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By Leon Merker

FLAME fusion growth of strontium titanate crystals was undertaken to obtain large transparent crystals on which physical data could be gathered. The fact that strontium titanate is a cubic crystal and probably has a high index of refraction indicated that it might be useful in optics. No large boules* of strontium titanate had been synthesized previously, and none have been found as natural occurrences. The flame fusion process, invented by Verneuil in 1904,1 was first applied to grow large crystals of ruby and has since been used extensively to grow crystals of corundum and spinel on a commercial scale. Only during the past nine years has this technique been applied to the growth of large single crystals of other high melting compounds such as rutile,2 mullite,3 and ferrites4 One of several significant advantages of the flame fusion technique over more conventional methods of growing crystals from a melt is that the crystals are grown without the use of melt containers. This fact alone excludes other methods of growing crystals from a melt whenever there are compounds with a melting point near 2000°C or above. Growth of the crystal, similar to that of a stalagmite, takes place inside a circular refractory furnace that does not contact the crystal, Fig. 1. This eliminates a serious source of impurities as well as the likelihood of multi-crystalline solidification along the container walls. The flame fusion technique is particularly advantageous for research because it produces large crystals quickly and at lower cost. A corundum crystal 25 mm long and 12 mm in diam can be grown in 2 to 3 hr. Operating conditions permit observation of the growing crystal during any stage of the process. The various flame patterns and a wide range of oxidation-reduction conditions can be investigated in a relatively short time. It should be pointed out that formation of the foot of the boule is the most critical step in growing an unfractured boule. When the tip of the sintered cone is fused to initiate crystal growth, the original area of fusion should be kept as small as possible so that one crystallite can assume dominance over all the others and propagate as a single crystal. If the boule start happens to consist of several crystals, usually the entire boule also contains several crystals. In many cases these tightly cohering crystals exhibit different crystallographic orientations. Although the basic technique of the original Verneuil process has been retained, refinements in method and burner design have been developed in recent years. For example, boule growth may be initiated on a seed crystal rather than by fusion of a sintered cone. The danger of multicrystalline or twinned boule starts is thus eliminated, and this procedure may also be used to grow boules of predetermined crystallographic orientation. Prior Art: Of the many attempts to produce artificial gem crystals, most early efforts% ere directed toward synthesis of .rubies and sapphires and diamonds. None of these efforts resulted in a process that was commercially practical. Without exception only tiny crystals of corundum were obtained, and those at excessive cost. Verneuil announced his process in 1904; Ravier6 in 1934 presented a detailed description of a commercial boule production plant. Descriptions of the German synthetic stone industry, the process details, and the equipment used have been published by Barnes7 and by Merker.'

Jan 1, 1956

By C. K. Eilerts, J. D. Ham

Laboratory research has been conducted to evaluate the characteristic effects of condensate saturation on the mobility of gas in typical reservoir rocks. A pump with two pistons provided phases in equilibrium at controlled flow rates and constant liquid-vapor volume ratios. Core samples were tested in a holder that permitted sealing steady-state phases in the pore spaces under flow test pressures for weighing with sufficient precision to give an accurate measure of the attained saturations. Parameters of the study were pressure, apparent velocity, flowing liquid-vapor volume ratio, fluid composition, core material and length-to-diameter ratio. Tests were conducted at 515 and 1,515 psia to determine the effect of pressure on the mobility-saturation relationship. Influence of the apparent velocities 0.30, 0.15 and 0.07 cm/sec and of five liquid-vapor volume ratios from 0.0001 to 0.01 was determined at 515 psia The principal fluid system was nitrogen and and separator liquid from a Gulf Coast condensate, but the effect of a condensate of different viscosity was also determined. The significance of a possible concentration of liquid near the outlet end of the test cores was investigated. Core materials included a consolidated sandstone and a low-permeability limestone. Relative mobility and liquid-vapor volume ratio relationships are concluded to be dependent on pressure, saturation and, to a lesser extent, on velocity. For each porous medium and fluid there is a minimum saturation essential to two-phase flow, and high velocities of flow have only limited effect on saturations in this range. INTRODUCTION It is now recognized that knowledge of the availability of a reservoir gas — the period that gas may be recovered from a reservoir at a given rate — is as important as the estimate of gas in place. When reservoir conditions are such that pressure decline owing to production will result in retrograde condensation, liquid saturation can increase in the structure around the production well in a way that may restrict flow capacity, and hence future availability. l Based on a numerical solution of transient radial flow of single-phase gas-condensate fluids, 2 a program for computing the accumulation of condensate in a reservoir and the effect of this condensate on deliverability has been developed. During this development a need evolved for data that described the influence of pressure, velocity of flow and condensed liquid on mobility as recovery progressed. This paper presents the results of experimental investigation to obtain insight into the mobility relationship at reservoir pressures of gas-condensate fluids. A core holder for flow tests at reservoir pressure was developed to weigh the core and its fluid contents under pressure to determine saturation. A specially constructed pump was used to drive a two-phase fluid through the core until a steady state prevailed. The core was used as a differential device, and properties measured were intensive rather than extensive. APPARATUS Fig. 1 shows a schematic representation of the major pieces of equipment used in the mobility determination. The weighable core holder is connected to a two-piston, constant-displacement pump. Attainment of steady-state flow is indicated by stability of the flow differential read from the high-pressure manometer. WEIGHABLE CORE HOLDER An important part of the data needed was the mobility-saturation relationship. This required that mobilities and saturations be measured at pressures, flow velocities and liquid-vapor volume ratios characteristic of condensate reservoirs.

