson

Oscar Johnson—In my opinion, the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. Comparing the entire groups of operators with those who have had the opportunity to make slow-speed mill studies, I think you will find the latter small in numbers. Most managers want the equipment worked to its maximum output. There are, however, some installations where plant and mill sizes are such that they can do the job with reduction of mill barrel speeds. The past and the present installations of the industry are laid out to get the most capacity for the least capital outlay. This is the case even with the plants of Chile Exploration, International Nickel, Morocco, and Anaconda, now under construction or being changed. The industry recognizes that most all equipment it buys today is good and can be depended upon for efficient performance. Under this scheme of things, I am doubtful that slow-speed ball mill operation will be generally applicable. With reference to the U. S. Bureau of Mines laboratory tests, I think table II could have been omitted. It is inconclusive as to maximum efficiency for the low-pulp level mill on hard ore. There should be no question about this point. However, data on mill speeds can be found to substantiate various theories as well as refute them. Gow, Guggenheim, Campbell and Coghill, in their paper on Ball Milling,&apos; believe their 2 x 2 ft laboratory mill reflects results that can be expected from large mills. If so, then referring to their table 11, they state, "The conclusion to be drawn from this second series is that high speed, not exceeding 72 pct of the critical, favors capacity, as before, but that with proper conditions of operation high speeds may give as good efficiency values as low speeds. In this case the efficiency values are nearly constant. A horizontal curve would indicate that the amount of grinding was directly proportional to the power expended, and these tests suggest that such a coildition can be made to exist in commercial operations." Table II (From Paper by Gow et a1)2 Speed. Pot Critical 32 42 52 62 72 82 Capacity: Surface tons per hr (65- mesh) 266 42.1 54.4 65.9 74.3 74.1 Surface tons per hr (200- mesh) 56.1 87.4 112.7 137.1 154.2 153.0 Efficiency: Surface tons per net hp hr (65-mesh) 35.7 36.3 36.3 35.4 34.3 32.3 Surface tons per net hp hr (200-mesh) 75.3 75.3 75.1 73.7 71.0 66.0 Ore in mill, 1.b. 98 100 100 113 122 165 The field performance data, table 111, represents much effort in its collection and preparation. But, one must realize that there are many variables that effect the efficiency of grinding mill operation, and too much must not be assumed as to the effect of some specific change. Possibly with changes in mill speed, the results might be more consistent by also a change in ball rationing, type of ball, volume of ball charge,. p.ulp level and amount of pulp in the mill, pulp consisting, design of liner, circulating load, etc. Also, changes in ore character must be reckoned with when evaluating grinding performance. At present the Climax Molybdenum Corp. is running at much reduced capacity. Mr. James Duggan informs me that at mill speeds of 17 rpm, they save a $0.025 per ton on liners and $0.025 per ton in power, but, if the demand for molybdenum increased, he would go back to higher speed to obtain maximum tonnage, as the values from the increased tonnage would far more than offset the one half saving at the slower speed. The Jnspiration ran a six months&apos; test between mills running 21 rpm and 23.5 rpm. The slower mills ground 10 pct less ore with a slight saving per ton, but when the reduced plant tonnage was checked back into the actual cost figures of concentration, the high-speed mills with their greater tonnage showed considerable advantage. To be convinced of possible practical results from the predictions in the conclusions, I think we would have to rely on the analysis of expert cost accountants to furnish the necessary proof figures. Hardinge and Ferguson are to be commended for the work in preparing this paper. I am convinced that our Massco engineers should go into higher speeds with our equipment. Harlowe Hardinge (authors&apos; reply)—For one, I heartily agree with Mr. Johnson&apos;s opening statement that the effect of mill speeds on grinding costs must be studied along with capital investment and dollars gathered together as profits. It was on this basis and for this reason the paper was written. Mr. Johnson, on the other hand, takes the position that, on the whole, low speeds are not justified from the economic standpoint, basing his principal reason on the fact that lower mill speeds cut mill capacities and hence reduce the gross income from the product produced. There is no denying this point. It is almost axiomatic. It is for this very reason that the overall advantage of lower mill speeds has been discounted and even overlooked. It was for this reason mainly that the paper was written in the first place. It is one thing to plan an efficient operation at the outset, basing one&apos;s figures on the tonnage requirements at the time, and it is quite another to be confronted with the problem of increasing the output of an existing installation at a minimum of capital expenditure. Economic consideration of a new installation is greatly influenced by referring to an old one. Too often, the analyst assumes that if this practice is followed in the new installation, one would not go wrong. It is just here that he may be wrong. Past practice and low capital expenditure are all too frequently given priority over the engineer&apos;s analysis of operating costs. When we are able to start fresh, we should give proper weight to other economic factors which do not exist in an old installation. It is these economic factors that make it possible to spend at the outset just a little more money and get it back in a matter of months and effect big savings for years to come. F. C. Bond—This paper is of considerable importance in that it emphasizes a modern trend to operate ball mills at somewhat slower speeds than formerly. We have checked the data in the paper with that obtained

