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By W. W. Whitaker, C. W. Manry, R. H. McLean

In an eccentric annulus, cement may favor the widest side and bypass slower-moving mud in the narrowest side. Tendency of the cement to bypass mud is a function of the geometry of the annulus, the density and flow properties of the mud and cement and the rate of flow. Bypassing can be prevented if the pressure gradient protluced from circulation of the cement and buoyant forces exceeds the pressure gradient necessary to drive the mud through the narrowest side of the annulus at the same velocity as the cement. In the absence of buoyant forces, one requirement for this balance is maintenance of the yield strength of the cement greater than the yield strength of the mud multiplied by the maximum distance from the casing to the wall of the borehole and divided by the minimum distance. If the yield strength of the cement is below this value, bypassing of mud cannot be prevented unless buoyant forces or motion of the casing significantly aid the displacement. INTRODUCTION Successful primary cementing leaves no continuous channels of mud capable of flow during well treatment and production. Prevention of channels requires care. Tep-litz and Hassebroek provide evidence of channels of mud after primary cementing in the field.' Channeling of cement through mud in laboratory experiments has also been reported.'-' Recommendations for improving the displacement of mud include (1) centralizing the casing in the borehole,'-" 2) attaching centralizers and scratchers to the casing and moving it during displacement,18 "3) thinning the isolating the cement by plugs while it is circulated down the casing,%( (5 establishing turbulence in the cement," and (6) holding the cement slurry at least 2 lb/gal heavier than the mud and circulating the cement slurry at a very low rate of flow.' Although much has been written about the above parameters, the relative importance of each has not been well defined. In this investigation, the mechanics of mud displacement are described through results from analytical models and experiments. The model chosen — a single string of casing eccentric in a round, smooth-walled, impermeable borehole — is analagous to casing centralized in a borehole which is not round and to placing more than one string of casing in a borehole. In each, some paths for flow are more restricted than others. A fluid flowing in the borehole may seek the least restricted, or most open, path. This tendency for uneven flow can lead to channeling of cement through mud unless preventive measures are taken. The analytical models describe channeling and give means of balancing the flow. Experimental data test the analytical models and illustrate effects of motion of the casing, differences in density and mud's tendency to gel. Results are encouraging. Piston-like displacement of mud by an equal density cement slurry is possible through proper balance of the flow properties of the mud and cement slurries to the eccentricity of the annulus. The more eccentric the annulus, the thicker must be the cement relative to the mud. If proper balance is not achieved. bypassing of mud by cement cannot be prevented without assistance from motion of the casing or buoyant forces. Increasing the rate of flow can help to start all mud flowing but cannot prevent channeling of cement through slower moving mud in an eccentric annulus. Thinning the cement slurry tends to increase channeling although the extent of turbulence in the annulus may be increased. Description of flow in an eccentric annulus begins in the next section. It is assumed that (1) the casing is eccentric and is stationary, (2) the mud and cement slurries have the same density and (3) the gel structure of the mud has been broken and the mud and cement follow the Bingham flow model. Effects related to these restrictions will be discussed. FLOW PATTERNS SlNGLE FLUID IN ANNULUS Flow of a single fluid through an eccentric annulus is illustrated in Fig. 1. Part A shows laminar flow of a Newtonian fluid. This distribution of flow was calculated by Piercy, Hooper and Winney.' In fully developed turbulent flow, the velocity distribution around the annulus is less distorted, but the flow still favors the widest part of the annulus Parts B, C and D of Fig. 1 are a qualitative representation of the flow of a Bingham fluid. The yield strength of the fluid increases the severity of bypassing compared to Newtonian flow. At a very low rate of flow, all flow is confined to that portion of the annulus which has the minimum perimeter-to-area ratio. The fluid shears on the perimeter of that area when the pressure gradient multiplied by the area just exceeds the yield stress of the fluid multiplied by the perimeter. Whether or not the minimum perimeter-to-area region encompasses all of the annulus or only a part (as shown in Part B) depends on the geometry of the annulus. If only a part begins to flow, increasing the rate of flow increases the area flowing until finally there is flow throughout the annulus.

By G. E. Pellissier, P. H. Salmon Cox, B. G. Reisdorf

Banding that occurred in plates rolled from the early production heats of 18Ni(250) maraging steel is described and related to the segvegation of certain alloying elements (nickel, molybdenum, titanium), the extent of which was quantitatively evaluated by means of electron-microprobe analysis. The effect of banding on mechanical properties is discussed, with particular reference to observed directional differences in plane-strain fracture toughness of plates. It is shown that banding originates as interdendritic segvegation during ingot solidification and persists in some degree through normal soaking and hot reduction to plate. The results of the study showed that heating sections of small laboratory-cast ingots at 2200°F for 4 hr was sufficient to markedly reduce microsegregation and to considerably improve mechanical properties. Hot rolling of 7-in.-thick ingot sections to 1/2-in.-thick plate effected a similar reduction of microsegregation, but resulted in even greater increases in ductility and toughness than that obtained by homogenization treatment alone. DURING the past few years, considerable attention has been directed towards the low-carbon, high-alloy maraging steels and in particular towards the 18Ni-8Co-5Mo-0.4Ti alloy. The steels of this group, having an excellent combination of high strength and toughness, have a number of advantages over their more conventional medium-carbon low-alloy, quenched-and-tempered counterparts. In the annealed condition, the maraging steels are in the form of a ductile marten-site; aging at a relatively low temperature, typically 900°F for 3 hr, increases greatly the strength through the precipitation of intermetallic compounds. One problem in the early production heats of maraging steel was that the finished plate frequently displayed a banded structure. Previous work on other steels1-' had established that banding in wrought products is either a direct or an indirect consequence of chemical segregation, which occurs during solidification and persists to some extent through normal thermal and mechanical treatments. For example, Smith and others: in a study of low-alloy steel, were able to correlate the severity of banding in the wrought product with the degree of interdendritic segregation of nickel and chromium in the as-cast ingot. The effect of banding on the mechanical properties of steels is usually considered to be detrimental, although there is only limited evidence to suggest that a marked improvement in properties can be obtained with less heterogeneous structures. Comparison of the longitudinal and transverse tensile properties of banded and of homogenized 4340 steel showed that only the transverse ductility was improved by homogenization, but even then the improvement was not commercially significant.' Conversely, homogenization of through-the-thickness tension specimens of quenched-and-tempered steel plate, containing 1.47 pct Mn, increased the strength by as much as 10 pct and the tensile ductility by at least a factor of twos5 This improvement was related to the elimination of manganese-rich bands, which also are one of the factors responsible for cold cracking in the heat-affected zone of metal-arc welds.7 In the present study the nature and severity of banding in early commercial 18Ni(250) maraging steel plate and in laboratory-melted 18Ni(250) maraging steel plate was determined. The effects of banding on plane-strain fracture toughness and the effects of thermal homogenization treatments on the strength, tensile ductility, and toughness of 18Ni(250) maraging-steel as-cast ingots and rolled plate were evaluated. In addition, the effects of hot deformation by rolling on the mechanical properties of ingots were determined. 1) STUDIES OF BANDING IN EARLY PRODUCTION PLATE The chemical composition of the steel (A) used in this part of the investigation is shown in Table I. Banding was not clearly evident in either as-rolled or annealed* plate, but annealed and agedc** plate had a banded structure. The typical banded condition, Fig. 1, consists of layers of unetched austenite (white) and dark-etching martensite in a light-etching martensitic matrix. X-ray diffraction measurements showed that this steel contained more than 6 pct austenite. An electron-probe X-ray microanalyzer (using a focused beam of electrons) was used to determine the composition of the bands and of the material between the bands with respect to the main alloying elements— nickel, molybdenum, titanium, and cobalt. The recorded X-ray intensities were converted to concentration values with the use of a standard of similar composition. To facilitate probe positioning, all analyses were conducted on specimens that had been given a light etch. The influence of this etching on the analytical results was negligible; analyses made on the identical area before and after etching yielded essentially the same concentration values. The results of the electron-microprobe analyses at selected points revealed that the layers of austenite and adjacent dark-etching martensite contained greater amounts of nickel, molybdenum, and titanium than did the surrounding matrix, Table 11. The austenite layers