By W. H. Triplett

DISCUSSION John G. Barry (Mexico)—"The Nerinea limestone," writes W. H. Triplett, p. 584, "is ... medium-bedded (0.5 to 1.0 m)...." This is the Zuloaga formation. It has always been described as thick-bedded (1.0 to 3.0 m). "Whether the marls and shales were less amenable to replacement," he goes on to say, ". . . is a matter of opinion." In general, it is probable that the thinner-bedded formations were less competent than the nearby thicker-bedded, so that the latter produced pre-mineral breccias when all were subjected to flexing stresses. With reference to Mr. Triplett's analysis, p. 584, under Lower Cretaceous, in the Taraises and Cupido formations some few horizons should be considered as possibly containing hidden orebodies. In the Potrero camp, shown on the general map in the northwestern part of Fig. 4, p. 587, several mineralized beds are known; they are found throughout the whole thickness of the Cuesta del Cura formation. With regard to intrusive rocks, p. 585, the general map, Fig. 4, shows that the Potrero and Noche Buena camps are near a third, monzonitic intrusive. It seems doubtful that the Aranzazu was any hotter than the Providencia camp. However, the former does contain large deposits of exogenetic silicates, which in large part occur within the Zuloaga limestone, as shown by Bergeats in a stereogram. At the Aranzazti camp the La Caja formation was only slightly changed, whereas it was altered highly at the Providencia, possibly en-dogenetically. That the temperatures at the Providencia camp were relatively high at one time is also shown by the tourmaline veinlets and lenses in the monzonite and by the garnets on Temeroso peak; high temperature mineralization has possibly been eroded. Maps and sections show that the Concepcion del Oro —Temeroso stock occupies the original locus of some 40 kms of sedimentary rocks. The remains of large roof pendants at Carmen and Animas indicate that stoping was active. Whether all the sedimentaries were stoped and assimilated presents a lively problem, a correlative of which would be an estimate of the original constitution of the invading instrusive rock. As to extrusive rocks, see p. 585, there is also a large thick area of the extrusives left near Noche Buena in the "La Caja" intramontane valley of the La Caja range. This place gave its name to the range. The volcanics are also said to occur in considerable amount in the Mazapil valley.'' Turning now to the remarks under Regional Structure, p. 586, as partly indicated on the general map, Fig. 4, the Mazapil Mountains of the Mazapil region are a continuous, U-shaped range including a northern leg of some 24 km, a southern leg of similar length, and a uniting base which lies to the East and which measures some 10 km in a S 20 E direction. Thus the U-shaped mountains are continuous through a length of 58 km and also contain one continuous anticline, the adjacent valleys being synclinal. The northern leg of the U is called the La Caja range, the base is called the Concepcion del Oro range, and the southern leg the Santa Rosa range. The ranges in northeastern Zacatecas and southern Coahuila contain anticlines and the valleys contain synclines, which where thin are necessarily highly compressed isoclines with very steep dips. Many of the anticlines also have isoclinal components which are overturned, original mushroom tops being indicated. The anticline in the base of the U of the Mazapil Region, Concepcion del Oro range, is a recumbent anticline, over to the ENE, with a necessarily subjacent recumbent syncline.

Jan 1, 1953

By J. H. Hamilton, J. R. Lewis, K. W. Heinlein, V. D. Hanson, J. M. 194-000-000-006 Vonfeld, J. P. Denny

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion NO. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and — -in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3h-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 34 in., and 1'/4x in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into YSXO which is cleaned in the fine coal plant and 3x for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1953

By William P. Roe, James F. Ellis, W. P. Fishel

This paper reports the distribution of sulphur between iron and titanium in Fe-Ti-S alloys and in Fe-Ti-C-S alloys. The compound TiS was found, which exists as a separate phase at temperatures below 1200°C. Titanium in steels reacts with sulphur in preference to carbon. THE general relationship between sulphides and oxides suggests that titanium should form a sulphide having properties similar to those of titanium oxide. Specifically, titanium should form a sulphide having a high melting point, indicating a stable compound of low solubility in iron. In order for titanium to function as a desulphurizer or sulphur-fixing agent, it must form a stable sulphide. In order for titanium to be useful in steels as a sulphur-fixing agent, it must react with sulphur in preference to carbon; and to prevent red shortness, the sulphide formed must have solubility characteristics such that grain-boundary precipitation of a low melting phase be prevented. The terms desulphurizer and sulphur-fixing agent when used in this paper mean that titanium effectively ties up the sulphur as a stable sulphide of titanium and prevents the formation of FeS. The partition of sulphur between iron and titanium was studied first in a series of Fe-Ti-S alloys with carbon absent, and then in similar alloys with carbon present. It has been established1 a that titanium forms in Fe-Ti-S alloys a sulphide of undetermined composition which can be identified microscopically, and that the titanium-sulphur compound does not respond to sulphur printing. It has been suggested" that titanium acts as a sulphur-fixing agent, although little proof has been given. A report% f The Advisory Committee on Metals and Minerals summarizes the existing knowledge concerning substitutes for manganese in steels. Distribution of Sulphur Between lron and Titanium with Carbon Absent The alloys for this investigation were made by -melting Armco iron, metallic titanium, and iron sulphide in alundum crucibles in an induction furnace. The titanium was added after the other ingredients had melted. In these alloys it is recognized that some TiO, is present, since the melts were made in the air and since no other deoxidizing agent was used; therefore, some of the titanium was not available for union with sulphur. Thirteen ingots were made. Ingots 2 to 8 were cast in baked-sand molds; ingots 12 and 13 were cast in metal molds; and ingot 9 was allowed to cool in the crucible in which it was melted. All ingots were annealed at 900°C for 3 hr and were cooled slowly in the furnace. Subsequent information indicates that this anneal had no effect upon the titanium sulphide particle size, since the sulphide does not go into solution at this temperature. The ingots as-cast were approximately 8 in. long and % in. diam. The compositions of the eight ingots and the results of the partition of sulphur are recorded in Table I. Total titanium and total sulphur were determined by standard gravimetric methods. Sulphur, as iron sulphide, was determined by the evolution method. Boiling HC1 (1:4) liberates the sulphur from iron sulphide, but leaves the titanium sulphide practically undecomposed. A complete separation of titanium sulphide and iron sulphide cannot be made by digesting these compounds in dilute HC1 since titanium sulphide was found to dissolve slowly. The amount of titanium sulphide decomposed will depend upon the time in contact with the acid and upon the particle size of the sulphide. The point