Jan 1, 1951

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By N. F. Schulz, H. A. Lex

Representative samples of typical manganiferous iron ores from the Cuyuna Range, Minn., were reduced to the metallic iron state at temperatures just short of fusion with an excess of coke in the manner prescribed by the R-N Direct Reduction Process. The magnetic separation characteristics of the reduced ores were determined at several grinds by means of the Davis magnetic tube concentrator. The efficiency of metallic iron concentration by magnetic separation was a direct function of the degree of metallization of the ore sample and of the degree of liberation at-tained in grinding. Some improvement of liberation characteristics was observed if a small amount of sodium chloride was present in the ore during reduction. Despite the extremely fine-grained structure of the crude ores, iron concentrates containing more than 90% Fe at iron unit recoveries of 90% or more were obtained from well-metallized samples of three of the four ores tested. The rejection of manganese to the tailings corresponding to such separations varied from 80% to 95%. The manganiferous iron ores of the Cuyuna Range in Minnesota constitute a major potential source of manganese in the United States provided that a technically and economically feasible process can be devised for its recovery. The iron and manganese of these ores occur chiefly as oxides or carbonates in the form of very small, irregular, discrete grains embedded in a matrix of quartz or other siliceous gangue. The present investigation was undertaken as a sequel to an earlier one conducted jointly by the U.S. Bureau of Mines and the R-N Corp. Those results indicated that the R-N Direct Reduction Process might be a means for recovering both a metallic iron concentrate and a marketable manganese by-product from Cuyuna manganiferous iron ores.&apos; The R-N Process is one of many proposed schemes for the treatment of crude iron ores involving the di- rect reduction of the iron content to metallic iron followed by physical extraction of the iron. In general, it consists of the following stepsz2 1) Iron oxide in crushed natural ores or iron concentrates is about 95% reduced to metallic iron at elevated temperatures but without fusion in a rotary kiln in the presence of a solid carbonaceous fuel (usually coke), limestone, and combustible gases. 2) The kiln product, consisting of metallized ore, excess coke, lime, and coke ash is cooled. The excess coke is recovered and recycled to the kiln feed. 3) The metallized ore is ground for liberation and magnetically separated to yield a metallic iron concentrate. 4) The metallic iron concentrate is agglomerated by a briquetting process. The reduction kiln temperatures must be high enough for the desirable chemical reactions to proceed at practical rates without causing fusion of any of the ore constituents. The time of exposure of the ore to the reducing conditions must be ample for 90% to 95% metallization of the iron oxides present. If more than 95% of the iron is metallized, however, difficulties may arise in the briquetting step, presumably because of accompanying higher carbon content of the metallic iron. Although not always necessary, powdered limestone or dolomite may be added at some time during reduction to aid in eliminating sulfur and phosphorus from the final product.3,4 Other additives, notably sodium chloride, when present during reduction, result in improved liberation characteristics of the metallic iron from certain reduced ores.&apos;v6 Under the reducing conditions normally employed, P(co + H2)= 1 atmosphere, and 1830&apos; to 2150°F (1000° to 1170°C), the R-N Process is claimed to be adaptable to a wide variety of low, medium, and high grade iron and manganiferous iron ores. The manganese oxides and carbonates are reduced mostly to nonmagnetic MnO which is rejected to the nonmagnetic tailings. Manganese-bearing pyroxenes of the original ore, however, may be rejected poorly, if at all, apparently because these minerals occur within the iron lattice or are entrapped in the metal particles.7 The investigation was limited to studies of the Cuyuna ores listed in Table I, which were reduced to the metallic iron state under various conditions