Jan 1, 1968

By Rudolph G. Wuerker

MUCH descriptive matter has appeared on the subject of suspension roof supports, or roof bolting, as it is more commonly called. The widespread introduction of roof bolting into coal mines and metal mines is truly phenomenal. Mine operators were quick to recognize the advantages of supporting wide openings without hindrance to machine maneuverability and ventilation. Although suspension roof support has long been installed at St. Joseph Lead Co. mines in southeast Missouri,'" its application to coal mining presented new problems, such as proper anchorage and bearing for the bolts, bolt diameter, and spacing of bolts. After continuous testing and experimenting at the mines, standard roof-bolting materials were determined.'!' The study reported in this paper is not concerned with such details as bolt diameter, which may be considered already solved in practice. In the tests discussed here, small models patterned on actual bolts were found to function in the same way and as satisfactorily as their prototypes. The aim of these tests was rather to investigate the influence of roof-bolting systems on the stress distribution around mine openings and to study the fracture patterns obtained in actual testing. Little was found about this in the literature, as testing of suspension roof methods and quantitative measurements are only now coming to the fore. Several suggestions and actual measurements have been made to evaluate critically the functioning of roof bolting systems, single roof bolts, and parts thereof. Outstanding among them is Bucky's outline of structural model tests.'" Since none of the suggested testing equipment was available, however, for the experiments discussed below, a different approach was chosen. The response of a mine roof under stress has often been compared to that of a beam. The slow coming down and bending through of beam or plate-like banks of shale, sandstone, or top coal is a familiar occurrence, extensively cited in the literature." It was felt that testing of roof-bolt systems installed in a concrete beam which was loaded in bending would be a fair approximation of the behavior of a mine roof underground. Another school of thought considers the roof behavior over an underground opening in connection with the stress distribution all around a circular or rectangular opening. This is more accurate, and leads to the concept of a dome-shaped zone of material destroyed under tensile stress. This is likewise a common sight in unsupported roadways where the continuous fall of roof results in what has been called the natural outline of roof fracture. This theory could not be tested and is treated separately in Appendix B. It is important to note that according to both assumptions the immediate roof fails in tension; the use of a beam in these tests, therefore, should give information valid for either of the two theories. With the testing equipment at hand it was possible to load concrete beams 6xlx0.5 ft under two-point loading, giving an equal bending moment over the center part in which the model bolts were installed. A comparison was made of the ultimate loads needed to break plain beams and beams in which roof bolts were installed. Arrangements were made with: 1—plain beams; 2—bolts with plate washers, some with holes drilled at 90" angles and others with holes drilled at 45" angles; 3—bolts with channel irons underneath; 4—bolts in holes filled afterward with cement; and 5—bolts anchored in a stronger stratum. The foregoing arrangement is made in order of increasing strength, as assumed from the theory of reinforced concrete. Likewise, laminated beams with wooden model bolts and with combinations of the foregoing set-ups were tested. All in all, 21 experiments were made out of the much greater number of combinations possible. There were, too, some trial tests. Enough observations from this limited number were made to interpret the behavior of mine roof, supported by various types of suspension bolts, at fracture. In present-day concepts, which have been proved by mathematical derivations and stress analyses, any opening driven underground will change the distribution and magnitude of the stresses existing around it. It does not matter whether the stresses become visible, as in rocks whose strength is less than the forces acting upon them, or whether they are invisible, as in the gangways lacking evidence of rock pressure. In this latter case the rocks can withstand changes in stress-distribution. To consider the mine roof as a beam, there are, with transversal loading, tensile stresses in the lower fiber and compressive stresses in the upper layers above the neutral axis of the beam. Beams of brittle material such as rock and concrete fail exactly as shown in Fig. 1. Nearly all model beams showed the same fracture pattern as that of a tension crack. The influence of support, by roof bolting or conventional

Jan 1, 1954

By J. D. Defilippi, E. M. Gilbert, K. G. Brickner

FCC chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Transformation to martensite is considered to be responsible for this behavior in some metastable Cr-Mn-N steels. However, very stable Cr-Mn-N steels also exhibit a ductile-to-brittle transition. The results of this study indicate that deformation faulting is the probable cause of the brittle behavior of stable Cr-Mn-N steels. Deformation faulting accounts for the ductile behavior of these steels in a tension test at -320°F and brittle behavior in an impact test at -320°F. Deformation faulting also accounts for the toPological features observed on the fracture surfaces of impact specimens of these steels. FACE- centered- cubic chromium-manganese-nitrogen (Cr-Mn-N) steels differ from most other fcc materials in that these steels undergo a ductile-to-brittle transition. Many Cr-Mn-N steels transform to martensite during deformation,l-5 and several investigatorsl-3 have suggested that the brittle behavior of these steels is caused by martensite formation. However, very stable Cr-Mn-N steels also exhibit brittle behavior. Schaller and Zackeyl reported that a very stable Cr-Mn-N steel (less than 3 pct martensite formed at -320°F) exhibited a transition temperature higher than that for steels in which large volume fractions of martensite formed during testing. The explanation given by Schaller and Zackey for this observation was that in the very stable steel the martensite, because of its higher interstitial content, was more brittle than that formed in their other steels. This explanation was questioned by Tisinai and samans4 and Baldwin.6 Moreover, because the toughness of stainless martensite at cryogenic temperatures is generally very low, this explanation does not account for Thompson's7 observation that small additions of nickel (1 to 3 pct) greatly improve the toughness of high nitrogen (0.35 pct) Cr-Mn-N steels. The present paper summarizes the results of an investigation of the low-temperature brittleness in very stable Cr-Mn-N steels. The importance of the mode of deformation on the toughness of these steels is discussed. Table I. Compositions of the Steels Invertigated, Pet Steel C Mn P S Si Ni Cr N - A 0.09 14.70 0.018 0.011 0.47 0.22 18.40 0.54 B 0.12 14.90 0.001 0.008 0.48 0.14 17.80 0.38 C 0.12 14.95 0.004 0.005 0.62 3.95 18.43 0.38 MATERIALS AND EXPERIMENTAL WORK The compositions of the steels investigated are shown in Table I. Steels A and B had compositions within the limits of a proprietary Cr-Mn-N stainless steel,* whereas Steel C was similar in composition to the proprietary steel except for its 3.95 pct Ni content. All steels were hot-rolled to 1/2-in. thick plate. The plates were subsequently annealed for 1 hr at 2000°F and water-quenched. Standard longitudinal and transverse Charpy V-notch impact specimens were machined from the annealed plates. Duplicate longitudinal and transverse impact specimens were tested at 212", 80°, 32", 0°, -100°,-160°,-200°,-256", and -320°F. Longitudinal tension-test specimens were also machined from the plates and tested at a crosshead speed of 0.05 in. per min at the aforementioned temperatures. The fractured impact and tension-test specimens of all three steels were examined to determine whether martensite had formed during testing. Magnetic, X-ray, electron-diffraction, and electron-microscopy techniques were used to detect the presence of martensite in the highly deformed areas of these specimens. Metallographic examination of highly deformed areas of impact and tension-test specimens revealed the presence of dark-etching bands, such as those shown in Fig. 1. These bands were observed only in deformed samples and were thought to be associated with the low-temperature brittleness of the Cr-Mn-N steels. Accordingly, a sample 1 in. wide by 3 in. long was cut from the 1/2-in.-thick plate of Steel C. This sample was surface-ground to a in. and then cold-rolled 60 pct at -320°F. Thin foils were prepared from the cold-rolled sample and examined in a JEM electron microscope. Brightfield, dark-field, and selected-area diffraction techniques were used to determine the cause of the dark-etching bands. Fractographic experiments were also performed. Impact specimens Of Steels A, B, and C were broken at -320oF, and the fracture surfaces of these specimens were immediately shadowed with carbon. The carbon replicas were examined in a Siemens electron microscope, and attempts were made to correlate the topological features of the fracture surfaces with the deformation mechanisms that could be occurring during an impact test of these steels.