Jan 1, 1952

By Caudle B. H., Cooper H. E. Jr., O. K. Kimbler

The results of studies of areal sweepout behavior in nine-spot injection patterns are presented in this paper. The ratio of the production rates of the two types of producing wells in a nine-spot pattern is considered in its effect on breakthrough. A model study was used to develop a method to predict the production histories of both side and corner wells and to develop the production history of the pattern or the field. INTRODUCTION The importance of areal sweepout behavior in injection operations has been recognized for a number of years. We now know that the fraction of a reservoir which will be reached by an injected fluid is a function of the geometric arrangement of the production and injection wells and of the mobility ratio of the fluids. Of these two, the mobility ratio (which is a measure of the relative ease with which the oil and the injected fluid can move through the reservoir) appears to have the greatest effect on recovery. The effect of mobility ratio on production history has been reported for most of the dispersed injection patterns (i. e., five-spot, staggered and straight-line drives).4-6 ere has been very little published on the nine-spot injection pattern. This may be because the two types of producing wells in the nine-spot pattern can—and sometimes should —be produced at different rates. This adds a second variable (the fist being mobility ratio) to be covered in a study of the nine-spot flooding network. Muskat1 has reported the sweep pattern efficiency at breakthrough for a mobility ratio of one at various ratios of producing rates for the two types of wells. For these conditions he found maximum oil production at breakthrough to occur when the corner well (the producing well farthest from the injection well) is produced 10.7 times as fast as the side well. Other investigatorsa2,3 have studied a few of the many possible operating conditions possible with this injection pattern. This paper presents the results of studies which are strictly applicable to a nine-spot injection pattern surrounded by other nine-spots in a homogeneous reservoir and which has no flowable gas present (no oil bank is formed). Although the full ranges of the variables mentioned above have not been covered, the results reported here should allow reasonable estimates of field operations to be made. EXPERIMENTAL The well spacing geometry of the nine-spot pattern is shown in Fig. 1. Here we see that each injection well is surrounded by eight production wells arranged in a square. Four of these producing wells are located at the corners of the square; the other four are in the midpoints of the four sides. These two types of producing wells are called "comer wells" and "side wells" respectively. It is the ratio of the producing rates of these two types of wells that affects the breakthrough recovery, as calculated by Muskat.' This ratio is defined as the total producing rate of a corner well divided by the total producing rate of a side well. The model used in this study represented one-eighth of a nine-spot pattern, as shown in Fig. 1. It contained the equivalent of one-fourth of a side well, one-eighth of a comer well, and one-eighth of an injection well. Because of these proportions, the actual producing rate ratios in the model were one-half of the ratios of producing rates as

Jan 1, 1965

By Olaf N. Rove

YEAR 1951 has been bright for the mining geologist. He has arrived after struggling for a generation or two to sell his wares through service to the operator, the mine superintendent, and the manager. But as he establishes himself on the operating front, he is faced with even greater challenges; namely, the development of basic geologic principles governing ore-forming processes and the occurrence and distribution of mineral deposits. These principles are needed to guide his ever-widening search into new areas. He must now stimulate the interest, confidence, and imagination of the mining executive and layman in fostering the research essential to expand rapidly the basic science of geology and its more specific applications to the mining industry. The hallowed time-tested tools of the prospector and the industry are no longer adequate. New basic data, principles, and ideas are needed to guide industry's exploration. The entry of Government into exploration, by lending money to prospectors and operating companies to partly finance exploration, is one of the major events of the year. This was one of the activities for which the Defense Minerals Administration was established in the Department of the Interior. DMA was staffed largely with men from industry, but the Bureau of Mines and the Geological Survey have acted as its technical advisors and have provided its field staff. Since the start of this work in May 1951 to November 19, 1951, the DMA has approved 208 exploration projects while denying 318 others. The contracts involve about eleven million dollars worth of exploration, of which Government's share is about sixty percent. A few contractors have already made discoveries and are into production to repay their loans; others have completed their projects without making a discovery. In November, the DMA was split into two successor units. The Defense Minerals Exploration Administration was set up in the Interior Department to carry out the exploration program. The Defense Materials Procurement Agency was organized as a separate agency to carry out the other functions of the former DMA, as well as general strategic materials procurement. The strategic materials group of the Economic Cooperation Administration was transferred to DMPA in order to centralize the procurement from foreign sources into one agency, although the authority and scope of activities of this group have not been announced as of the middle of December. The DMA-DMEA-DMPA programs are making large demands upon the technical manpower of the Geological Survey and Bureau of Mines. It is still too early to evaluate with confidence the productiveness of this diversion so far as the immediate and long-range effects are concerned. Many of the individuals associated with these programs, as well as others in the industry, are convinced that from a long-range national viewpoint, the regular programs of both the Survey and the Bureau equal or even exceed in importance the current emergency mineral activities of these two agencies. Uranium Uranium continued to be the glamour-girl metal of the mineral industry, and at the request of the Atomic Energy Commission uranium and thorium were included in the DMA exploration program. Industry's intensive prospecting and mining activities in 1950 were further expanded early in 1951 when the Atomic Energy Commission announced an increased price schedule and a new bonus payment