Jan 1, 1969

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc at temperatures below 200°C has been studied using both single crystal and polycrystal samples. Anomalous results were obtained for single crystal samples, the data indicating that in some cases grain boundary diffusion predominated. These anomalous results are presumed to be due to low angle lineage boundaries in the single crystals. When volume diffusion occurred in either single or polycrystal samples, the values for the diffusion coefficient were as much as several orders of magnitude larger than would be expected from high temperature data. ONSIDERABLE work has been done on self-^-*diffusion at temperatures in the neighborhood of two thirds of the melting temperature (in OK) and higher, but very little has been done at lower temperatures. This is particularly true of self-diffusion in single crystals. This paper reports work on self-diffusion in zinc at temperatures below 200 °C where both polycrystalline and single crystal samples have been used. The measurements were made using both the sectioning and absorption techniques. The experiments on diffusion at low temperatures were initiated primarily for three reasons: to obtain data from single crystal diffusion covering a wide range of temperatures, to obtain values of the activation energy for grain boundary diffusion, and to obtain, if possible, a lower limit to the temperatures at which the absorption technique may be used. It is possible to determine whether volume or grain boundary diffusion predominates at low temperatures by analyzing the manner in which the concentration of the diffusing atoms varies with the depth of penetration. The analysis is possible only for the sectioning technique. For volume diffusion and for the boundary conditions of the present experiment, the curve of the logarithm of the concentration, C, vs the square of the penetration depth, x, is a straight line with the slope proportional to — 1/D. If grain boundary diffusion predominates, Fisher&apos; has shown that a curve of In C vs the first power of the penetration depth should be a straight line. This linear dependence of concentration on depth has been observed experimentally by several investigators. (See, for example, refs. 3 and 4.) Following Fisher&apos;s analysis, the grain boundary diffusion coefficient can be written as where 8 is the grain boundary width, D, is the volume diffusion coefficient at the temperature involved, t is the time of diffusion, C is the concentration of diffusing material, and x is the depth of penetration. A more general analysis employing the same model as Fisher&apos;s but with fewer assumptions has been given by Whipple.&apos; In contrast to Fisher&apos;s analysis the more general analysis of Whipple does not always yield a straight line relation between In C and x. Recently Turnbull and Hoffman have discussed both analyses and have applied the Fisher-Whipple model to a more refined dislocation model of the grain boundary. They have also discussed the possibility of a large effect of grain boundary direction on diffusion. In the case of the absorption technique, for which results are also given, one simply gets a value for the diffusion coefficient with no indication of the predominating mechanism. Experimental Techniques Single crystals of 99.99+ pct Zn were grown using a modified Bridgman method. Polycrystal samples were prepared in three grain sizes (small, about 4 mm2; medium, about 9 mm&apos;; and large, about 25 mmz) by quenching, air cooling, and furnace cooling. The grains of the polycrystalline samples tended to be columnar, with some preferred texture such that the c-axis was inclined at about 20" to 25" from the normal to the diffusion face, particularly in the medium and large grain size samples. The samples were cut from the rod, polished, and heavily etched, and faces cut accurately parallel using a jeweler&apos;s lathe. They were again etched to remove the lathe smear and annealed for 3 hr at 250" to 300°C. After annealing, they were etched, examined, and the orientation determined by Laue back reflection photographs. They were then electroplated with Zn. The plated surfaces were examined for uniformity; nonuniform coatings were removed by etching and the samples replated without additional preparation. For the diffusion anneals, the samples were placed in pairs, with active faces together, in evacuated Pyrex tubes. Constant temperature baths were used, and the variation in temperature did not exceed ±l°C, Diffusion runs were made at l00°,

Jan 1, 1957

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2&apos;s are based mainly on CO2-natural gas mixtures. Poettmann&apos;s work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.&apos;8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966