Jan 1, 1970

By W. F. Chiao

Ultrasonic attenuation, a, measurements in the frequency range of 5 to 55 mc per sec have been studied to determine their quantitative relationship with the following three variables of mixed microstructures in steels: 1) the volume percent, XF, of polygonal fer-rite in mixed structures of martensite and polygonal ferrite in Fe-Mo-B alloys: 2) volume percent, XA, of retained austenite plus martensite aggregates in high-carbon steel; and 3) substructural differences between 100 pct bainitic ferrite structures formed at various temperatures. The quantitative relationship obtained in the first two conditions by plotting a us the known structural parameters can be expressed, respectively, as: where al, a 2 and C1, Cz are constants. In the third condition the nature of the attenuation depends on the state of dislocations generated at the transformation temperatures and also on the alloy composition. From these measured results, the mechanism of ultrasonic attenuation caused by these mixed microstructures can also be studied. MUCH interest has recently been shown in the application of ultrasonic attenuation and wave velocity measurements to the study of the microstructural characteristics of steels. The general aims of most of the investigations in this field can be grouped into two categories: one is to study the mechanisms of ultrasonic losses caused by the characteristic phases in the microstructure of steel,''' and the other is to develop nondestructive test methods and applications for quality control.~' 4 Apparently no work has been done on the evaluation of ultrasonic attenuation meas -urements as a means of quantitative determination of a given phase in the microstructure of a steel. It is well-established that the decomposition of austenite results in four main microstructural constituents—polygonal ferrite, pearlite, bainite, and martensite—and that each phase has different mechanical properties. Thus, when a steel consists of mixed microstructures, the mechanical properties can often be related to a quantitative measure of the volume percent of each phase present. This study relates ultrasonic attenuation measurements to: 1) the volume percent of polygonal ferrite in mixtures of martensite and polygonal ferrite in Fe-Mo-B alloys; 2) the substructural differences between 100 pct bainitic ferrite structures formed at various temperatures; and 3) the vol- ume percent of austenite in austenite plus martensite aggregates in a high-carbon steel. The choice of the specimen materials was based on the laboratory stocks which were suitable to produce the required mixed microstructures for this study. EXPERIMENTAL PROCEDURES Materials and Heat Treatment. Polygonal Ferrite Plus Martensite Structures. This mixture of phases was produced in a vacuum-melted Fe-Mo-B alloy. The alloy was hammer-forged at 1900" ~ to a -f-in.-sq bar. By isothermally heat treating the alloy at 1300° F for various times and then water quenching, variations in the amount of polygonal (or proeutectoid) ferrite can be controlled in a microstructure in which the balance of the material is martensite. In the present work, four different times of isothermal transformation were adopted; after heat treatment, the four specimens were machined for ultrasonic measurements. The compositions, heat treatments, and dimensions of the four specimens are listed in Table I. 100 pct Bainite Structures Formed at Different Temperatures. It has been well-established by Irvine et al.= that the presence of molybdenum and boron in ferrous alloys can retard the formation of polygonal proeutectoid ferrite and expose the bainitic transformation bay, so that a more acicular or bainitic ferrite can be obtained over a wide range of cooling rates. Their investigation6 also showed that the mechanical properties of fully bainitic steels are usually closely dependent on the substructural characteristics of the steels. For studying the substructural characteristics in completely bainitic structures, six Fe-Ni-Mo alloys, of which five were free from carbon addition and one with 0.055 pct C addition, were selected so that a wide range of hardness values for 100 pct bainitic ferrite structures could be produced by normalizing at 1900" F followed by air cooling. The different bainitic transformation temperatures were recorded during air cooling. All of the alloys were vacuum-melted and then forged at 1900" F to square bars. Data on the six specimens of these structure series are summarized in Table 11. Austenite Plus Martensite Structures. The high-carbon steel used to study austenite plus martensite structures was vacuum-melted and then forged into Q-in.-sq bar. The series of mixed structures of austenite plus martensite was produced by quenching the specimens from the austenitizing temperature to room temperature and then refrigerating them at various temperatures within the range of martensite transformation to produce different amounts of retained austenite. Data on the four specimens of this series are listed in Table 111. Quantitative Analysis of the Microstructures. The microstructures containing martensite plus polygonal ferrite were analyzed by the point-counting technique.

Jan 1, 1969

By Carrol M. Beeson

Reasons are given for using a Boyle's-law porosimeter in conducting core analysis for either routine or research purposes. Among other things, it is pointed out that such a porosimeter permits the measurement of all basic properties on the same sample, thereby eliminating the sources of error inherent in the use of adjacent samples. References are made to investigations of gas adsorption on various porous materials, to show that the use of helium in Boyle's-law porosimeters reduces to negligible proportions the error due to the adsorption or desorption of the operating gas. Two Boyle's-law instruments are described. which permit accurate and rapid measurements of porosity. Schematic sketches and explanation:; are included, along with derivations of equations required in performing precise determinations. Summaries of data obtained during calibration are tabulated and analyses of the data are resented as indications of the precision and accuracy of each device. Comparisons are also shown for measurements made with each of the instruments on the same test pieces and cores. INTRODUCTION An accurate porosimeter, operating on the principle of Boyle's law. is of considerable value in the analysis of cores for either routine or research purposes. This is due primarily to the fact that the measurement of porosity with such an instrument leaves the sample free of contamination by any liquid. When used in conjunction with an extraction apparatus' for determining oil and water saturations, a Boyle's-law porosimeter permits the measurement of all basic properties on the same sample. This eliminates the sources of error inherent in the use of adjacent samples, or the necessity of determining porosity after all other properties have been obtained. Large errors may result from combining measurements made on adjacent samples in order to obtain a single property. This type of error is definitely involved when oil and water are measured with one sample, and the pore vo1ume is measured with an adjacent one. Furthermore, the source of error would be present to some extent, even if the analyst could choose the samples so they were truly adjacent from a geological standpoint. The use of adjacent samples in routine core analysis also necessarily decreases the probability of correlating core properties. For example, the chance of correlating the "irreducible" interstitial-water saturation with permeability, is bound to be greatly reduced by measuring these properties on "adjacent" samples. For research purposes, amplification is scarcely required concerning the greater flexibility of a method for measuring porosity which leaves the core free of contamination by any liquid. Even under those circumstances which require that the core be saturated with a liquid, a previous measurement of porosity with a gas is useful in determining the degree of saturation that has been attained in the process. Furthermore, for comparable accuracy, porosity usually may be determined more rapidly with a gas than with a liquid. This advantage of the Boyle's-law instrument is most outstanding when the determination time is compared with that required in obtaining porosity by evacuation of the core followed by saturation with a liquid of known density. Several porosimeters which operate on the principle of Boyle's law have been described2,3,4,5,6,7 in the literature. No comparison will be attempted between those instruments and the ones described herein. Before helium gas became readily available, Boyle's-law porosimeters were subject to an appreciable error due to the adsorption of the operating gas on the surface of the core solids. There is considerable direct and indirect evidence in the literature to support the contention that the adsorption of helium on porous solids is negligible at room temperature. In discussing the use of Boyle's-law porosimeters, Washburn and Bunting2 stated that "for most ceramic bodies dry air is a satisfactory gas, but hydrogen will be required in some instances. Helium could, of course, be employed for all types of porous materials at room temperatures or above." Howard and Hulett8 obtained evidence that the adsorption of helium was negligible at room temperatures, even on activated carbon ; for the density measured with this gas was unaffected by changes in pressure or by changes in temperature from 25 °C to 75 °C. For oil-well cores, Taliaferro, Johnson, and Dewees" obtained lower porosities with helium than with air, but apparently did not study helium adsorption. From the work of these investigators, it follows that the use of helium in Boyle's-law porosimeters reduces the error due to gas adsorption to negligible proportions. This makes it possible to construct instruments which permit the determination of porosity with (1) a high degree of accuracy, (2) with great rapidity, and (3) without contamination. THE KOBE POROSIMETER The fundamental design of the Kobe Porosimeter was developed by Kobe, Inc., which firm built about 12 of the instruments during 1936 and 1937. Since that time, seven or eight more have been constructed with their permission, making a total of about 20 that have been put into operation.