Jan 1, 1952

By G. W. Nabor, H. J. Ramey

A blotter-type electrolytic model was utilized to prepare flow diagrams for a field test of the in-situ combustion process. It is pointed out that the areal sweep of a combustion pattern is similar to sweep patterns that would be developed at an infinite mobility ratio, which exists (approximately) across a combustion front because of the complete removal of liquids from the sand behind it. The precision of the blotter method was tested by comparison with results obtained by other techniques and was found to be satisfactory. The blotter-type model will not furnish as much information as more elaborate and expensive potentiometric models, but its speed of operation and ease of construction make it a highly satisfactory tool to determine areal sweep patterns. A tabulation of sweep efficiency and mobility ratio is furnished for various well geometries. INTRODUCTION In connection with the first field experiment with the in-situ combustion method of oil recovery," flow diagrams for the unique well geometry and boundary conditions involved in the subject test were developed. From these diagrams, information concerning the areal sweep and distribution of flow was obtained. A survev of the literature on potentiometric models, utilized to solve two-dimensional flow problems,1,2,3,4,5,6,8,9,10 indicated that the information desired could be obtained by means of a blotter-type model by making certain modifications in the technique. The following discussion describes the application of the modified blotter-type electrolytic model to the solution of the problem of the flow of gases in an oil reservoir for an engineering appraisal of the progress of the combustion front during the first field experiment. Considerable information has been published on the theoretical aspects of electrical model techniques. One author stated that:' "The models are based on the observation that since the velocity of an ion in an electrolytic system is proportional to the potential gradient, just as the velocity of a fluid particle in a porous medium is proportional to the pressure gradient, the paths of the ions in the electrolytic systems must be similar to those of the fluid particles in a porous medium with the same geometry and equivalent boundary conditions." This suggestion of a real analogy has been established repeatedly by comparisons of analytic derivations with model results. The analogy between the movement of a combustion front and the model results is not as apparent, since the combustion process differs from water flooding and gas cycling in that the velocity of the burning front is different from the velocity of the injected fluid at the front in combustion. Analogy between electric current flow and movement of the burning front exists because the local velocity of the burning front is proportional to the air (mass) velocity at this point (assuming frontal temperatures are at least as high as the ignition temperature of the fuel). Most model studies fall into one of two categories: (1) electron conduction, or (2) ionic conduction models. Examples of these are models which employ as flow media either a thin metal sheet, or a porous blotter saturated with an electrolyte, respectively. Of the two, the porous blotter model, an ionic conduction model, appears to be the most adaptable to the flow problem that results when using in-situ combustion. This problem requires that the mobility of the particles in the model be controlled analogous to the mobility of gas flowing through burned sand of high permeability to gas and then through oil sand of lower permeability to gas. Although the blotter model has heretofore been

Jan 1, 1955

By M. R. Annis

Drilling mud rheological and gel property changes due to elevated temperatures frequently cause problems in drilling deep wells. A laboratory investigation of the effects of time, temperatures up to 3001; and mud composition on these properties was made with concentric-cylinder, rotational viscometers of the Farm type. The viscometers were sealed from the atmosphere to prevent dehydration of the sample. Gel strengths were found to be more sensitive than viscosities to changes in temperature and mud cornposition. The high-temperature gel strengths of bentonitic clay drilling fluids were not predictable from low-temper.atl4t-e measurements. At high temperatures, [lie clay flocculates. The floccu-lation temperature depends on the concentration and type of solids in the mud and the degree of chemical defloccula-tion. As the bentonite content of a mud increases, floccrrla-tion temperature decreases. Lignosulfonnte treatment raises the flocculation temperature. To minimize adverse high-temperatrrre effects on mud properties, the mud should be maintainted at minimum solids content, properly treated with. a defloccullant which is stable at the maximum ten?perature encountered and maintained at a pH high enough to insure activation of the deflocculant for the duration required. The Methylene Blue Test for cation exchange cnpacity of a clay was found to be a useful guide in deter.niinirig when a mud contains a dangerously high clay conWnt. INTRODUCTION In drilling a well it is desirable, for several reasons, to know the effects of time and temperature on the rheological and gel properties of the drilling fluid in the hole. Problems associated with drilling fluids normally occur down-hole: so it is reasonable to be interested in the properties of drilling fluids at the conditions which exist down-hole. It has long been observed that high pump pressures are often needed to start circulation after a trip and that the "bottom-up" mud that is circulated back to the surface is usually more viscous than it was before "cooking" at the bottom of the hole for several hours. Burk-hardt' showed that a knowledge of rheological proper-ties of muds under down-hole conditions is necessary to predict pressure surges. He showed that the viscosity of a mud greatly influences the magnitude of pressure surges and the likelihood of lost returns. McLean et aL~ showed that the rheological properties of a mud under down-hole conditions are very important to cementing operations. This paper presents data showing the effects of time and temperature on rheological and gel properties of water-base drilling fluids. Measurements of gel strengths and rheological properties were made with two different concentric-cylinder rotational viscometers of the Fann type. One was the conventional six-speed viscometer modified to operate at temperatures up to 350F and at the vapor pressure of the liquid at test temperature. The other viscometer was newly designed to operate at temperatures up to 500F and pressures up to 1,000 psi. Tests with both instruments were made under essentially the same operating conditions. The new viscometer is shown in Fig. I. In this investigation, great emphasis has been placed on the rheological properties of clay suspensions, since clays are largely responsible for a mud's thixotropic and gel-