Jan 1, 1950

By T. Cantwell, N. C. Rasmussen, H. E. Hawkes

Beryl is a mineral that may be difficult to distinguish from quartz by casual field inspection. The easily recognized green color and hexagonal crystal form of coarse-grained beryl are by no means universal, even in beryl from pegmatitic deposits. If it occurred as a fine-grained accessory mineral in an igneous rock, it would almost certainly escape detection unless samples were submitted for petrographic or chemical analysis. There may be substantial deposits of some beryllium mineral, other than beryl, that has been overlooked because that mineral also closely resembles the common rock-forming minerals. A reliable and simple method of identifying beryllium minerals and determining the beryllium content of a rock would be helpful in exploration. This article describes preliminary experiments in applying nuclear reaction to the qualitative identification of beryl and to the semiquantitative determination of the beryllium content of rock samples. Gaudin,1,2 the first to apply a nuclear reaction in detecting beryllium minerals, developed a method that irradiates the sample with gamma rays, which react with beryllium nuclei to produce neutrons. The neutrons are then measured with standard equipment. The cross section for this reaction is about 1 millibarn. The cross section is a measure of the probability that a reaction will take place, for example, between a beryllium nucleus and an incident gamma ray or alpha particles.3-5 At 1-millibarn cross section for the reaction, satisfactory performance required a source strength of the order of 1 curie (3.7 x 10"' disintegrations per sec, where each disintegration releases one or more gamma rays). The reactions will not take place if the gamma radiation is below a minimum energy, in this case 1.63 mev. The size of the source and the energy of the radiation made heavy shielding necessary for these experiments, both to reduce the background count of the neutron counter and to safeguard personnel. The original discovery of the neutron by Chad-wick in 1932 resulted from experiments with another nuclear reaction, induced by bombarding beryllium with alpha particles in which the products are carbon-12 and neutrons. The equation for this reaction is as follows:' " ,Be" + ,He'? 6C12 + 8,n' [1] re-particle neutron In the above nuclear equation (Eq. 1), the sub- script number indicates the number of protons in the nucleus (the atomic number) and the superscript the total number of neutrons and protons (approximately the atomic mass). For the alpha-neutron reaction the cross section is about 250 milli-barns, or 250 times that of the gamma-neutron reaction used by Gaudin. The positively charged alpha particle is repelled by the positive charge of the beryllium nucleus; it must, therefore, have a certain minimum energy in order to approach close enough to the beryllium nucleus to react. For reaction with the beryllium nucleus, the lower limit of the alpha-particle energy is 3.7 mev. The alpha-neutron reaction, with polonium-210 as an alpha source, was selected for the present experiments. Alpha particles are emitted by polonium-210 at 5.30 mev, which is adequate for the reaction with beryllium. Furthermore, this isotope of polonium emits alpha particles with negligible associated gamma radiation, thus eliminating the necessity of shielding. The half-life of polonium-210 is 138 days. Inasmuch as alpha particles carry a possible charge and are large compared with most nuclear particles, their energy is rapidly dissipated in passing through matter. Their range in standard air is 3.66 cm,3 and they penetrate only a few tens of microns into a mineral sample. The short range in air can be minimized by preparation of a flat sample surface that can be brought very close to the alpha source during analysis. On the other hand, short range of alpha particles in air lessens the radiological health hazard and makes it possible to use this method without shielding. It must be emphasized, however, that the alpha emitters are potentially very dangerous if they enter the human body. Polonium must be handled with extreme caution. The literature has reported experiments on the yield of neutrons from reaction of alpha particles with beryllium nuclei. Feld" reports that in intimate mixtures of polonium and beryllium, 3 x 106 eutrons per sec are produced per curie of polonium. Elsewhere in the same reference it is stated that a sandwich-type source yields about one third as many neutrons as an intimate mixture. A table of neutron yields for full energy polonium alpha-particles on thick targets as reported by Anderson7 is the basis of Table I. From Table I it can be deduced that the elements most likely to interfere, i.e., those that also produce neutrons when bombarded by alpha particles, are boron and fluorine. These data also show that it will probably not be possible to determine very small quantities of beryllium in rocks because of the masking effects of the major elements, sodium, magnesium, and aluminum. The neutrons emitted in the alpha reaction are detected by another nuclear reaction. Either of the

Jan 1, 1960

By A. J. Shaler

The subject of the mechanism of sintering has received much attention in the past few years, particularly since the beginning of the series of AIME seminars in powder metallurgy of which this paper introduces the fourth. In the first of these, F. N. Rhines1 brought together and discussed the available experimental data on the sintering of pure metallic powder, and succeeded in bringing to a sharp focus the attention of workers in this field on the established observations which a satisfactory theory must explain. Several other authors3,5,6 have, in the last few years, studied the phenomena that occur when cold metallic powders, loose or in the form of compacts, are first brought to elevated temperatures. Some workers' in the field of friction have recently studied the adhesion of solid metal surfaces when they are brought into close contact. These researches have indicated that several separate mechanisms operate simultaneously, at least during the first part of the sintering process. Some of them have been called transient mechanisms4 because they are in general not absolutely necessary to sintering. Powders may be so prepared and so treated that these transient phenomena do not take place during subsequent sintering. This does not mean, of course, that their industrial and scientific importance is any less than that of the steady-state phenomena. The latter are changes that go on during sintering no matter how the powders are made or treated; they cannot be divorced from sintering. One way to analyze the process of sintering into its component parts is perhaps to distinguish between these transient and steady-state phenomena. Some of the transient phenomena have been studied in the past few years. Huttig3 has shown that, when the temperature of metallic powder is slowly raised, the following events generally occur in order: (1) physically adsorbed gases are desorbed; (2) there is an atomic rearrangement of the surface, a sort of two-dimensional "surface-reciystallization"; (3) there is a breakdown of chemically adsorbed surface compounds; (4) there is a recrystalliza-tion in the volume of the metal. All these changes are shown by Huttig and his coworkers to be completed fairly rapidly at lower temperatures than those generally used in sintering and are therefore not a part of the mechanism whereby the density of a mass of powder continues to change after long heating at an elevated temperature. But the first and third of these changes release gases in quantities which may or may not help to control the steady-state mechanisms, depending on when the voids become isolated from the outside of the compact. Among the phenomena studied by Steinberg and Wulff,8 there is the effect on sintering of residual stresses arising from the pressing operation. They found that the lateral surfaces of a green compact of iron are under a longitudinal residual tension-stress of the order of magnitude of half the yield-point for solid iron. If the outside surface is in tension, the core must be under longitudinal compression. When the compact is heated, the surface residual stress is thermally relieved first, and the compact therefore initially expands in the direction of its axis. This is a transient phenomenon, if for no other reason than the possibility of sintering unpressed powders, as demonstrated by Delisle,9 Libsch, Volterra and Wulff10 and others.1 The subject of recrystallization is dealt with further in a separate section, in view of its prominent place in sintering literature. It, too. is one of these transient phenomena. Among the steady-state parts there may be distinguished the attraction between particles and its consequences, the spheroidization of voids in the compacts, and the densification or swelling of the compact. There is considerable evidence4,7 showing that cold metallic surfaces, when brought to within a few interatomic distances of one another, are attracted to each other by forces of the order of many thousands of pounds per square inch. A calculation, discussed in greater detail in another section, shows that this force changes but slightly when the temperature of the surfaces approaches the melting point. Actual measurements of forces of adhesion of this magnitude have been made by Bradley12 on some nonmetals, but none has yet been made on cold or hot metals. This force is of sufficient magnitude to cause some plastic deformation in powder compacts, as will be shown below. A second force of steady-state nature is due to the surface tension, which probably has the same origin as the force of attraction between surfaces.164 A paper by Udin, Shaler, and Wulff1,3 gives the results of precise direct measurements of its value for solid copper. The demonstration of the tendency for the surface tension to shrink a pore was long ago given by Gibbs.17 He showed that its effect on a curved surface between two phases is equivalent to a pressure perpendicular to that

Jan 1, 1950

By C. van Dijk

In Sept., 1960, a steam-drive project was started in the solution-gas drive area of the Schoonebeek field. A part(ern of three five-spots and one four-spot was selected covering an area of 65 acres. The pay in the project area has good lateral continuity and dips slightly to the northeut; it is about SO ft thick and permeability increases from 1,000 and at the bottom to approximately 10,000 md at the top. The oil originally in place was 12.6 X 10' bbl. The oil has an in situ viscosity of about 180 cp. At the start of the steam drive the cumulative primary production due to. solution-ga.7 drive amounted id 4 Percent of the oil originally in place. Reservoir pressure had dropped about 120 psi and no significant primary re-.serves remained. Some 11.3 million bbl of steam (all steam quantities are expressed in barrels of water vaporized) have been injected, resulting in production of an additional 4.1 X I0 9bl of oil, or 33 percent of the oil originally in place. This corresponds to a cumulative oil-stearn rario of 0.37 bbllbbl. It appears that the steam preferentially moves r updip while liquids are produced mainly from downdip wells observations indicate that tile steam flows through only the upper part of the formation. The lateral steam distribution in the pattern is satisfacrory since several prodriction wells hardly reacted and, hence, cori tributcd little to the oil production. Production performance and results from material balance calcutlations agree satisfactorily with the results of large-,scale laboratory experiments. On the basis of these experirmental results the .steam drive, together with a cold water follow-up. is expected to bring ultimate recovery to a value of crt leas: 50 percent of the oil originally in place. No serious production problems have been encountered. However, due to mechanical fuilure, two old prodriction wells and one injection well had to be replaced. An extension of the. steam drive in this area is under connstruction. Introduction The Schoonebeek oil field, discovered in 1943 and developed after World War 11, is situated in the eastern part of the Netherlands. The main oil reservoir in this field is the Valanginian sand. A completely sealing fault divides this reservoir into two areas (Fig. 1): the southwestern part of the sand body where primary production is ob- tained by means of a solution-gas drive, and the remain. der where edge-water drive is the production mechanism. In the greater part of the field the reservoir consists of a single, unconsolidated sand body. The net thickness ranges from 30 to 100 ft and the top is between 2,400 and 2,800 ft below sea level. Formation permeability varies from approximately 10,000 md at the top to values of the order of 1,000 md at the bottom, and porosity is about 30 percent. The reservoir contains a paraffinic oil of 25" API gravity with an in situ viscosity of 160 to 180 cp. Initial oil saturation was high (85 to 90 percent). The relatively large quantity of oil in place (more than 10' bbl), and the low ultimate primary recoveries expected from this field — approximately 15 percent stock-tank oil initially in place (STOIIP) for the water-drive area and 5 percent STOIIP for the solution-gas drive area — clearly indicate ample scope for secondary recovery. Because ies-ervoir and crude characteristics made this field suitable for thermal secondary recovery, a hot-water drive project was started in the water-drive area about 10 years ago. A few years later a steam drive and an in situ combustion project were started in the solution-gas drive area. This paper deals with the performance of the steam-drive project, which was started in Sept., 1960, and which is still in operation. Design of Steam-Drive Project, An experimental investigation of the steam-drive process carried out by schenk in 19561 indicated that under schoonebeek conditions steam injection could be an attractive secondary recovery method. the findings and encouraging results of a pilot test in the Mene Grande field in venezuela,i led to the design of a steam-drive project in the schoonebeek field, Pruject Site and Pattern In 1958 the reservoir pressure in the solution-gas drive area had decreased to about 120 psi, and oil production rates of wells in this area had dropped to 7 to 10 B/D. The cumulative primary production was about 4 percent STOIIP, leaving an oil saturation of approximately 85 percent. In view of the large amount of oil left behind in the reservoir, the solution-gas drive area was selected for the planned steam-drive project. The area in the vicinity of Well S1 3 (Fig. 2) was considered to be suitable since it is at least partly isolated from the rest of the field by faults and the sand is relatively thick (about 80 ft).