By S. M. Brisbane

THE life of refractory linings in rotary cement kilns can be shortened by uneven or inadequate support of the kiln and its shell and by variations in the conditions of operation. Alteration of these factors may, according to their nature, bring about mechanical deterioration of the lining or promote chemical attack. Chemical attack has been described elsewhere.1-4 The distortion of cement kilns has been discussed in a general manner by Rochow,6 ho indicates the amount of distortion which may occur in an unlined shell, and by Rosenblad: who states that the deformations of the shell are greatest above the trunnions. The present article indicates the extent of the distortion of a kiln to an oval shape in certain selected positions and the deviation from a straight line of the kiln along its length between two supports. The cement kiln is a long, hollow, rotating cylinder consisting of steel plates which may be either welded or riveted together. This shell is supported on tires, frequently 60 ft apart, which roll on trunnions. The large mass of the kiln causes distortion of its cross-section; it becomes slightly oval, i.e., diameters lengthen as they become horizontal and shorten as they become vertical. There is also a tendency for the shell to bow between supporting tires; this bowing may be upwards or downwards depending on the position of the weight forces and the supports. The extent of the deviations from the ideal kiln shape was investigated. Observations described in this paper were made on the shell of the clinkering zone between the first and second tires of two of the kilns at the Geelong works of Australian Portland Cement Pty. Ltd. The kilns were both 400 ft long and 10 ft diam with a welded enlarged burning zone 11 ft 6 in. diam. The shell was fabricated from mild steel and in this section its thickness was 1 in. It was lined with 41/2 in. of chemically bonded magnesite-chrome bricks which were jointed with mild steel plates. The kilns operate on a 4 pct slope and the speed may be varied between 0.75 and 1.68 rpm. The wet process is used; kilns are coal fired and are fitted with integral coolers. Temperatures within the kiln are difficult to determine with any accuracy because of the absence of black body conditions, but surface temperatures are probably in the range 1420° to 1470°C. Average shell .temperatures at the two positions at which the deformation studies were made were 370°C and 355"C respectively. Methods: In determining the ellipticity it was necessary to measure the lengths of the vertical and horizontal diameters while the kiln was in operation; data obtained from a stationary kiln would not have the same practical significance. For this purpose the four points V, W, X, and Y at the ends of two mutually perpendicular diameters were marked on one kiln. The point X is shown in Fig. 1. For the measurement of the length of the vertical diameter a vertical column, to which a horizontally aligned telescope was attached, was placed 10 ft from the kiln. The telescope could be racked up and down in a vertical plane. Two sets of readings were taken, one set when each of the points V, W, X, and Y was at its maximum height above the

Jan 1, 1957

By W. W. Gerberich

SINCE the original formulation of fracture mechanics concepts,&apos;y2 relatively little work has related the fracture mechanics description of metal behavior on a gross, structural component scale to the behavior of its microstructural constituents. The purpose of this note is to suggest the utilization of fracture mechanics to describe material behavior on a microscopic scale. A Fracture Concept for Two-Phase Structures. A critical displacement concept considering the tough unidirectional phase in a relatively brittle matrix is first examined. It is assumed that a flaw exists at position 1 as depicted in Fig. 1. As the crack moves from position 1 to 2 the plastic zone could be of the shape described with the size approximated by the Dugdale3 model: where c is the half-crack length, OO is the applied stress, and oyS is the yield strength. Hahn and Rosen-field4 have presented a simple fracture criterion for homogeneous materials based upon the displacement at the crack tip. They also have shown the equivalence of the critical displacement, v*, to fracture toughness by Kc = (2v*oysE)1/2 [2] The displacement at the crack tip is given by and the displacement at any distance in front of the crack tip may be determined knowing the plastic zone size and utilizing the development of Goodier and Field.5 Recalling Fig. 1, the value of v* for fracture in material M1 may be calculated from Eq. [2] providing the critical stress intensity factor is known. As the material is loaded, when vc > vM1 the crack moves from position 1 to position 2 where it encounters the tough second phase. If vc2 < vm2, then the crack will be arrested providing the width of the M2 phase is sufficiently large. This condition is necessary since the displacement at position 2 has increased due to the longer crack length. Thus, the displacement at the distance X (representing the dimension of the second phase) in front of the crack may be larger than the critical displacement for failure in the brittle material. If v, > vm, then failure will proceed in the brittle material. The value of v, may be calculated as indicated above. This latter consideration is the same as predicting fracture of a brittle second phase at some distance in front of a crack located in a ductile matrix. Experimental Evidence. On a macrostructural scale, tungsten wires in a ductile Be-Cu matrix are seen to fracture well ahead of the main crack front in Fig. 2. Utilizing a Kc value of 14.2 ksi-in.1/2 obtained by Schroder et al.6 for as-received tungsten, the critical displacement 2v*, for fracture is calculated from Eq. [2] to be about 6.5 X 10-5 in. The crack tip displacement, 2vc, is calculated from Eq. [3] to be 0.0028 in. indicating that fracture would occur at a considerable distance in front of the crack tip. From the ratio of v*/vc and the plastic zone estimate of Eq. [I], the distance in front of the crack tip at which a tungsten wire should fracture is calculated to be about 0.195 in. As shown in Fig. 2, a fractured wire occurs at a distance of 0.140 in. (fractured in three places), not at 0.250

Jan 1, 1968

By J. B. Clark, A. S. Yue

PfANN1 has shown that when a cylinder of molten binary alloy freezes directionally, the solute distribution can be described analytically by cg=k(l-g)k-1 [1] in which Cg is the solute concentration in the solid at the point where a fraction g of the original liquid has frozen and Co is the initial solute concentration. The term k is the effective distribution coefficient of the solute and is defined as the ratio Cx/CL where Cl is the solute concentration in the main body of the liquid. Both the slope and the intercept at -log (1 - g) = 0 of a logarithmic plot of Eq. [I.] provide a measure of k. Under conditions of freezing where diffusion in the solid is negligible and the solute concentration in the liquid is uniform, the effective distribution coefficient k, derived as above, is equal to the equilibrium distribution coefficient taken from the phase diagram. However, under ordinary freezing conditions, even though solid-state diffusion is negligible, the solute rejected from the freezing solid does not have sufficient time to diffuse uniformly throughout the main body of the liquid. A concentration gradient is formed in a boundary layer in front of the advancing solid-liquid interface as pointed out by Rutter and Chalmers.&apos; Thus, under these conditions, the concentration of the freezing liquid in the boundary layer is higher than that predicted from the equilibrium phase diagram and consequently the effective distribution coefficient k, obtained from directional freezing experiments, is larger than the equilibrium distribution coefficient. The symbol k will designate the effective distribution coefficient in the discussion which follows. In this paper, the determination of the effective distribution coefficient is demonstrated for several dilute binary alloys and a polynary magnesium alloy. The effect of freezing rate on the value of the derived k is presented in detail. An example for the calculation of the solidus in a dilute binary solution using the experimentally determined effective distribution coefficient is given. MATERIALS STUDIED Binary magnesium alloys of copper, nickel, and zinc containing approximately 0.10 wt pct solute and a polynary alloy containing approximately 0.10 wt pct each of several elements were selected for study. The spectrographic analyses of these alloys are given in Table I. The analyses are believed accurate to within +5 pct of the stated value. EXPERIMENTAL PROCEDURE Extruded rods of the alloys, 3/8 in. in diam and 11 in. long were used for directional freezing studies. The alloy rods were melted horizontally in a high-purity graphite boat by a Nichrome-wound tube furnace which moved parallel to the length of the rod. The boat was supported inside a Vycor tube suitably connected to provide a protective atmosphere of dry SO2. For an experimental run, the following procedure was used. The alloy rod was cleaned in dilute HNO, and dried. The graphite boat containing the alloy rod was placed within the Vycor tube and the tube connected to the gas train&apos; The &apos;ystem was purged for 20 min with dry argon and then a flow of dried SO, was maintained for the duration of the run. The movable furnace was positioned and either all or a desired portion of the alloy rod was melted. After attainment of steady-state temperature gradients the molten bar was solidified from one end to the other at a controlled rate by pulling the furnace along the length of the bar at the desired speed. At the conclusion of the run, the directionally frozen alloy rod was analyzed spectrographically at 1 1/4-in. intervals.