Jan 1, 1969

By W. C. Leslie

The textures of cold-rolled and of annealed iron are compared with those of an iron-0.8 pct copper alloy in which the amount of precipitation after cold rolling was controlled. Previously published pole figures -for cold-rolled and for annealed iron are confirmed. The effects of precipztatiotz after cold rolling are to retain the cold-rolled texture after annealing, to inhibit the formation of the usual allnealing texture, and to produce elongated recrys-tallized ferrite grains. It is suggested that the inhibition of new textures by precipitation after cold rolling is a general phenomenon. A great deal of attention has been paid to the development of texture during the secondary or tertiary recrystallization of ferritic alloys, but very little work seems to have been done on the control of texture during primary recrystallization. If such control were attained, it might be possible to simplify the processing of oriented materials or to change the characteristics of current cold-rolled and an-nealed products. From previous experience, it seemed likely that texture could be controlled by recrystallizing a supersaturated solid solution. Green, Liebmann, and Yoshidal found that the formation of preferred orientation in aluminum (40 deg rotation about <111> relative to the deformed matrix) was inhibited when iron was retained in supersaturated solid solution in the strained aluminum. The authors attributed this inhibition to iron atoms in solid solution. There is, however, an alternative explanation. Green et al, took a highly supersaturated solution of iron in strained aluminum and heated it to an unspecified temperature for recrystallization. It is probable that precipitation occurred prior to and during recrystallization, and it is proposed that the inhibiting agent is this precipitate, rather than the iron atoms in solid solution. It is important to note that precipitation before cold work is ineffective; the effective precipitate is that formed after cold working and either before or during recrystallization. The location and distribution of the precipitate are critical. Precipitation in such a manner has been found to have profound effects upon kinetics of recrystallization and the microstruc-ture of the recrystallized alloys.2-4 It would be surprising, indeed, if this were accomplished with no change in texture. Because of the relative simplicity of the system, and because of previous experience,4-7 it was decided to determine the effect of precipitation on texture in an alloy of iron and copper. Bush and Lindsay5 found an unspecified change in texture in cold-rolled and annealed low-carbon rimmed steel sheets when the copper content exceeded 0.1 pct. MATERIALS In earlier work, the rate of recrystallization of a low-carbon steel was greatly decreased by 0.80 pct copper, and, after the proper treatment, the recrystallized ferrite grains were greatly elongated.4 Accordingly, it was decided to investigate the effect of precipitation on texture at this level of copper content. The iron and the iron-copper alloy were made from high-quality electrolytic iron and OFHC copper, vacuum-melted in MgO crucibles, cast, hot-rolled to 0.2 in., then machined to 0.150 in. The compositions are given in Table I. The plates were heated to 925°C and brine quenched, twice. This produced a ferrite grain size of ASTM 0 in the iron and ASTM 1 in the Fe-Cu alloy. Disk specimens were cut from the heat-treated plates, repeatedly polished and etched, then used to determine (110) and (200) pole figures by reflection. Despite the complication of large grain size, these pole figures strongly indicated a random texture. PROCEDURES The copper content in solid solution in ferrite before cold rolling and recrystallization, and hence, the amount that could precipitate during the recrys-tallization anneal, was controlled at three levels by heat treatment. The specimens as quenched from 925° C were presumed to have all the copper, 0.80 pct, in solid solution. Other samples of the quenched alloy were aged 5 hr at 700°C to retain about 0.5 pct Cu in solid solution.6 A third set of quenched specimens was reheated to 700°C, then slowly cooled in steps, to reduce the amount of copper in solid solution to a very low level. All specimens were cold-rolled 90 pct, from 0.150 to 0.015 in. thick. The rolling was done in one direction only, i.e., the strip was not reversed between passes, with a jig on the table of the mill to keep the short specimens at 90 deg to the rolls. The rolls were 5 in. in diameter and speed was 35 ft. per min. Machine oil was used as a lubricant. In a supersaturated alloy, the maximum effect of the copper precipitate on microstructure and on recrystallization can be developed by a treatment at 500°C, after cold rolling and before recrystallization.&apos;

Jan 1, 1962

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By Benny Langston, Frank M. Stephens

Although little information is available concerning small-scale equipment for dust collection in laboratories, it is possible to adapt standard equipment for laboratory use. Dust from laboratory processes may be collected by cyclone separators, filters, electrostatic separators, scrubbers, and settling chambers. IN recent years much attention has been given to recovery, treatment, and disposal of dusts discharged into the atmosphere from operations of industry. considerable data has been accumulated on both operation and design of dust-collector equipment for commercial installations. On the other hand, there is almost no published data on design and construction of small-scale equipment to handle dust problems that arise in the ore-dressing laboratory. Dust-collection equipment such as multiclones, single-cyclones, scrubbers, chemical and mechanical filters, settling chambers, and electrostatic separators has proved its efficiency for collecting dust in industry. In the laboratory, however, the engineer is faced with the problem of collecting small quantities of dust, inexpensively, without diverting the major effort from the metallurgical problem to the problem of collecting dust produced by the process. For most applications standard dust-collection equipment is too large for use in the laboratory; however, for control of dust in large working areas it is often possible to use a standard dust collector, such as an air filter, with branch ducts to eliminate a health hazard. For example, the well-furnished sample-preparation room containing small jaw crushers, rolls, and pulverizers, in addition to the riffles and screens necessary for preparation of samples, presents a perennial source of dust. The authors&apos; experience has shown that a combination system consisting of overhead branch ducts to the individual equipment and floor ducts with grills, where applicable, connected to a central dust collector effectively removes dust generated in preparation of samples. Fig. 1 is a sketch of a downdraft dust-collector for table installation. Similar systems can be built with floor grids. For portable equipment such as laboratory vibrating screens this type of installation with a steel grill to support the heavy load is reasonably efficient. Overhead branch ducts to individual crushing and grinding equipment, although efficient, must be carefully controlled by dampers to prevent excess loss or a change in the composition of the sample. Change in sample composition can result from excess velocity, which causes selective removal of constituents of low specific gravity. Fig. 2&apos; shows the theoretical effect of terminal velocity on spherical particles of different specific gravities in air and water under action of gravity. Fig. 3 shows the effect of air velocity on composition of CaCO, coal mixtures. Although the entrainment of dust particles in a moving air stream is the basic mechanism by which all dust-collection equipment functions, usually intake velocity of the dust-collection system must be controlled to prevent loss of part of the sample. As an example of what may happen when excess velocities are used, a mixture of 50 pct coal and 50 pct limestone was crushed to —10 mesh and fed to a pulverizer equipped with an overhead dust-collection system. Fig. 4 shows the overhead dust-collection equipment used in this test. The pulverizer was set to give a product 95 pct —100 mesh in two stages. Velocity of air passing over the lip of the pulverizer was measured with an anemometer. After grinding, the finished product was analyzed to show the amount of calcium carbonate present. Fig. 3 shows graphically the increase in calcium carbonate as velocity through the dust-collection duct was increased. These data show that at a velocity of 1 ft per sec little if any of the coal was entrained by the overhead draft. At the maximum velocity, about 6.5 ft per sec, approximately 7 pct more coal was entrained than calcium carbonate. From an operating standpoint, this problem can be remedied easily by dampering the line to control velocity. The lowest velocity commensurate with satisfactory dust control should be used to prevent excess loss and, in some cases, selective dust loss. Collection of Dust in Laboratory Processes As in industry, the engineer desires to collect efficiently the dust produced by processes being investigated on a laboratory scale. However, in the collection of laboratory dusts he is faced with two additional problems: 1—The volumes of gas and the quantity of dust that must be recovered are small when compared with the capacity of standard dust-collector equipment, which must be scaled down in design except for collection of dust from large pilot-plant operations. 2—In addition, because of the variety of problems studied in the process laboratory, the engineer cannot design today a dust collector that will meet the conditions imposed by the processes of tomorrow. Sometimes, therefore, he must compromise collection efficiency to minimize the cost of fabrication and the amount of time diverted from the metallurgical to the dust-control problem. For collection of dust from laboratory processes a cyclone separator, filters, electrostatic separators, scrubbers, and settling chambers can usually be adapted for small-scale operations. The following