Jan 1, 1961

By E. E. Donath

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

Jan 1, 1953

By Henry A. Stiff, and Lawrence E. Davis

The authors previously presented a method for predicting the tendency of oil field waters to deposit calcium sulfate. The present paper gives a similar method for calcium carbonate. Methods for predicting calcium carbonate scaling tendencies in fresh waters have been available for some time, but these could not be used for brines. By experimentally deriving the value of the K term in the Langelier equation, a method has been developed which applies to waters of high salt content. A statistical study is included which shows that the experimentally derived values of K are in good agreement with actual conditions. Several applications of the final equation to production practice are given. INTRODUCTION The authors previously presented a method for predicting the formation of calcium sulfate scale in oil field waters.&apos; Although calcium sulfate deposition is important in production operations, the majority of scale problems involve calcium carbonate. The present communication discusses a method by which the formation of this type of scale in oil field waters can be predicted. Calcium carbonate precipitation is caused by a shift toward carbonate in the carbonate-bicarbonate-carbon dioxide equilibrium. When equilibrium shifts in the other direction, the precipitate goes back into solution. Since there is usually considerable delay between the establishment of an equilibrium and the precipitation or solution of calcium carbonate, unstable conditions exist in which a water will precipitate or dissolve calcium carbonate on standing. Tillmans? who did a major part of the early work on carbonate scaling, pointed out that the condition of equilibrium not only indicates the tendency of a water to scale but also is an indication of its corrosive properties. Previously precipitated calcium carbonate combines with iron to form a dense crust which inhibits corrosion. If the water tends to dissolve carbonate, the scale becomes porous, and electrolytic corrosion takes place. Tillmans1 work was extended by several investigators until in 1934 Langeliers developed an equation setting forth the conditions of carbonate equilibrium. By the use of this equation the pH of a water at equilibrium can be calculated. If the actual pH is higher than the calculated pH, the water has a tendency to form scale. If it is lower. the water has a tendency to be corrosive. Langelier&apos;s equation can be expressed in a simple form as follows: SI = pH-pCa-pA lk-K where: SI is the stability index. A positive index indicates scale formation. A negative index indicates corrosion. pH is the pH of the water sample, as actually determined. pCa is the negative logarithm of the calcium concentration. pAlk is the negative logarithm of the total alkalinity. K is a constant, the value of which depends on the total salt concentration and the temperature. This equation has been shown to apply to waters with totaI solid concentrations as high as 4.000 ppm. In fact, control of fresh water treatment by means of this equation has been standard text-book practice for a number of years. Nomographs have been worked out so that the stability index of a fresh water sample can be determined in a matter of minutes. Most oil field waters, however, contain well over 4,000 ppm of salts and for this reason the usual application of Langelier&apos;s equation can not be made. By an empirical method we have extended the application of the Langelier equation to waters of high salt concentration. By the use of this equation the tendency of oil field waters to deposit calcium carbonate can be predicted.

Jan 1, 1952

By D. W. Loughridge

INTRODUCTION Raising capital in the 1990s is a timely subject. However, many of us thought why should raising capital in the 1990s prove to be unlike it was in the 19805, the 1970s, the 1%0s, or earlier? There are a lot of creative people in banking and in corporate treasury departments. New tools and techniques are continuing to emerge, many of which are discussed in other papers in this book. While we have new financing tools at our disposal, the underlying issue has not changed. Projects and investments must be judged on their own merits. If they cannot be justified by conventional financial analysis, they should not be built. If they can be justified, it is likely that the financing will be available. The challenges faced in raising capital in this decade will persist to the next. The issues of the 1980s -- currency fluctuation, disruptive merger and acquisition activity, commodity price volatility, political risk, and debt crisis -- will all persist in an increasingly international business environment. I will focus on the financing we have just completed for the Escondida Copper Project in Chile. The Escondida financing is structured along the classic project financing model developed in the late 1970s, but it deals with issues of the 1980s and the 1990s. The financing was intriguing, not just because of the technical issues involved, but also the challenge of reaching an agreement in a large and diverse group. Escondida had the one essential feature that made its financing possible. It was commercially very attractive. It would produce at low cost a commodity (copper concentrates) that direct consumers felt would be in tight supply. The project had the direct support not only of its sponsors, but also its customers, and, very importantly, its host government. The non- recourse financing of Escondida would not have been possible without the support of these parties, and without the robust economics that made this effort worthwhile. The issue was more complicated. Operations in all parts of the world entail some political exposure. This project is in Chile, where there was a constitutional requirement that a plebescite be held when the project would be in its early stages. This plebescite would determine the fate of a 15 year old military dictatorship. The project is copper, a commodity generally deemed to be in surplus. Copper has a history of price volatility (whose price has varied from $.58 to $1.53 per pound over the past two years). It is politically sensitive, not only in Chile, but in the United States, Canada and other developed countries. The project is international, with all the problems of dealing with a variety of currencies, a variety of cultures, and a variety of laws and commercial practices. The project is also large and capital intensive, with a total cost of U.S. $1.1 billion. ESCONDIDA PROJECT Escondida, the largest known copper ore body in the world, was discovered in March of 1981, by Utah International in a joint venture with Getty Oil Company. In 1984, both Utah and Getty were involved in ownership changes, Utah being acquired by BHP. A later restructuring of the ownership of Escondida resulted in BHP, as manager, carrying a 60% interest, Rio Tinto-Zinc Corporation (RTZ) 30%, and a consortium of Japanese companies led by Mitsubishi Corporation with 10%. The Japanese consortium is incorporated as JECO (Japan Escondida Corporation). This ownership structure, which spread ownership around the world, was the first tangible step toward managing both the commercial and political risk associated with the project.