Jan 1, 1955

By E. J. Rapperport, J. P. Pemsler

The thermodynamic activities of zinc in six solid solution Cu-Zn alloys ranging from 5 to 35 at. pct Zn were determined experimentally in the temperature range 400° to 600°C. This low temperature investigation was canducted in order to evaluate techniques developed to utilize the inherently high sensitivity of atomic absorption flocesses in the measurement of thermodynamic activities. Analytical expressions ,for the activity and actizlity coeflcient are given for the six alloys in the temperature ranges investigated. RELATIVELY few experimental methods are available for investigation of thermodynamic activities of alloys, especially in the solid state. The techniques most frequently used have been the electrochemical potential and the effusion methods, both of which have severe limitations in many instances. It is therefore desirable to expand the ability to perform such measurements in order to obtain new information as well as to provide an additional independent verification capability. In this work, we present a significant improvement in the spectrophotometric method for sensing small vapor pressures in static absorption cells. Similar techniques have been used previously;1"5 however, applications had been limited to relatively high pressures, often greater than 1 torr. Prior investigators have, for the most part, used broad spectral sources such as xenon or mercury lamps, and high intensity arcs. Hollow cathode sources were first suggested in 1956 6 and were used soon afterwards.4&apos;5 These sources offer significant improvements in sensitivity and freedom from interfering spectral lines.&apos;-&apos; EXPERIMENTAL High purity zinc was obtained from Cominco Products, Inc., and copper from American Smelting and Refining Co. Both elements were of 99.999 pct purity. Copper-zinc alloys were vacuum melted in a high fired carbon crucible with each alloy pulled from the melt as a 4 -in. diam bar. The bars were swaged to -1/4 in. rods and vacuum annealed for 160 hr at 800° + 1°C. Samples for gross chemical analysis were taken at intervals along the length of the rods to ascertain the axial zinc gradient. Electron microprobe analysis of homogenized specimens indicated that the alloys had uniform compositions over their cross sections on a macro (200 p) and micro (1 u) scale to better than *1 pct (20) of the gross composition. This tolerance was determined by counting statistics, rather than assured composition fluctuations. All SiO 2 windows were high-ultraviolet-transmission grade to minimize intensity losses. Silica absorption cells were scrupulously cleaned consecutively in organic solvents, dilute HF, and distilled water before use. The empty cells were then flamed while under a dynamic vacuum, cooled, and removed to an argon-filled glove bag. Alloy pieces were cut and filed in the glove bag to produce fresh surfaces, and then loaded into the cells. The loaded cells were temporarily sealed, removed from the glove bag, reevacuated to 10-5 torr or better, and permanently sealed. The instrument used is schematically shown in Fig. 1. The spectral emission from a commercially made hollow cathode lamp (A) of a selected element is focused through an absorption cell (B) inside a well-controlled furnace (C). The intensity of the transmitted beam is measured using the spectrometer* (D) &apos;Techtron model AA4 atomic absorption spectrometer. which contains a grating (E) that disperses the light prior to impingement on the photomultiplier (F). The monochromator grating is adjusted so that only the wavelength of interest is measured. The power supply delivered an interrupted voltage to the lamp, causing a chopped radiation output to be transmitted. The detector read only the intermittent component of radiation incident upon it, so that all continuous noise signals (furnace radiation, and so forth) were eliminated. Three recording thermocouples contained in the muffle furnace were positioned along the length of the absorption cell: one at each end and one at the center. An effort was made to keep the ends of the cell several degrees hotter than the center to avoid window condensate. Appropriate thermal corrections were then necessary to relate cell pressure to radiation attenuation. Water-cooled heat shields, as shown in Fig. 1, were found to aid signal stability by protecting the hollow cathode and the photomultiplier from furnace radiation. The furnace had a 2-in. diam muffle, Kan-thal wound, with SiO 2 windows at its ends to minimize convective effects. The hollow cathode radiation was masked and focused to form a conic beam that was a maximum of { in. diam within the furnace. Thus, the 1.5 in. diam absorption cell easily contained the entire beam. The furnace was mounted on ball-bearing slides with positive positioning detents. This arrangement allowed the removal of the entire furnace assembly from the radiation path, position [I], Fig. 1, so that frequent sampling of the unattenuated beam intensity could be obtained. In all cases the beam intensity was kept constant to 0.1 pct as judged by readings taken immediately before and immediately after data collection. Only data for absorptions of less than 80 pct were utilized, as systematic deviations from linearity were found for greater absorptions.

Jan 1, 1970

By J. D. Miller, J. E. Sepulveda

Tar sand deposits in the state of Utah contain more than 25 billion bbl of in-place bitumen. Although 30 times smaller than the well-known Athabasca tar sands, Utah tar sands do represent a significant domestic energy resource comparable to the national crude oil reserves (31.3 billion bbl). Based upon a detailed analysis of the physical and chemical properties of both the bitumen and the sand, a hot-water separation process for Utah tar sands is currently being developed in our laboratories at the University of Utah. This process involves intense agitation of the tar sand in a hot caustic solution and subsequent separation of the bitumen by a modified froth flotation technique. Experimental results with an Asphalt Ridge, Utah, tar sand sample indicated that percent solids and caustic concentration were the two most important variables controlling the performance of the digestion stage. These variables were identified by means of an experimental factorial design, in which coefficients of separation greater than 0.90 were realized. Although preliminary in nature, the experimental evidence&apos; gathered in this investigation seems to indicate that a hot-water separation process for Utah tar sands would allow for the efficient utilization of this important energy resource. The projected increase in the ever-widening gap between the domestic energy demand and the domestic energy supply for the next few years has motivated renewed interest in energy sources other than petroleum, such as tar sands, oil shale and coal. Although a number of research programs on the exploitation of national coal and oil shale resources have already been completed, very few programs have been initiated on the processing of tar sand resources in the United States. In recognition of their significance as a domestic energy resource, investigators at the University of Utah have designed an extensive research program on Utah tar sands. An important phase of this program, and the main subject of this publication, is the development of a hot-water process for the recovery of bitumen from Utah tar sands, as a preliminary step toward the production of synthetic fuels and petrochemicals. The term "tar sand" refers to a consolidated mixture of bitumen (tar) and sand. The sand in tar sand is mostly a-quartz as determined from X-ray diffraction patterns. Alternate names for "tar sands" are "oil sands" and "bituminous sands." The latter is technically correct and in that sense provides an adequate description. Tar sand deposits occur throughout the world, often in the same geographical areas as petroleum deposits. Significantly large tar sand deposits have been identified and mapped in Canada, Venezuela and, the United States. By far, the largest deposit is the Athabasca tar sands in the Province of Alberta, Canada. According to the Alberta Energy Resources Conservation Board (AERCB),2,3 proved reserves of crude in-place bitumen in the Athabasca region amount to almost 900 billion bbl. To date, this is the only tar sand deposit in the world being mined and processed for the recovery of petroleum products. Great Canadian Oil Sands, Ltd. (GCOS) produces 20 million bbl of synthetic crude oil per year. Another plant being constructed by Syncrude Canada, Ltd. is expected to produce in excess of 40 million bbl of synthetic crude oil per year. According to the Utah Geological and Mineral Survey (UGMS), tar sand deposits in the state of Utah contain more than 25 billion bbl of bitumen in place, which represent almost 95% of the total mapped resources in the United States.4 The extent of Utah tar sand reserves seems small compared to the enormous potential of Canadian tar sands. Nevertheless, Utah tar sand reserves do represent a significant energy resource comparable to the United States crude oil proved reserves of 31.3 billion bbl in 1976.5 Tar sands in Utah occur in 51 deposits along the eastern side of the state.4 However, only six out of these 51 deposits are worthy of any practical consideration (Fig. 1). As indicated in Table 1, Tar Sand Triangle is the largest deposit in the state and contains about half of the total mapped resources. Information regarding the grade or bitumen content of Utah deposits is still very limited. The bitumen content varies significantly from deposit to deposit, as well as within a given deposit. In any event, the information available6-8 seems to indicate that Utah deposits are not as rich in bitumen as the vast Canadian deposits which average 12 to 13% by weight.9 Although many occurrences of bitumen saturation up to 17% by weight have been detected in the northeastern part of the state (Asphalt Ridge and P. R. Spring), the average for reserves in Utah may well be less than 10% by weight. Separation Technology As in any other mining problem, there are two basic approaches to the recovery of bitumen from tar sands. In one