Jan 1, 1990

By Robert C. Collins, Clifford L. Jewett

The development and production of artificially colored roofing granules have been key factors in the success of the asphalt roofing industry. They provide protection for the asphalt from solar radiation and satisfy the home-owner&apos;s desire for a wide range of attractive colors. As a result, the asphalt shingle has become the most commonly used roofing material today. In addition to providing a stimulus to the asphalt roofing industry, artificial methods of coloring granules completely changed the nature of granule production from one of quarrying, crushing, and screening to a complex technical operation. Today&apos;s roofing granules are the result of many years of research, and they are produced in modern plants to exact specifications. History Asphalt roofing materials available today are the product of a long evolution of technological development. Forerunners of the present bituminous products, appearing as early as 1780, were primitive constructions of burlap saturated with crude tar or pitch. An early improvement to this basic effort was the dusting of talc, mica, or other finely ground material on the coated surfaces to keep the roofing from sticking to itself in storage. At times some pigmentation was added with the dusting material for initial color, but this was far from satisfactory. In fact, this early product possessed none of the qualifications of a good roof surfacing material. It was not economical; it was difficult to handle and apply; it was not attractive; it provided no resistance to fire; and it would not withstand the elements as well as other products then in use. Methods and machines were soon devised to saturate endless webs of felt with asphalt from the fast-growing petroleum industry. Even though saturated felt became available, this product of rags and wood fiber had almost the same limitations as burlap and tar. Even with heavier coatings of asphalt applied to both sides of the sheet for rigidity and longer life, the product still lacked color and fire resistance. Further, it was found that constant exposure to the sun soon caused the asphalt to become brittle, and it eventually cracked and leaked. This led to the first important use for crushed mineral products on asphalt-coated shingles and provided the key to the subsequent growth of the asphalt roofing industry. When a layer of crushed mineral was embedded in the surface exposed to the weather, the asphalt coating was protected from ultraviolet light and retained its elasticity over a much longer period of time. In addition to this protection, the mineral surfacing provided some resistance to fire. Fire resistance in the past had been found only in the expensive slate or tile roofs and the unattractive and expensive metal roof coverings which were then available. The most common mineral granule applied to the early asphalt roofing products as they began to make their first significant advances after 1900 was screened waste from slate quarries. Slate granules being available in dull shades of red, green, black, purple and a few other miscellaneous colors did provide a degree of color. Since slate has a flat platelike cleavage, it provides a cheap protective cover for the asphalt-coated sheets. Records show that coarse slate screenings were used for asphalt roofing as early as 1906. As the asphalt roofing industry developed, many other natural colored rocks and minerals were used to coat the surfaces of the roofing. The list included silica

Jan 1, 1975

By S. A. Braley

THE first commercial production of bituminous coal in the United States was in 1820, and formation of acid in the areas from which the coal was removed began at that time. Thus it is 130 years since the development of mine acid began. The coal operator has had to deal with the acid water produced in his mines, and his losses from corrosion of pumps and equipment have been tremendous. Other industries and the public have been forced to spend large amounts for their water requirements because of the acid discharge from the mines. There are many contradictions in the literature on this subject probably because of variations in the analytical procedures followed and differences in the methods of calculation and reporting. The opinions previously expressed may be summarized as follows: The production of mine acid has been looked upon as a simple chemical reaction wherein the oxygen of the air has reacted with pyrite to produce ferrous sulphate and free sulphuric acid. This reaction appears in many chemistry texts and generally has not been considered worthy of further study. Since the measurement of hydrogen ion concentration or activity was developed and expressed in terms of pH, indicator and instrumental methods for pH determination have become readily available, making it natural to think of it as a measure of acid content. Special purpose analytical methods applicable to potable waters, sewage effluents, and boiler waters, based in general upon the determination of what may be regarded as impurities, have been applied to more concentrated solutions constituting mine discharges, without reference to the fact that these specialized procedures had been developed to serve as operating guides for water-treatment plants. It has been assumed that the pounds of acid deliv- Table I. Showing pH and Titratable Acid of Varying Concentrations of Ferrous and Ferric Sulphates Ferric Ferrous ion Acldfty Ion Acidity (Fe+++) ppm CaCO3 We++) ppm CaCOa ppm PA equiv. PPm pH equiv. 11.200 1.80 30,000 11,200 3.98 20,000 5,600 2.01 15,000 5,600 4.15 10,000 2,800 2.21 7,500 2,800 4.41 5,000 1.120 2.48 3,000 1,400 4.68 2.500 560 2.60 1,500 140 5.00 250 280 2.65 750 28 5.00 50 112 2.81 300 56 3.07 150 28 3.38 75 ered by a mine was roughly a constant varying with the number of acres mined, and that the concentration of the acid in the drainage was inversely proportional to the volume of flow. Increased flow was thought to result in a dilution of the acid produced. When the Sanitary Water Board of the Commonwealth of Pennsylvania established a fellowship at Mellon Institute, the first approach to the problem was to review some of the chemical reactions involved and their relation to acid production. Since the sulphates of iron were among the principal constituents of coal-mine drainage, the first studies were based upon solutions of chemically pure ferrous and ferric sulphate. These are both neutral salts, that is, the iron and the sulphate are equivalent, but they produce acid reactions in water solution because as salts of strong acids with weak bases, they hydrolyze to form acid solutions. Solutions of each salt, of varying concentrations, were prepared and the pH, titrable acidity and iron and sulphate