Jan 1, 1979

By R. T. Hukki

John F. Myers (Consulting Engineer, Greenwich, Corm.)—Since the art of comminution has lain practically dormant for many years, it is very interesting that R. T. Hukki approaches the subject with a new concept. One is reminded of the research carried on by A. W. Fahrenwald of Moscow, Idaho, a few years ago. Fahrenwald mounted a steel bowl on a vertical shaft. The balls and ore placed in the bowl were rotated at fast speeds, thus simulating the supercritical speeds used by Hukki. The rolling action of the balls against the smooth shell liner has pretty much the same effect. The action is horizontal in one case and vertical in the other. Both researchers report good grinding activity. It is also constructive that such able investigators give to the students of comminution their interpretation of their laboratory results in terms of large-scale operation. History shows that it takes a lot of time for such radically new ideas to be absorbed by the industry. Typical of this is the present-day activity of cyclone classification in primary grinding circuits. The idea of cyclone classification has been kicking around for 30 or 40 years. Certainly we all suspect that the ponderous grinding mills of today, and their accessory apparatus, large buildings, etc., will ultimately give way to small fast units, just as this has occurred in other industries over the past 50 years. At the moment there is no evidence that ball and liner wear is prohibitively high. In fact, at the time Fahrenwald was demonstrating his high-speed horizontal machine at the meeting of the American Mining Congress, several years ago, he assured this writer that the balls retained their shape much longer than they do in conventional tumbling mills. Rods and balls that slide (as some operators in uranium plants are experiencing) get flat. Apparently the balls have a rolling action. Mr. Hukki&apos;s references to the processing capacity of the Tennessee Copper Co. mills is adequate. Those studying this subject will be greatly interested in the paper presented by Richard Smith of the Cleveland-Cliffs Iron Co. at the annual meeting of the Canadian Institute of Mining and Metallurgy in Vancouver April 24, 1958. This paper will be published during the latter part of 1958 in the Canadian Institute of Mining and Metallurgy Bulletin. Hukki&apos;s pioneering spirit is to be commended. R. T. Hukki (author&apos;s reply)—It has been heartening to read the objective discussion by J. F. Myers. The sincerity of his opinions is further strengthened by the fact that the article he has discussed contradicts in a major way the parallel achievements of his life work. Myers is right in his opinion that in general it takes a long time before new ideas are accepted by the industry. On the other hand, revolutions usually take place at supercritical speeds. There are many indications at present that both the unit operation of grinding and the related subject of size control are now just about ripe for a revolution. In grinding, brute force must ultimately give way to science. Rapid progress can be anticipated in the following fields: 1) Autogenous fine grinding at supercritical speeds will be the first advance and the one that will gain recognition most easily on industrial scale. At this moment, little Finland appears to be leading the world. Crocker recently made a statement that in nine cases out of ten, your own ore can be used as grinding medium more effectively and far more economically than steel balls. This is true. The present author would like to introduce a supplementary idea: In eight cases out of the nine cited above, it can be done at the highest overall efficiency in the supercritical speed range. Fine grinding must be based on attrition, not impact. The path of attrition may be vertical, horizontal, even inclined. 2) In coarse grinding, the conventional use of rods is sound practice. However, even the rods can be replaced by autogenous chunks large enough to offer the same impact momentum as the rods. To obtain the momentum, the chunks must be provided with a free fall through a sufficient height in horizontal mills operated at supercritical speeds. Coarse grinding must be based on impact. Detailed analysis of the subject may be found in a paper entitled "All-autogenous Grinding at Supercritical Speeds" in Mine and Quarry Engineering, July 1958. 3) All conventional methods of classification, including wet and dry cyclones, are inefficient in sharpness of separation. Continuous return of huge tonnages of finished material to the grinding unit with the circulating load is senseless practice. In the near future the present methods will be either replaced or supplemented by precision sizing. These three fields are also the ones to which J. F. Myers has so admirably contributed in the past. Fine Grinding at Supercritical Speeds. By R. T. Hukki (Mining EnGineERInG, May 1958). Eq. 9, page 588, should be as follows: T , c, (a — 6&apos;) n D Ltph On page 584 of the article the captions for Figs. 4 and 5 have been placed under the wrong illustrations and should be interchanged.

Jan 1, 1959

By E. R. Borcherdt

IT is notable that the first large-scale mine operation equipped entirely with detachable bits was the Badger State mine of the Anaconda Copper Mining Co. in Butte, Montana, just 30 years ago. This mine in 1922 was producing approximately 1200 tons of ore per day. Much of the data presented in C. L. Berrien&apos;s article&apos; describing the development and installation of the Hawkesworth detachable drill bit were obtained from these operations. As in any pioneering effort, no precedent existed and many difficult problems required solution, so that the changeover to detachable bits at all Butte hill mines was not completed for 6 years. There was widespread disbelief as to the probable efficiency of the new installation. Some attempts were made in 1931 by the owners of the Hawkesworth patents to interest Ontario gold mine operators in the bit. These efforts were not successful, but they undoubtedly stimulated thinking which resulted in the invention and patenting of several well-known Canadian detachable bits, one of which is now a widely used throwaway bit. The success of the Butte installation also led to the development of the threaded type of bit connections by several well-known manufacturers, and in 1935 these bits were introduced to the mining industry on a national scale. The original Hawkesworth bit was not provided with a water hole but, depended upon water passing through the clearance opening between the tongue in the bit and the groove in the rod to flush cuttings from the drill hole, see Fig. 1. In December 1935 it was found that this method of introducing drilling water to the bit face resulted in high dust counts. To correct this a water hole was drilled on the central axis of the bit, passing through the tongue. Unfortunately, quenching water would rise through the small water hole, spot-hardening the tongue to cause breakage, never completely eliminated. In the fall of 1936 large-scale tests indicated that savings would be effected by use of a threaded type of bit, which was therefore adopted as standard for all Butte mines. This type of bit was used until 1947, when it was superseded by a one-use slip-on type. Since the first use of the Hawkesworth bit every detachable bit of importance has been investigated, and where advantages which might reduce costs or increase efficiency were indicated, substantial tests of the bit were carried on in the Butte mines. When tests demonstrated the advisability of changing from one kind of detachable bit to another the change was made at one level or in one area each day until the new rod and bit equipment was used throughout the mine. This involved a minimum of cost and disruption of drilling. Intelligent selection of a detachable bit to obtain optimum results requires careful consideration to achieve a balance between the three principal types of equipment used in the drilling process: 1—drill bits, 2—drill steel, and 3—drilling machines. Optimum results imply maximum output and minimum cost per unit of output. Since every rock type differs in drillability and it is generally impractical to provide equipment for more than one or two types of rock which may occur in one operation, selection of equipment must encompass average drilling conditions. However, on exceptional occasions several widely differing conditions may make it mandatory to provide equipment best suited to each condition. The choice of rock-drilling equipment is a most controversial subject and one that is further complicated by unreliable and frequently misleading performance claims. Small operators without the means for making accurate evaluations of equipment frequently suffer from these over-enthusiastic claims. It is apparent from experience in rock drilling throughout the world that rock drillability is not alike in any two places, and that selection of proper equipment can only be made after conducting thorough trials of various types of equipment. Some recent drilling tests in tactite and hornstone at the Darwin, California mine of the Anaconda Co. present some interesting clues on rock drillability. Microscopic examination of thin sections of these rocks reveals that mineral composition and rock texture are equally important in governing drillability. The Darwin hornstone is at times so abrasive that the carbide bit cutting edges become flattened to 3/32 in. in 2 to 4 ft of drilling, and some carbide bits were dulled to this point after 9 to 10 in. of drilling. This wear was determined to be the proper point for resharpening to eliminate carbide insert breakage or breakage of the steel rod when drilling with 1½ to 1?-in. bits, with a drifter of 2 3/4-in. diam and 90 to 100 psi air pressure, see Supplement A. Before considering the merits of various bit designs it may be well to review the mechanics of drilling rock with percussion drills. A sharp bit cuts by penetration and chipping. The amount of penetration governs the amount of chipping and depends upon the contact area of the cutting edge, the foot-