Jan 1, 1952

By E. E. Anderson, R. L. Newacheck, J. Kohl

Radioactive materials were used underground before the advent of the nuclear reactor. Radium containing ores have been mixed with cements and other materials for later location in oil wells by gamma ray logging since 1940.1 Perforating bullets have been marked with radium salts,, and radioactive materials have been added to drilling muds to find the cause of "lost circulation."&apos; More recently colloidal suspensions of radioactive cobalt-60 and silver-1103 and solutions of 1-1314 have been used in waterflooding operatiorns to determine injection profiles, flow paths and water velocities. In this paper a recent and interesting underground tracer application is discussed. Development work and field engineering were carried out under the direction of Tracerlab, lnc., with assistance from personnel of the client. A gaseous tracer, argon-41, was used in an attempt to determine the cause of leakage from an underground gas storage reservoir. STATEMENT OF PROBLEM This gaseous tracer application was carried out for the Natural Gas Storage Co. of Illinois. This company has developed an underground gas storage field 1,750 ft below the surface of the earth near the village of Herscher, Ill., about 60 miles south of Chicago. The total volume of gas stored in the field was estimated to be about 13 billion cu ft in the spring of 1954. The field has a maximum estimated storage capacity of 90 billion cu ft. The gas is contained in the Galesville sandstone, previously a water bearing formation of about 25 per cent porosity. The water as it is pushed out by the gas forms a barrier for the gas around the edge of the reservoir. Over the top and beneath the bottom of the reservoir are located several layers of impervious rock, which barring cracks or unplugged and unknown wells should act as seals. Twenty-one injection and withdrawal wells were drilled into the Herscher reservoir and gas injection was begun during the summer of 1953. After a few weeks of gas injection, evidence of gas leakage was detected at the surface; water wells began bubbling and losing prime, and dry spots in the fields indicated gas leakage from uncharted oil wells. In every case, the leakage could not be traced back any further than the water bearing formations a few hundred feet below the surface. An extensive search was made to locate uncharted oil wells which were believed to be possible channels for the gas from the storage formation to the water containing formation. Long-time residents in the area assisted in the location of several abandoned oil wells. The wells when located were cleaned out and either used as vent wells to relieve the gas pressure in the water formations, or were plugged with cement. None of the wells even approached depths which would endanger the soundness of the storage reservoir. All of the injection wells were tested for leaks in the casings by conducting neutron surveys and by other techniques. To detect any leakage up through the cement-filled annulus surrounding the casing, a section of the casing wall in one well was milled out. Then, plugs were installed above and below the cut-out section and pressure applied to the annulus, which proved conclusively that the cement was sound in that well. The well was then plugged with cement and abandoned. In another well, ammonia was injected into the well and a temperature log was made. It was hoped that a leak would be re-

Jan 1, 1956

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

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

By Robert M. Asimow, Bisuddhi Riddhagni

THE use of back-reflection Laue photographs for crystal orientation is standard in many research projects. The time required for the orientation of any given crystal depends largely on luck and the skill of the investigator. In any case, where large numbers of crystals are used, this time can be quite considerable when the standard methods involving a Greninger chart and Wulff net are employed. For this reason the technique described below was developed. This new procedure applicable for cubic crystals (without preparation of new charts) largely eliminates the skill and luck factors and makes possible the determination of orientation in minutes. The procedure works in the following way: the Laue photograph is examined and arbitrarily an important hyperbola is picked out. An important hyperbola is defined as one which contains some spots through which several hyperbolas pass. Such a hyperbola inevitably corresponds to a low-index zone axis. The angles between the reflection planes causing all the spots on this hyperbola can be read directly from a Greninger chart in the usual manner. If the hyperbola contains more than five spots, these interplanar angles will positively identify the zone axis and the indices of each of the reflecting planes. However, initially since neither the zone axis nor the Miller indices of a diffraction spot are known, there are a very large number of possibilities that must be considered. Using tables of interplanar angles to check out every possibility would be quite tedious, so that this approach is not generally used. Instead, various poles are plotted on a stereographic projection. In the cubic system, however, it is possible to plot out once and for all the angles between all planes of a particular zone axis up to some upper limit of Miller indices. This has been done for all low-index zone axes in Fig. 1. Given these charts, it is quite a simple matter to identify the spots of the unknown hyperbola. All that is necessary is to plot the angles read off the Greninger chart to the same scale as Fig. l(b) on a strip of paper. Then this strip can be slid along each zone axis of Fig. l(a) until a good fit is obtained. Once this is accomplished, the Miller indices of each spot are given and thus the orientation problem is solved. To check, it is possible to pick a second hyperbola and see whether a compatible solution is obtained. This is most conveniently done by picking for the second hyperbola one that contains a spot common with the first. If the specimen axis is chosen parallel to the incident X-ray beam, then usually the [ loo] hyperbola will appear on the film as one of the more important hyperbolas and consequently will be either chosen initially or as a check. Using the [100] hyperbola, after the (001) or (011) spots have been identified, the latitude and longitude of the specimen axis can be read directly from the Greninger chart so that it is unnecessary to use a Wulff net for the entire orientation procedure. This makes the operation not only quicker but more accurate. Of course, if neither the first nor second hyperbolas correspond to [loo] then a third hyperbola can be chosen.

Jan 1, 1967