Jan 1, 1954

By M. C. Fuerstenau, D. W. Fuerstenau

Studies of the collection of alkali and ammonium halides utilizing vacuum flotation techniques and contact angle measurements show that ionic size controls the flotation of techniquesthese halides with amine salts measurementsas collector. Contact angles of air bubbles on sylvite in saturated brines were withaminemeasured salts asascollector.a function of such variables as collector addition, length of collector chain, and pH of the brine. No contact occurs between halite and an air bubble in brines containing dodecylammonium acetate as collector. LONG-CHAINED aliphatic amine salts have been used for the separation of sylvite (KCl) from halite (NaCl) by flotation.1,2 It is puzzling how these two minerals, which are so similar chemically and crystallographically, can be separated by this method. Gaudin" has postulated that the difference in floatability of halite and sylvite with salts of primary amines depends on ionic size: In the case of amine flotation, the cation would attach itself to the chloride. I have a speculation there, which I cannot prove, that the ammonium group, that is the —NH3 group in the amine, floats potassium chloride because the dimensions of this grour, as it has been measured in other compounds is almost identically the dimensions of the potassium ion, quite different from the sodium ion, and so it fits where potassium had been, in place of it and not attached to it. Apparently, because an aminium ion (RNH3+) is much larger than a sodium ion, it cannot fit into the lattice of halite. Taggart also has speculated that ionic size may control the floatability of sylvite.4 The object of this experimental investigation has been to test this hypothesis and to study what controls the adsorption of cationic collectors at the surface of sylvite. Since collection is to be approached from the viewpoint of ionic size, the ionic radii that are of interest in this work are presented in Table I. The values of the ionic radii of the ions listed in Table I, except NH4+, are those given by Pauling." Several different values for the radius of the ammonium ion have been given, but that of Goldschmidt6 seems to be preferred. The radius of the charged head of a dodecylammonium ion is assumed to be the same as that for the ammonium ion. Little experimental work has been reported in the technical literature concerning the separation of sylvite from halite by flotation. Guyer and Perren studied the separation by flotation of 50 pct binary mixtures of NaCl, KC1, NH,Cl, NaNO3, KNO3, K2SO4, and Na,SO, using either oleic acid or a sodium sul-fonate as collector.&apos; It is possible to measure floatability under actual flotation conditions where all three phases, air- water-mineral, are present by vacuum flotation tests and contact angle measurements.9 Both of these techniques were used in the experimental approach in this paper. Experimental Method and Materials The vacuum flotation tests were run with glass-stoppered pyrex graduated cylinders. Twenty-five ml graduates were used to test the floatability of all salts studied except rubidium and cesium salts. For each test distilled water containing the desired collector concentration was saturated with the salt to be floated. Sufficient salt (—48 mesh) was added to leave about 2 ml of solids in the bottom of the graduate. After the graduate had been agitated several minutes to saturate the solution with air, a vacuum was applied. If the salt were floatable in the collector solution, the gas bubbles attached themselves to the particles, and the particles floated to the surface. In determining the floatability of the expensive Rb and Cs halides, the experiments were run in 10 ml graduates with about 11/2 ml of collector solution initially. Contact angles were measured in the usual manner except that the solutions had to be previously saturated with the mineral to avoid dissolution of the crystal. Solutions for studying contact angles were made by adding the desired amount of collector to a saturated brine, giving the collector concentration in molarity. The mixture was agitated until dissolution of the collector was complete, with the exception of those concentrations greater than about millimolar. At these high concentrations complete dissolution of the collector was impossible. The face of the mineral to be tested was a freshly cleaved crystal of halite or sylvite. The mineral was placed in the brine and conditioned with collector for at least 15 min, which was found to be long enough to obtain a maximum value for the contact angle. The temperature remained constant during each experiment. The experiments were run at 24°C ±2°C. For contact angle measurements, a crystal of halite from Carlsbad, N. M., was used. Several samples of sylvite were used in this work: a crystal of sylvite from Stassfurt, Germany; a crystal from Carlsbad, N. M.; and a crystal of chemically pure potassium chloride. Saturated brines were made from reagent grade chemicals and distilled water.

Jan 1, 1957

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication&apos;, a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication&apos;, a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By H. E. Stauss, J. Hino

INTEREST in silicon has arisen again in the past decade as a result of improvements in crystal rectifiers.&apos; Although the preparation of silicon was first reported by Berzelius in 1880, the early product was of relatively low purity, and only the need for rectifiers in World War II led to the production of a 99.9+ pct pure powder. This material in crystalline form was consolidated into massive silicon for use, and the method developed was to melt it with selected added constituents as "doping" agents. Melting techniques, therefore, are of great importance. There are two basic problems in producing silicon ingots free of doping additions; one is the prevention of spitting and the other is prevention of cracking of the ingot during freezing. The most satisfactory arrangement yet developed for producing massive silicon is to melt and freeze in a cylindrical quartz crucible surrounded by a concentric heating element and concentric radiation shields or insulation. For example, use can be made of a tubular heater with a high frequency generator as the source of power and reflecting shields of alundum cylinders. The spitting of silicon is related to gas evolution, and the gas comes from two primary causes—adsorbed gas and the reaction products of silicon and the crucible. Gas is also released from bubbles contained in the quartz crucible walls. Improved removal of adsorbed gas can be achieved by means of controlled melting and freezing. The seriousness of the problem in vacuo is reduced with an electrically operated mechanical movement of the high frequency power coil. The upper portion of the powder charge is melted first and the high frequency coil lowered until the powder is completely molten. During cooling the high frequency coil is raised slowly. These means also reduce the final nonviolent extrusion of large beads of metal through the ingot top during freezing. Better control of spitting and bead extrusion is obtained when melting is done under helium at. atmospheric pressure instead of in vacuo. The problem of reaction between silicon charge and crucible in practice is confined to the reaction between silicon and quartz. This2 apparently is: Si + SiO2 + 2SiO The part that this reaction plays in spitting has not been isolated for separate study. SiO is a volatile vapor at the melting point; of silicon and is released freely during melting in vacuo, but hardly at all in helium at atmospheric pressure. The cracking of ingots is a major difficulty in melting silicon, and its prevention requires special melting techniques or the addition of "toughening" agents such as aluminum or beryllium.&apos; The cracking of the ingots has been explained as being the result of the expansion that occurs upon freezing; although direct observation of freezing ingots reveals visible cracks on the surface only after a red heat has been reached, suggesting that cracking is the result of differential contraction of silicon and quartz. Silicon wets quartz, and the ingot adheres tightly to the crucible. Therefore as ingot and crucible cool, the two either have to pull apart, or at least one must crack. Surprisingly, in spite of the relative thinness of the quartz and the thickness of the ingot, the ingot and the crucible both crack. Microscopic and X-ray4 studies fail to show any plastic flow other than twinning in the ingots. Slow cooling fails to prevent cracking. Another possible solution to cracking is to weaken the crucible. Use of thin-walled crucibles finally led to success with fused quartz crucibles with a wall thickness of 0.25 to 0.50 mm. With such thin-walled fused quartz crucibles consistently uniform success is secured in producing sound ingots 30 mm in diam from the purest available grade of silicon (99.9+) without the use of any type of addition. Melts are made in the size range of 50 to 100 g. Omission of a deliberately added doping agent is not sufficient to insure pure ingots. The reaction of silicon with crucibles and the resultant solution of impurities in the silicon is well-established." In this laboratory, the presence of Al, Be, and Zr has been found spectroscopically in ingots melted in contact with alumina, beryllia, and zircon. The best crucible materials reported in the literature are MgO and SiO2. Use of MgO in this laboratory has resulted in a heavy deposit of magnesium on the furnace walls, showing that a reduction of the magnesia occurred and the resulting magnesium removed from the melt by volatilization. In the case of quartz, the silica is reduced and SiO liberated to deposit on the equipment walls. There probably is real danger that oxygen is dissolved in the ingot when either magnesia or silica is used as the crucible material. Preliminary analyses by Dean Walter in his vacuum unit in this laboratory6 indicate the presence of oxygen in undoped silicon melted in quartz.

Jan 1, 1953